Catalysts doi: 10.3390/catal14030200
Authors: Xueqin Li Yan Lu Peng Liu Zhiwei Wang Taoli Huhe Zhuo Chen Youqing Wu Tingzhou Lei
The thermo-chemical conversion of biomass wastes is a practical approach for the value-added reclamation of bioenergy in large quantities, and pyrolysis plays a core role in this process. In this work, poplar (PR) and cedar (CR) were used as staple wood biomasses to investigate the apparent kinetics of TG/DTG at different heating rates. Secondly, miscellaneous wood chips (MWC), in which PR and CR were mixed in equal proportion, were subjected to comprehensive investigations on their pyrolysis behavior and product evolution in a fixed bed reactor with pyrolysis temperature, catalyst, and the flow rate H2O steam as influencing factors. The results demonstrated that both PR and CR underwent three consecutive pyrolysis stages, the TG/DTG curves shifted to higher temperatures, and the peak temperature intervals also enhanced as the heating rate increased. The kinetic compensation effect expression and apparent reaction kinetic model of CR and PR pyrolysis were obtained based on the law of mass action and the Arrhenius equation; the reaction kinetic parameter averages of Ea and A of its were almost the same, which were about 72.38 kJ/mol and 72.36 kJ/mol and 1147.11 min−1 and 1144.39 min−1, respectively. The high temperature was beneficial for the promotion of the pyrolysis of biomass, increased pyrolysis gas yield, and reduced tar yield. This process was strengthened in the presence of the catalyst, thus significantly increasing the yield of hydrogen-rich gas to 117.9 mL/g-biomass. It was observed that H2O steam was the most effective activator for providing a hydrogen source for the whole reaction process, promoted the reaction to proceed in the opposite direction of H2O steam participation, and was beneficial to the production of H2 and other hydrocarbons. In particular, when the flow rate of H2O steam was 1 mL/min, the gas yield and hydrogen conversion were 76.94% and 15.90%, and the H2/CO was 2.07. The yields of H2, CO, and CO2 in the gas formation were significantly increased to 107.35 mL/g-biomass, 53.70 mL/g-biomass, and 99.31 mL/g-biomass, respectively. Therefore, H2 was the most dominant species among gas products, followed by C-O bond-containing species, which provides a method for the production of hydrogen-rich gas and also provides ideas for compensating or partially replacing the fossil raw material for hydrogen production.
]]>Catalysts doi: 10.3390/catal14030199
Authors: Stefan S. Warthegau Magnus Karlsson Robert Madsen Pernille Rose Jensen Sebastian Meier
Reaction mixtures of naturally abundant aldoses and CH nucleophiles allow for the formation of functionalized furan precursors using low temperatures and metal-free catalysis in aqueous solutions of dilute base catalysts. We employ in situ NMR assays to clarify the mechanism and kinetics of the conversion. Catalysis serves a double role in ring-opening of stable aldoses such as glucose and xylose and facilitating the subsequent reactions with CH acids such as malononitrile or cyanoacetamide. Resultant acyclic products are shown to convert quickly to a monocyclic product prior to the slower formation of a more stable bicyclic intermediate and dehydration to tri-functionalized furan. Especially the reversible 5-exo-dig ring closure entailing oxygen attack onto a nitrile carbon is surprisingly fast with an equilibrium vastly towards the cyclic state, sequestering reactive groups and allowing the selective conversion to tri-functionalized furan. The reaction hinges on the fast formation of intermediates without CH acidity and competes with the oligomerization of CH nucleophiles. Insight derived from in situ NMR analysis shows the prowess of high-resolution in situ spectroscopy in clarifying the interplay between catalysts and reactants. Such insight will be vital for the optimization of reactions that upgrade biorenewables under benign conditions.
]]>Catalysts doi: 10.3390/catal14030198
Authors: Ana Carla S. L. S. Coutinho Joana M. F. Barros Marcio D. S. Araujo Jilliano B. Silva Marcelo J. B. Souza Regina C. O. B. Delgado Valter J. Fernandes Jr. Antonio S. Araujo
Heterogeneous catalysts containing cobalt and molybdenum supported on mesoporous materials types SBA-15 and AlSBA-15 were synthesized for application in the HDS reactions of thiophene in the n-heptane stream. The materials were synthesized by the hydrothermal method using Pluronic P123 as a template. The calcined SBA-15 and AlSBA-15 supports were submitted to co-impregnation with solutions of cobalt nitrate and ammonium heptamolybdate, aiming for the production of 15% in mass of metal loading with an atomic ratio of [Co/(Co + Mo)] = 0.45. The obtained materials were dried and calcined to obtain the mesoporous catalysts in the forms of CoMo/SBA-15 and CoMo/AlSBA-15. The catalysts were characterized by XRD, TG/DTG, SEM, and nitrogen adsorption. From XRD analysis, it was verified that after the decomposition of the cobalt and molybdenum salts, MoO3, Co3O4, and CoMoO4 oxides were formed on the supports, being attributed to these chemical species, the activity for the HDS reactions. The catalytic activity of the obtained catalysts was evaluated in a continuously flowing tubular fixed-bed microreactor coupled on-line to a gas chromatograph, using an n-heptane stream containing 12,070 ppm of thiophene (ca. 5100 ppm of sulfur) as a model compound. The synthesized catalysts presented suitable activity for the HDS reaction, and the main obtained products were cis- and trans-2-butene, 1-butene, n-butane, and low amounts of isobutane. The presence of 1,3-butadiene and tetrahydrothiophene (THT) was not detected. A mechanism of the primary and secondary reactions and subsequent formation of the olefins and paraffins in the CoMo/SBA-15 and CoMo/AlSBA-15 mesoporous catalysts was proposed, considering steps of desulfurization, hydrogenation, dehydrogenation, THT decyclization, and isomerization.
]]>Catalysts doi: 10.3390/catal14030197
Authors: Qingfeng Teng Junkang Sang Guoxin Chen Haoliang Tao Yunan Wang Hua Li Wanbing Guan Changsheng Ding Fenghua Liu Liangzhu Zhu
On-site hydrogen generation from ammonia decomposition is a promising technology to address the challenges of direct transportation and storage of hydrogen. The main problems with the existing support materials for ammonia decomposition catalysts are their high cost and time-consuming preparation process. In this work, ammonia decomposition catalysts consisting of in situ-formed nano-Ru particles supported on a naturally abundant mineral fiber, attapulgite (ATP), were proposed and studied. Also, 1 wt.% Ru was uniformly dispersed and anchored onto the surface of ATP fibers via the chemical method. We found that the calcination temperatures of the ATP support before the deposition of Ru resulted in little difference in catalytic performance, while the calcination temperatures of the 1Ru/ATP precursor were found to significantly influence the catalytic performance. The prepared 1 wt.% Ru/ATP catalyst (1Ru/ATP) without calcination achieved an ammonia conversion efficiency of 51% at 500 °C and nearly 100% at 600 °C, with the flow rate of NH3 being 10 sccm (standard cubic centimeter per minute). A 150 h continuous test at 600 °C showed that the 1Ru/ATP catalyst exhibited good stability with a degradation rate of about 0.01% h−1. The 1Ru/ATP catalyst was integrated with proton ceramic fuel cells (PCFCs). We reported that PCFCs at 650 °C offered 433 mW cm−2 under H2 fuel and 398 mW cm−2 under cracked NH3 fuel. The overall results suggest low-level Ru-loaded ATP could be an attractive, low-cost, and efficient ammonia decomposition catalyst for hydrogen production.
]]>Catalysts doi: 10.3390/catal14030196
Authors: Muhammad Naseem Akhtar
This research work is focused on the transformation of light alkane (propane) into high-value aromatics using gallo-alumino-silicate catalysts. Two sets of gallo-alumino-silicates were synthesized for this study. In the first set, the ratio of Ga/(Al+Ga) was modified, while the Si/(Al+Ga) ratio was held constant. In the subsequent set, the Si/(Al+Ga) ratio was adjusted, while maintaining a consistent Ga/(Al+Ga) ratio. This approach aimed to directly assess the impact of each ratio on catalyst performance. The comprehensive characterization of all catalysts was conducted using various instrumental techniques, i.e., BET surface area, XRD, NH3-TPD, 27Al, 71Ga and 29Si MAS NMR, and XPS. A gradual reduction in the percentage of crystallinity and rise in meso-surface area was noticed with a rise in Ga/(Al+Ga) ratio. The total acidity (NH3-TPD) demonstrated a decline as the Si/(Al+Ga) ratio increased, attributed to an overall decline in Al3+ or Ga3+ species. The XPS intensity of the Ga 2p3/2 peak rose in correlation with an elevated ratio of Ga/(Al+Ga), suggesting the formation of extra-framework Ga species. The propane conversion, aromatic yield, and aromatization/cracking ratio exhibited an increase with an increasing Ga/(Al+Ga) ratio, reaching an optimum value of 0.46 before declining. Conversely, an appreciable drop in the conversion of propane and yield of aromatics was detected with the rise in Si/(Al+Ga) ratio, attributing to the decline in acidity. The catalyst having a Ga/(Al+Ga) ration of 0.46 exhibited the highest propane conversion and aromatic yield of 83.0% and 55.0% respectively.
]]>Catalysts doi: 10.3390/catal14030195
Authors: Zaheer Abbas Md Mostakim Meraz Wenhong Yang Weisheng Yang Wen-Hua Sun
The present study explored machine learning methods to predict the catalytic activities of a dataset of 165 α-diimino nickel complexes in ethylene polymerization. Using 25 descriptors as the inputs, the XGBoost model presented the optimal performance among six different algorithms (R2 = 0.999, Rt2 = 0.921, Q2 = 0.561). The results of the analysis indicate that high activity is related to the presence of polarizable atoms and less bulky substituents within the N-aryl group. This approach offers valuable insights on the variation principle of catalytic activity as a function of complex structure, helping to effectively design and optimize α-diimino Ni catalysts with desirable performance.
]]>Catalysts doi: 10.3390/catal14030194
Authors: Haijie Sun Wen Zhang Xiaohui Wang Zhihao Chen Zhikun Peng
The synthesis of nylon 6 and nylon 66 can be performed, starting with the selective hydrogenation of benzene to cyclohexene, which is deemed to be environmentally friendly and cost-saving and to have higher atom efficiency. Nano-Ru catalyst was synthesized via a precipitation method. The prepared catalyst was evaluated in the selective hydrogenation of benzene toward cyclohexene generation in the presence of ZnSO4 in a liquid batch reactor. The promotion effect of the addition of amines, i.e., ethylenediamine, ethanolamine, diethanolamine, and triethanolamine, was investigated. The fresh and spent catalysts were thoroughly characterized by XRD, TEM, AES, N2-sorption, FT-IR, and TPR. It was found that the addition of amines could significantly improve the catalytic selectivity toward cyclohexene formation in the presence of ZnSO4. This was attributed to the formation of (Zn(OH)2)5(ZnSO4)(H2O)x (x = 0.5, 3 or 4) through the reaction between ZnSO4 and the amines, which could be chemisorbed on the Ru surface. This led to retarding the formation of cyclohexane from the complete hydrogenation of benzene and, thus, increased the catalytic selectivity toward cyclohexene synthesis. Therefore, with the presence of ZnSO4, the amount of chemisorbed (Zn(OH)2)5(ZnSO4)(H2O)x increased with increasing amounts of added amines, leading to a decline in the catalytic activity toward benzene conversion and selectivity toward cyclohexene generation. When 7.6 mmol of diethanolamine and 10 g of ZrO2 were applied, the highest cyclohexene yields of 61.6% and 77.0% of benzene conversion were achieved over the Ru catalyst. Promising stability was demonstrated after six runs of catalytic experiments without regeneration. These achievements are not only promising for industrial application but also beneficial for designing other catalytic systems for selective hydrogenation.
]]>Catalysts doi: 10.3390/catal14030193
Authors: Takato Mitsudome
This review introduces transition metal phosphide nanoparticle catalysts as highly efficient and reusable heterogeneous catalysts for various reductive molecular transformations. These transformations include the hydrogenation of nitriles to primary amines, reductive amination of carbonyl compounds, and biomass conversion, specifically, the aqueous hydrogenation reaction of mono- and disaccharides to sugar alcohols. Unlike traditional air-unstable non-precious metal catalysts, these are stable in air, eliminating the need for strict anaerobic conditions or pre-reduction. Moreover, when combined with supports, metal phosphides exhibit significantly enhanced activity, demonstrating high activity, selectivity, and durability in these hydrogenation reactions.
]]>Catalysts doi: 10.3390/catal14030192
Authors: Juan Su Nannan Zhan Yuan Tan Xiangting Min Yan Xiao Botao Qiao
The use of gold nanoparticles (Au NPs) as catalysts has gained widespread attention in various reactions due to their high activity and selectivity under mild reaction conditions. However, one major challenge in utilizing these catalysts is their tendency to aggregate, leading to catalyst deactivation and hindering their amplification and industrial application. To overcome this issue, herein, we used a method by coating the surface of Au NPs with a thin layer of SiO2, which resulted in the formation of a superior catalyst denoted as Au@SiO2/ZA. Characterization studies revealed that the SiO2 layer is coated on the surface of Au NPs and effectively prevents the aggregation and growth of the gold particles during the reaction process, which makes the catalyst display excellent stability in furfural (FF) oxidative esterification to methyl furoate (MF). Moreover, the stabilization strategy is not limited to SiO2 alone. It can also be extended to other oxides such as ZrO2, CeO2, and TiO2. We believe this work will provide a good reference for the design and development of an efficient and stable gold catalyst for the oxidative esterification reaction.
]]>Catalysts doi: 10.3390/catal14030191
Authors: Hangxin Xie Li Lv Yuan Sun Chunlai Wang Jialin Xu Min Tang
Effective electrochemical reduction of carbon dioxide to formate under mild conditions helps mitigate the energy crisis but requires the use of high-performance catalysts. The addition of a third metal to the binary metal catalyst may further promote the electrochemical reduction of carbon dioxide to formate. Herein, we provided a co-electrodeposition method to grow CuSnBi catalysts on pretreated copper foam and discussed the effects of both pH value and molar ratio of metal ions (Cu2+, Sn2+, and Bi3+) in the electrodeposition solution on the electrocatalytic performance of CO2 to HCOO−. When the pH value of the electrodeposition solution was 8.5 and the molar ratio of Cu2+, Sn2+, and Bi3+ was 1:1:1, the electrode showed the highest FEHCOO− of 91.79% and the formate partial current density of 36.6 mA·cm−2 at −1.12 VRHE. Furthermore, the electrode kept stable for 20 h at −1.12 VRHE, and FEHCOO− was always beyond 85% during the electrolysis process, which is excellent compared to the previously reported ternary metal catalytic electrodes. This work highlights the vital impact of changes (pH value and molar ratio of metal ions) in electrodeposition liquid on catalytic electrodes and their catalytic performance, and refreshing the electrolyte is essential to maintain the activity and selectivity during the electrochemical reduction of CO2 to HCOO−.
]]>Catalysts doi: 10.3390/catal14030190
Authors: Hao Wang Wenjun Zhang Dalong Zheng Yubei Li Jian Fang Min Luo Jichang Lu Yongming Luo
Sulfur-resistant Mo-based catalysts have become promising for the one-step synthesis of methanethiol (CH3SH) from CO/H2/H2S, but the low reactant conversion and poor product selectivity have constrained its development. Herein, we synthesized K-MoS2/Al2O3 and K-Mo2C/Al2O3 catalysts via the sulfurization and carbonization of K-Mo-based catalysts in the oxidized state, respectively. During the synthesis of CH3SH, both K-Mo2C/Al2O3 and K-MoS2/Al2O3 showed excellent catalytic performance, and the activity of the former is superior to that of the latter. The effect of different treatments on the catalytic performance of Mo-based catalysts was investigated by XRD, BET, Raman spectroscopy, H2-TPR, and reactants-TPD characterization. The results showed that the sulfide-treated sample showed stronger metal-support interactions and contributed to the formation of K2S, which exposed more active sites and stabilized the formation of C-S bonds. Carbonized samples enhanced the activation of H2, which promoted the hydrogenation of the intermediate species of carbonyl sulfide (COS) and thus improved the selectivity of CH3SH.
]]>Catalysts doi: 10.3390/catal14030189
Authors: Nur Nabaahah Roslan Harry Lik Hock Lau Nurul Amanina A. Suhaimi Nurulizzatul Ningsheh M. Shahri Sera Budi Verinda Muhammad Nur Jun-Wei Lim Anwar Usman
A large variety of pharmaceutical compounds have recently been detected in wastewater and natural water systems. This review highlighted the significance of removing pharmaceutical compounds, which are considered indispensable emerging contaminants, from wastewater and natural water systems. Various advanced oxidation processes (AOPs), including UV-H2O2, Fenton and photo-Fenton, ozone-based processes, photocatalysis, and physical processes, such as sonolysis, microwave, and electron beam irradiation, which are regarded as the most viable methods to eliminate different categories of pharmaceutical compounds, are discussed. All these AOPs exhibit great promising techniques, and the catalytic degradation process of the emerging contaminants, advantages, and disadvantages of each technique were deliberated. Heterogeneous photocatalysis employing metal oxides, particularly anatase TiO2 nanoparticles as catalysts activated by UV light irradiation, was reviewed in terms of the electron–hole separation, migration of the charge carriers to the catalyst surfaces, and redox potential of the charge carriers. This brief overview also emphasized that anatase TiO2 nanoparticles and TiO2-based nanomaterials are promising photocatalysts, and a combination of photocatalysis and other AOPs enhanced photocatalytic degradation efficiency. Finally, the challenges of applying anatase TiO2-based photocatalysis in environmental remediation and wastewater treatments to degrade pharmaceutical compounds, including mass spectroscopic analysis and a biological activity test of by-products of the emerging contaminants resulting from photocatalysis, are summarized.
]]>Catalysts doi: 10.3390/catal14030188
Authors: Wang-Mi Chen Bei-Dou Xi Ming-Xiao Li Mei-Ying Ye Jia-Qi Hou Yu-Fang Wei Cheng-Ze Yu Fan-Hua Meng
The catalytic cracking of pyrolysis gasification tar into H2 has garnered significant attention due to its exceptional conversion efficiency. In this study, the effects of pollutant concentration, residence time, weight hourly space velocity (WHSV), and reaction temperature on the hydrogen performance of LaFe0.5Ni0.5O3 perovskite were comprehensively investigated. Results revealed that moderate pollutant concentration (0.3 g/L), low-medium residence time (250 SCCM), and low WHSV (0.24 gtoluene/(gcat·h)) facilitated efficient interaction between LaFe0.5Ni0.5O3 and toluene, thus achieving high hydrogen production. An increase in reaction temperature had minimal effect on the hourly hydrogen production above 700 °C but caused a significant increase in methane production. Additionally, the effects of oxygen evolution reactions, methane reactions, and methane catalytic cracking reactions of perovskite induced by different reaction conditions on tar cracking products were discussed in detail. Compared to previous reports, the biggest advantages of this system were that the hydrogen production per gram of tar was as high as 1.002 L/g, and the highest hydrogen content in gas-phase products reached 93.5%, which can maintain for approximately 6 h. Finally, LaFe0.5Ni0.5O3 showed good thermal stability, long-term stability, and catalyst reactivation potential.
]]>Catalysts doi: 10.3390/catal14030187
Authors: Kwangho Park Kyung Rok Lee Sunghee Ahn Hongjin Park Seokyeong Moon Sungho Yoon Kwang-Deog Jung
The practical application of formic acid production through the hydrogenation of CO2 has garnered significant attention in efforts to tackle the challenges associated with (1) achieving net-zero production of formic acid as a chemical feedstock and (2) improving hydrogen storage and transport. This study focuses on demonstrating the continuous operation of a trickle bed reactor for converting CO2 into formate using palladium on activated carbon (Pd/AC). Optimal temperature conditions were investigated through a dynamic operation for 24 h, achieving the maximum productivity of 2140 mmolFA·gPdsurf.−1·h−1 at 150 °C and 8 MPa, with an H2/CO2 ratio of 1:1; however, catalyst deactivation was observed in the process. Stability tests performed under continuous operation at 120 °C and 8 MPa with an H2/CO2 ratio of 1:1 indicated a gradual decline in productivity, culminating in a 20% reduction after 20 h. A comprehensive analysis comparing fresh and spent catalysts revealed that the diminished catalytic activity at elevated temperatures was attributed to the partial sintering and leaching of Pd nanoparticles during the hydrogenation process. These findings offer insights for the future development of novel Pd-based catalyst systems suitable for continuous hydrogenation processes.
]]>Catalysts doi: 10.3390/catal14030186
Authors: Kai Guo Hui Zhang Changxuan Zhang Xining Guo Huiying Li Zhourong Xiao
Large-scale hydrogen production by the steam reforming of long-chain hydrocarbon fuel is highly desirable for fuel-cell application. In this work, LaNiO3 perovskite materials doped with different rare earth elements (Ce, Pr, Tb and Sm) were prepared by a sol-gel method, and the derivatives supported Ni-based catalysts which were successfully synthesized by hydrogen reduction. The physicochemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N2 adsorption–desorption isotherms, H2 temperature-programmed reduction, and X-ray photoelectron spectroscopy. The catalytic performance of the as-prepared catalysts for hydrogen production was investigated via the steam reforming of n-dodecane. The results showed that the catalyst forms perovskite oxides after calcination with abundant mesopores and macropores. After reduction, Ni particles were uniformly distributed on perovskite derivatives, and can effectively reduce the particles’ sizes by doping with rare earth elements (Ce, Pr, Tb and Sm). Compared with the un-doped catalyst, the activity and hydrogen-production rate of the catalysts are greatly improved with rare earth element (Ce, Pr, Tb and Sm)-doped catalysts, as well as the anti-carbon deposition performance. This is due to the strong interaction between the uniformly distributed Ni particles and the support, as well as the abundant oxygen defects on the catalyst surface.
]]>Catalysts doi: 10.3390/catal14030185
Authors: Luigi di Bitonto Enrico Scelsi Hilda Elizabeth Reynel-Ávila Didilia Ileana Mendoza-Castillo Adrián Bonilla-Petriciolet Martin Hájek Ahmad Mustafa Carlo Pastore
In this work, a closed-loop strategy for the management and valorization of winery waste was proposed. The exhausted pomace and grape stalks that are typically obtained from white wine industries were used as a source of simple sugars, namely, glucose and fructose, and of lignocellulosic feedstock for the preparation of selective catalysts for the 5-hydroxymethylfurfural (5-HMF) production from fructose. A novel synthetic procedure was developed for the synthesis of iron-sulfonated magnetic biochar catalysts (Fe-SMBCs). Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), BET surface area, porous structure analysis and determination of total amount of acid sites were performed in order to characterize the physico-chemical properties of the synthesized systems. Then, these heterogeneous catalysts were successfully tested via the dehydration of simple sugars into 5-HMF by using methyl isobutyl ketone (MIBK) and gamma valerolactone (GVL) as co-solvents. The optimum 5-HMF yield of 40.9 ± 1.1%mol with a selectivity of 59.8 ± 2.6%mol was achieved by adopting the following optimized conditions: 0.1 g of catalyst, volume ratio of GVL to H2O = 2 to 1, 403 K, 6 h. In addition, the catalyst was easily recycled using an external magnetic field and used for at least five reaction cycles without significant loss of catalytic activity.
]]>Catalysts doi: 10.3390/catal14030184
Authors: Ke Yu Jingyuan Zhang Yuting Hu Lanqi Wang Xiaofeng Zhang Bin Zhao
Metal-organic framework (MOF)-based materials with abundant pore structure, large specific surface area, and atomically dispersed metal centers are considered as potential electrocatalysts for oxygen-evolution reaction (OER), while their ligand-saturated metal nodes are inert to electrocatalysis. In this work, heteroatom doping and interface engineering are proposed to improve the OER performance of Co-MOF-74. Using two-dimensional Ti3C2Tx MXene as a conductive support, Ni-doped Co-MOF-74 (CoNi-MOF-74/MXene/NF) was in situ synthesized through a hydrothermal process, which exhibits excellent OER and hydrogen evolution reaction (HER) properties. For OER, the CoNi-MOF-74/MXene/NF achieves a current density of 100 mA/cm2 at an overpotential of only 256 mV, and a Tafel slope of 40.21 mV/dec. When used for HER catalysis, the current density of 10 mA/cm2 is reached at only 102 mV for the CoNi-MOF-74/MXene/NF. In addition, the two-electrode electrolyzer with CoNi-MOF-74/MXene/NF as both the cathode and anode only requires 1.49 V to reach the current density of 10 mA/cm2. This work provides a new approach for the development of bimetallic MOF-based electrocatalysts.
]]>Catalysts doi: 10.3390/catal14030183
Authors: Jiarong Ma Run Zhou Yu Tu Ruixin Ma Daimei Chen Hao Ding
Ni3Si2O5(OH)4 rods (NS) were synthesized via a hydrothermal method, employing natural wollastonite as a template. The hierarchical Ni3Si2O5(OH)4 rods exhibited vertically oriented nanosheets, resulting in a substantial increase in the specific surface area (from 2.24 m2/g to 178.4 m2/g). Subsequently, a CdS/Ni3Si2O5(OH)4 composite photocatalyst (CdS/NS) was prepared using a chemical deposition method. CdS was uniformly loaded onto the surface of the Ni3Si2O5(OH)4 nanosheets, successfully forming a heterojunction with Ni3Si2O5(OH)4. The CdS/NS photocatalyst in the presence of lactic acid as a sacrificial agent demonstrated an impressive H2 production rate of 4.05 mmol h−1 g−1, around 40 times higher than pure CdS. The photocorrosion of CdS was effectively solved after loading. After four cycles, the performance of CdS/NS remained stable, showing the potential for sustainable applications. After photoexcitation, electrons moved from Ni3Si2O5(OH)4 to the valence band of CdS, where they interacted with the holes via an enhanced interface contact. Simultaneously, electrons in CdS transitioned to its conduction band, facilitating hydrogenation. The enhanced performance was attributed to the improved CdS dispersion by Ni3Si2O5(OH)4 loading and efficient photogenerated carrier separation through the heterojunction formation. This work provides new perspectives for broadening the applications of mineral materials and developing heterojunction photocatalysts with good dispersibility and recyclability.
]]>Catalysts doi: 10.3390/catal14030182
Authors: Guido Busca
Chemical technologies provide processes for the large-scale production of materials (i [...]
]]>Catalysts doi: 10.3390/catal14030181
Authors: Hassan H. Hammud Waleed A. Aljamhi Dolayl E. Al-Hudairi Nazish Parveen Sajid Ali Ansari Thirumurugan Prakasam
Hierarchically graphitic carbon that contained nickel nanoparticles (HGC-Ni (1), (2), and (3)) were prepared by the pyrolysis of three metal complexes as follows: nickel 2,2′-biyridine dichloride, nickel terephthalate 2,2′-bipyridine, and nickel phenanthroline diaqua sulfate, respectively, in the presence of anthracene or pyrene. SEM indicated that the structure of the HGC-Ni samples consisted of nickel nanoparticles with a diameter of 20–500 nm embedded in a thin layer of a hierarchical graphitic carbon layer. The EDAX of HGC-Ni indicated the presence of nickel, carbon, and nitrogen. Chlorine, oxygen, and sulfur were present in (1), (2), and (3), respectively, due to the differences in their complex precursor type. XRD indicated that the nanoparticles consisted of Ni(0) atoms. The turnover frequency (TOF) for the reduction of p-nitrophenol (PNP) increased for catalysts HGC-Ni (3), (2), and (1) and were 0.0074, 0.0094, and 0.0098 mg PNP/mg catalyst/min, respectively. The TOF for the reduction of methyl orange (MO) increased for catalysts (3), (1), and (2) and were 0.0332, 0.0347, and 0.0385 mg MO/mg catalyst/min, respectively. Thus, nickel nano-catalysts (1) and (2) provided the highest performance compared to the nano-catalysts for the reduction of PNP and MO, respectively. The first-order rate constant (min−1) of HGC-Ni (3), with respect to the reduction of PNP, was 0.173 min−1, while the first-order rate constant (min−1) for the reduction of MO by HGC-Ni (1) was 0.404 min−1. HGC-Ni (3) had the highest number of cycles with respect to PNP (17.9 cycles) and MO (22.8 cycles). The catalysts were regenerated efficiently. HGC-Ni exhibited remarkable electrochemical capacitance characteristics in the present study. This material achieved a notable specific capacitance value of 320.0 F/g when measured at a current density of 2 A/g. Furthermore, its resilience was highlighted by its ability to maintain approximately 86.8% of its initial capacitance after being subjected to 2500 charge and discharge cycles. This finding suggests that this HGC-Ni composite stands out not only for its high capacitive performance but also for its durability, making it an attractive and potentially economical choice for energy-storage solutions in various technological applications.
]]>Catalysts doi: 10.3390/catal14030180
Authors: Xiaoxiao Dong Chengnan Zhang Prasanna J. Patil Weiwei Li Xiuting Li
Metal–organic frameworks (MOFs) are regarded as excellent carriers for immobilized enzymes due to their substantial specific surface area, high porosity, and easily tunable pore size. Nevertheless, the use of UIO−66 material is significantly limited in immobilized enzymes due to the absence of active functional groups on its surface. This study comprised the synthesis of UIO−66 and subsequent modification of the proline (Pro) on UIO−66 through post-synthetic modification. UIO−66 and UIO−66/Pro crystals were employed as matrices to immobilize Rhizopus oryzae lipase (ROL). The contact angle demonstrated that the introduction of Pro onto UIO−66 resulted in favorable conformational changes in the structure of ROL. The immobilized enzyme ROL@UIO−66/Pro, produced via the covalent-bonding method, exhibited greater activity (0.064715 U/mg (about 1.73 times that of the free enzyme)) and stability in the ester hydrolysis reaction. The immobilized enzymes ROL@UIO−66 (131.193 mM) and ROL@UIO−66/Pro (121.367 mM), which were synthesized using the covalent-bonding approach, exhibited a lower Km and higher substrate affinity compared to the immobilized enzyme ROL@UIO−66/Pro (24.033 mM) produced via the adsorption method. This lays a solid foundation for the industrialization of immobilized enzymes.
]]>Catalysts doi: 10.3390/catal14030179
Authors: Galin Borisov Vasil Bachvarov Rashko Rashkov Evelina Slavcheva
In this research, a thin layer of multi-metallic non-precious catalyst is prepared by electroplating from an electrolyte bath containing Ni, Co, and Fe sulfates over pressed commercial nickel foam electrode. The composition of the deposited catalytic film and its morphology are characterized by scanning electron microscopy (SEM) with energy dispersion X-ray (EDX) techniques. The efficiency of the prepared binder-free electrodes for electrochemical water splitting is investigated in a self-designed short water electrolysis stack with zero-gap configuration of the integrated single cells and hybrid electrical connections. The separator used is a commercial Zirfon Perl 500 membrane, doped with 25% KOH. The performance of the catalyst, the single cells, and the developed electrolyzer stack are examined by steady state polarization curves and stationery galvanostatic stability tests in the temperature range 20 °C to 80 °C. The NiFeCoP multi-metallic alloy demonstrates superior catalytic efficiency compared to the pure nickel foam electrodes and reliable stability with time. The single cells in the stack show identical performance and the cumulative stack parameters strictly follow the theoretical considerations. The applied hybrid electrical connections enable scaling of both the stack voltage and the passing current, which in turn ensures flexibility with regard to the input power and the hydrogen production capacity.
]]>Catalysts doi: 10.3390/catal14030178
Authors: Silvia Álvarez Torrellas Juan García Rodríguez
Water is a basic resource and is required by all living beings on our planet [...]
]]>Catalysts doi: 10.3390/catal14030177
Authors: Suresh Sagadevan Is Fatimah
Currently, catalysis represents an exciting research area [...]
]]>Catalysts doi: 10.3390/catal14030176
Authors: Zhenchao Xu Eun Duck Park
The dry reforming of methane (DRM) is a promising method for controlling greenhouse gas emissions by converting CO2 and CH4 into syngas, a mixture of CO and H2. Ni-based catalysts have been intensively investigated for their use in the DRM. However, they are limited by the formation of carbonaceous materials on their surfaces. In this review, we explore carbon-induced catalyst deactivation mechanisms and summarize the recent research progress in controlling and mitigating carbon deposition by developing coke-resistant Ni-based catalysts. This review emphasizes the significance of support, alloy, and catalyst structural strategies, and the importance of comprehending the interactions between catalyst components to achieve improved catalytic performance and stability.
]]>Catalysts doi: 10.3390/catal14030175
Authors: Antia Fdez-Sanromán Marta Pazos Emilio Rosales Angeles Sanromán
This comprehensive review explores recent advancements in immobilization strategies for graphitic carbon nitride (g-C3N4), a metal-free photocatalyst that has gained significant attention for its optical and physicochemical properties comparable to traditional photocatalysts like TiO2. However, a critical challenge regarding their application has emerged from the difficulty of its recovery due to its powdery nature. Therefore, several alternatives are being explored to immobilize this material, facilitating its recovery and reuse. This review systematically categorizes various physical and chemical immobilization techniques, providing an in-depth analysis of their advantages, drawbacks, and applications. Techniques such as encapsulation, electrospinning, casting, and coating, along with their adaptations for g-C3N4, are thoroughly examined. Additionally, the impact of these strategies on enhancing the photocatalytic efficiency and operational stability of g-C3N4, particularly in environmental applications, is also assessed. Thus, this review aims to provide valuable insights and guide future research in the realms of photocatalysis and environmental remediation. The review contributes to the understanding of how immobilization strategies can optimize the performance of g-C3N4, furthering its potential applications in sustainable and efficient environmental solutions.
]]>Catalysts doi: 10.3390/catal14030174
Authors: Paola Semeraro Roberto Comparelli
The removal of contaminants from wastewater, which are produced by human activities, and the development of new means of renewable energy production are the main issues that need to be addressed to solve environmental problems [...]
]]>Catalysts doi: 10.3390/catal14030173
Authors: Xiaolin Xu Mengna Ding Shiwen Yu Fujian Lv Yun Zhang Yingchun Miao Zhenfeng Bian Hexing Li
Antibacterial coordination compounds have attracted tremendous attention ascribed to their excellent designability. However, how the morphological evolution of these complexes influences their antibacterial and physicochemical properties has never been investigated based on proposed mechanisms. Thus, a series of Co–HOAT coordination compounds synthesized from inorganic to organic cobalt sources were prepared. We propose that with the same HOAT ligand, inorganic Co–HOAT nanosheets possess higher sterilization rates compared with organic Co–HOAT nanoparticles. This is explained by the different steric hindrance of cobalt sources. Relatively small steric hindrance could lead to ample active positions for inorganic cobalt ions to coordinate with both N and O atoms in HOAT. Meanwhile, organic Co2+ ions could only unite with N atoms in HOAT. Furthermore, by theoretical calculation, cobalt ions with adequate coordination sites are beneficial for developing nanosheet morphologies. Meanwhile, the Co–HOAT complexes with a lower density of electron clouds present higher sterilization rates due to the anchoring effect of electrostatic attraction. The proposed mechanism is that Co2+ released from compounds could cause multiple toxic effects to bacteria anchored by Co–HOATs. Finally, Co–HOATs’ behaviors have excellent antimicrobial properties without environmental limitations. In conclusion, the Co–HOATs appear to be a potential antibacterial catalyst in the antimicrobial field.
]]>Catalysts doi: 10.3390/catal14030172
Authors: Wei Liu Shiqi Chen Ziwei Mei Liang Li Hong Tao
With the widespread application of plant remediation technology in the field of soil remediation, there was an increasing stock of hyperaccumulating plant tissues containing heavy metals, but there was currently a lack of effective disposal methods. In the preliminary research process, researchers used the copper hyperaccumulating plant Elsholtzia Harchowensis to prepare biochar material electrodes and successfully used them in the electrocatalytic reduction of carbon dioxide (CO2) process. Due to the previous research being conducted in aqueous solutions, the hydrogen evolution reaction (HER) on the working electrode surface has a certain impact on the Faraday efficiency (FE) of carbon-containing products. In order to further improve the electrocatalytic reduction performance of biochar materials, this study was based on B- and N-doped biochar prepared from Elsholtzia Harchowensis as raw material. The influence mechanisms of electrode surface hydrophobicity and electrolyte components (PC/water) on the CO2RR and HER were studied, respectively. After dropwise coating PTFE on the surface of Cu/C-BN material, the hydrophobicity of Cu/C-BN-PT material was improved, and the effect on the active sites of the catalyst was relatively small without changing the structure and elemental characteristics of the original electrode. In a 1.0 M KHCO3 solution, the Faraday efficiency of H2 in Cu/C-BN-PT material decreased by 20.1% compared to Cu/C-BN at −0.32 V (vs. RHE), indicating that changing the hydrophilicity of the material can significantly inhibit the HER. In a solution of PC/water at a ratio of 9:1 (V:V), the FE of converting CO2 to methane (CH4) at −0.32 V (vs. RHE) reached 12.0%, and the FE of carbon monoxide (CO) reached 64.7%. The HER was significantly inhibited, significantly improving the selectivity of electrocatalytic CO2.
]]>Catalysts doi: 10.3390/catal14030171
Authors: Jianlei Jing Wei Liu Tianshui Li Xiaoqian Ding Wenhai Xu Mengze Ma Daojin Zhou Yaping Li Xiaoming Sun
The development of high-entropy anodes, known for their excellent catalytic activity for water oxidation, can depress the energy consumption of hydrogen production by water electrolysis. However, the complex preparation methods and poor stability hindered their practical application. In this work, a one-step co-precipitation method has been modified to rapidly synthesize ultrathin high-entropy layered double hydroxide containing Ni, Co, Fe, Cr, Zn. Through the rational selection of metal elements, the stability of the optimized anode under Ampere-level current density has been significantly improved. Compared to NiFe-LDH, the active site leaching of high-entropy LDH is reduced by 42.7%, and as a result, it achieves a performance decay that is approximately eight times lower than that of NiFe-LDH. Experiment results show that the active sites in the high-entropy LDH can maintain a relatively low oxidation state both before and after activation, thus preventing material deactivation caused by excessive oxidation.
]]>Catalysts doi: 10.3390/catal14030170
Authors: Abdelaziz Imgharn Tingwei Sun Jimmy Nicolle Yassine Naciri Abdelghani Hsini Abdallah Albourine Conchi Ania
The adequate optical properties, low cost, and thermal stability of graphitic carbon nitride and molybdenum oxide make them both promising materials for photocatalytic applications. However, they both suffer from strong recombination of their photogenerated charge carriers. Therefore, searching for strategies that enable an efficient charge carrier separation is desirable for improving the photocatalytic performance of both semiconductors. In this work, we have synthesized a g-C3N4/MoO3 heterojunction by a facile solid dispersion approach to the pristine semiconductors that allows a uniform dispersion of the two phases in the heterojunction. The resulting hybrid photocatalyst exhibits light absorption features similar to pristine g-C3N4 and presents an improved separation of the photogenerated charge carriers, likely through a Z-scheme between both semiconductor phases, as inferred by photoelectrochemical measurements. As a result, the g-C3N4/MoO3 heterojunction showed better photocatalytic activity than the individual semiconductors and good cycling stability for the degradation of methylparaben and its reaction intermediates. We drew these conclusions based on total organic carbon (TOC) measurements.
]]>Catalysts doi: 10.3390/catal14030169
Authors: Ganeshraja Ayyakannu Sundaram Rajkumar Kanniah Krishnamoorthy Anbalagan Kaviyarasan Kulandaivelu Héctor Valdés
Micrometer-sized polycrystalline anatase particles are widely used in materials and life sciences, serving as essential components in photocatalytic materials. The ability to tailor their composition, shape, morphology, and functionality holds significant importance. In this study, we identified and examined the non-destructive route of Copper(II) implantation at the surface of polycrystalline TiO2. The [Cu(en)(Im)2]2+ complex ion demonstrated a remarkable affinity to concentrate and bind with the semiconductor’s surface, such as anatase, forming a surface-bound adduct: ≡TiO2 + [Cu(en)(Im)2]2+ → ≡TiO2//[Cu(en)(Im)2]2+. The misalignment of Fermi levels in TiO2//[Cu(en)(Im)2]2+ triggered electron transfer, leading to the reduction of the metal center, releasing Copper(I) in the process. Although less efficient, the released Copper(I) encountered a highly favorable environment, resulting in the formation of the surface complex TiO2:CuIIsc. The implanted Cu(I) was converted back into Cu(II) due to re-oxidation by dissolved oxygen. The penetration of the metal ion into the surface level of the polycrystalline TiO2 lattice was influenced by surface residual forces, making surface grafting of the Cu(II) ion inevitable due to surface chemistry. FTIR, UV–vis, Raman, XRD, EPR, and surface morphological (SEM, EDAX, and HRTEM) analyses identified the typical surface grafting of the Cu(II) cluster complex on the anatase surface matrix. Moreover, the XRD results also showed the formation of an impure phase. The TiO2 polycrystalline materials, modified by the incorporation of copper complexes, demonstrated an enhanced visible-light photocatalytic capability in the degradation of Rhodamine B dye in aqueous solutions. This modification significantly improved the efficiency of the photocatalytic process, expanding the applicability of TiO2 to visible light wavelengths. These studies open up the possibility of using copper complexes grafted on metal oxide surfaces for visible-light active photocatalytic applications. Moreover, this investigation not only showcases the improved visible-light photocatalytic behavior of copper-modified TiO2 polycrystalline materials, but also underscores the broader implications of this improvement in the advancement of sustainable and efficient water treatment technologies.
]]>Catalysts doi: 10.3390/catal14030168
Authors: Marco F. Paucar-Sánchez Mónica Calero Gabriel Blázquez Rafael R. Solís Mario J. Muñoz-Batista María Ángeles Martín-Lara
This work reports the study of the catalytic pyrolysis of rejected plastic fractions collected from municipal solid waste whose mechanical recovery is not plausible due to technical or poor conservation issues. The chemical recycling using catalytic pyrolysis was carried out over commercial zeolites formulas, i.e., HY and HZSM-5, in which Ni or Co metals were deposited at two different loadings (1 and 5%, wt.). The presence of these transition metals on the zeolitic supports impacted the total production of compounds existing in the liquid oil. The samples were characterized in terms of structural, chemical, and morphologic properties, and the production of different fuel fractions (gasoline, light cycle oil, and heavy cycle oil) was correlated with a combined parameter defined as a ratio of Acidity/BET area.
]]>Catalysts doi: 10.3390/catal14030167
Authors: Jongkyu Kang Eun Duck Park
Methane is an abundant and relatively clean fossil fuel resource; therefore, its utilization as a chemical feedstock has a major impact on the chemical industry. However, its inert nature makes direct conversion into value-added products difficult under mild conditions. Compared to the gas-phase selective oxidation of methane, there have been several recent advances in the liquid-phase conversion of methane. This review categorizes the reports on the liquid-phase selective oxidation of methane according to the solvent and oxidant used. The advantages and disadvantages of each approach are discussed. High yields of methyl bisulfate as a methanol precursor can be achieved using SO3 in sulfuric acid; however, more attention should be paid to the separation process and overall economic analysis. However, the aqueous-phase selective oxidation of methane with in situ generated H2O2 is quite promising from an environmental point of view, provided that an economical reducing agent can be used. Based on the current state-of-the-art on this topic, directions for future research are proposed.
]]>Catalysts doi: 10.3390/catal14030166
Authors: Tom Vandevyvere Maarten K. Sabbe Joris W. Thybaut Jeroen Lauwaert
Basic oxides such as CaO and MgO were added to a γ-Al2O3 support in NiCu-catalyzed hydrodeoxygenation of anisole. A commercial CaO-MgO-γ-Al2O3 was compared to a benchmark γ-Al2O3 and in-house variants with sequential oxide impregnation prior to NiCu impregnation. CaO did not have a significant impact on activity compared to the benchmark, while MgO improved NiCu dispersion, enhancing activity. Co-impregnation of CaO and MgO resulted in intermediate activity. Despite decreased demethoxylation, likely due to moderated support acidity, both CaO-modified and the commercially supported catalysts showed improved stability over 48 h Time On Stream.
]]>Catalysts doi: 10.3390/catal14030165
Authors: Kristin Hölting Sebastian Götz Miriam Aßmann Paul Bubenheim Andreas Liese Jürgen Kuballa
Immobilisation plays an important role in the industrial application of enzymes. The stabilisation and reusability of immobilised enzymes reduce the cost of the catalyst and facilitate their use in continuously operated reactors. For this purpose, an applicable type of immobilisation needs to be identified. In this study, we investigate the conversion of CDP and PolyP to CTP by NDP polyphosphate phosphotransferase 3 from Ruegeria pomeroyi (RpPPK2-3) and describe the covalent immobilisation of RpPPK2-3. In order to select a suitable carrier for the immobilisation of RpPPK2-3, a screening with different amino methacrylate (glutaraldehyde-pre-activated) and epoxy methacrylate carriers was carried out. The epoxy methacrylate carrier ECR8209M (Purolite®) was found to be the most suitable. With a half-life of 462 d when stored at 6 °C and a 50-fold reusability with a 93% residual activity, the immobilised enzyme showed a higher stability compared to the soluble enzyme with a half-life of 0.04 d. Although the half-life of the soluble enzyme could be increased to 32 d by adding PPi, it could not reach the stability of the immobilisate. Due to the resilience of the immobilisate, it is suitable for application in continuous reactor set-ups, e.g., packed-bed reactors.
]]>Catalysts doi: 10.3390/catal14030164
Authors: Munira Siddika Nazmul Hosen Raed H. Althomali Jehan Y. Al-Humaidi Mohammed M. Rahman Mohammad A. Hasnat
Hydrogen peroxide is a promising substitute for fossil fuels because it produces non-hazardous by-products. In this work, a glassy carbon GC was anodized in sulphuric acid at +1.8 V to prepare the working electrode. It was utilized to investigate the oxygen reduction reaction (ORR) in a basic medium containing 0.1 M NaOH as a supporting electrolyte. The objective of this investigation was to synthesize hydrogen peroxide. X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), linear polarization, cyclic voltammetry (CV), and rotating disk electrode voltammetry (RDE) were performed for characterization and investigation of the catalytic properties. The RDE analysis confirmed that oxygen reduction reactions followed two electrons’ process at an activated GC electrode. Hence, the prepared electrode generated hydrogen peroxide from molecular oxygen at a potential of around −0.35 V vs. Ag/AgCl (sat. KCl), significantly lower than the pristine GC surface. The transfer coefficient, standard reduction potential, and standard rate constant were estimated to be 0.75, −0.27 V, and 9.5 × 10−3 cm s−1, respectively.
]]>Catalysts doi: 10.3390/catal14030163
Authors: Tsuyoshi Ochiai Takeshi Nagai Kengo Hamada Tomoyuki Tobe Daisuke Aoki Kayano Sunada Hitoshi Ishiguro
The coronavirus disease 2019 pandemic has increased the demand for anti-viral products. Photocatalytic materials are used to develop coatings and air purifiers that inactivate severe acute respiratory syndrome coronavirus 2. However, the methods for evaluating the anti-viral performance of photocatalytic materials are time-consuming. To address this problem, herein, we propose a screening test for the anti-viral performance of photocatalytic materials based on the ‘acetaldehyde decomposition test’—an air purification efficiency test used to evaluate the decomposition performance of photocatalytic materials. This test is suitable for screening multiple samples and conditions in a short period. The temporal variation in the acetaldehyde concentration was approximated using an exponential function, similar to the temporal variation in the viral infection values. Thereafter, the slope of the regression line for the acetaldehyde concentration over time was used as an indicator in the screening tests. When the anti-viral performance and acetaldehyde decomposition tests were conducted on the same photocatalytic material, a correlation was observed between the slopes of the regression lines. Overall, the proposed screening test shows good potential for evaluating the anti-viral performance of photocatalytic materials.
]]>Catalysts doi: 10.3390/catal14030162
Authors: Chia-Hung Kuo Hui-Min David Wang Chwen-Jen Shieh
Enzymes play an important role in biomedical, cosmetic and food applications, and their effects are mainly related to their specific reactions and catalytic activity [...]
]]>Catalysts doi: 10.3390/catal14030161
Authors: Andrés R. Alcántara
The worldwide market for active pharmaceutical ingredients (APIs) is currently in a favourable condition [...]
]]>Catalysts doi: 10.3390/catal14030160
Authors: Elisabete P. Carreiro Hans-Jürgen Federsel Gesine J. Hermann Anthony J. Burke
Deep eutectic solvents (DESs) are a mixture of two or more components, and at a particular composition, they become liquids at room temperature. When the compounds that constitute the DESs are primary metabolites namely, amino acids, organic acids, sugars, or choline derivatives, the DESs are called natural deep eutectic solvents (NADESs). NADESs fully represent green chemistry principles. These solvents are highly welcome, as they are obtained from renewable resources, and gratifyingly are biodegradable and biocompatible. They are an alternative to room-temperature ionic liquids (RTILs). From the pharmaceutical industry’s point of view, they are highly desirable, but they unfortunately have been rarely used despite their enormous potential. In this review, we look at their impact on the asymmetric catalytic synthesis of key target molecules via metal-based catalysis, biocatalysis, and organocatalysis. In many cases, the NADESs that have been used are chiral and can even promote enantioselective reactions; this crucial and very exciting aspect is also discussed and analyzed.
]]>Catalysts doi: 10.3390/catal14030159
Authors: Shun Li Xinbo Liu Xinyue Zhang Youling Wang Shanliang Chen Yong Liu Yuqiao Zhang
The current scenario sees over 60% of primary energy being dissipated as waste heat directly into the environment, contributing significantly to energy loss and global warming. Therefore, low-grade waste heat harvesting has been long considered a critical issue. Pyroelectric (PE) materials utilize temperature oscillation to generate electricity, while thermoelectric (TE) materials convert temperature differences into electrical energy. Nanostructured PE and TE materials have recently gained prominence as promising catalysts for converting thermal energy directly into chemical energy in a green manner. This short review provides a summary and comparison of catalytic processes initiated by PE and TE effects driven by waste thermal energy. The discussion covers fundamental principles and reaction mechanisms, followed by the introduction of representative examples of PE and TE nanomaterials in various catalytic fields, including water splitting, organic synthesis, air purification, and biomedical applications. Finally, the review addresses challenges and outlines future prospects in this emerging field.
]]>Catalysts doi: 10.3390/catal14030158
Authors: Shanshan Sun Xiaoyu Peng Xingcui Guo Xiufang Chen Di Liu
The exploitation of highly efficient solvent-free catalytic systems for the selective aerobic oxidation of benzylic compounds to produce corresponding ketones with molecular oxygen under mild conditions remains a great challenge in the chemical industry. In this work, Au-Pd nanoparticles supported on porous carbon catalysts were fabricated by the borax-mediated hydrothermal carbonization method and the chemical reduction method. The physicochemical properties of Au-Pd bimetallic samples were examined by XRD, N2 sorption, SEM, TEM, and XPS techniques. The Au-Pd nanoparticles have successfully immobilized on the spherical carbon support with a porous structure and large surface area. A solvent-free catalytic oxidation system was constructed to selectively convert indane into indanone with Au-Pd nanocatalysts and O2. In contrast with a monometallic Au or Pd catalyst, the resulting bimetallic Au-Pd catalyst could effectively activate O2 and exhibit improved catalytic activity in the controlled oxidation of indane into indanone under 1 bar O2. A total of 78% conversion and >99% selectivity toward indanone can be achieved under optimized conditions. The synergistic effect of Au and Pd and porous carbon support contributed to the high catalytic activity for aerobic benzylic compound oxidation. This work offers a promising application prospect of efficient and recyclable Au-Pd nanocatalysts in functional benzylic ketone production.
]]>Catalysts doi: 10.3390/catal14020157
Authors: Zhiming Ma Lei Wang Guangyu Li Tao Song
The utilization and development of biomass resources is an efficient solution to mitigate the fossil energy crisis. Based on the advantages of mild reaction conditions, rapid reaction, and high conversion, the synthesis of 2,5-furandicarboxylic acid (FDCA) by the electrocatalytic oxidation of 5-hydroxymethylfurfural (HMFOR) has attracted considerable attention. This review will summarize the recent advances of HMFOR to FDCA, including the reaction pathway and mechanism, as well as the catalytic performance of various heterogeneous electrocatalysts. The challenges and prospects for HMFOR are also focused on. Finally, it is expected that this work may provide guidance for the design of high-efficiency electrocatalysts and thereby accelerate the industrialization process of biomass utilization.
]]>Catalysts doi: 10.3390/catal14020156
Authors: Husnain Ahmad Abbasi Maha M. Al Moneef Jahanzeb Khan Muhammad Hafeez Muhammad Usman Hameed Muhammad Abdullah Khan Shabnam Shahida Habib Ahmad Abbasi Sook-Keng Chang
In this study, we engineered a sub-70 nm nanocomposite of ZnO/Zn2TiO4 using a low-temperature solution-phase method with titanium isopropoxide and zinc acetate as precursors, and isopropyl alcohol and water as solvents. The investigation focused on nanocomposite growth by varying precursor and surfactant concentrations and their efficiency within different pH ranges. All three ZnO/Zn2TiO4 nanocomposites exhibited hexagonal wurtzite ZnO and Zn2TiO4 structures. The crystallite size in these nanocomposites ranged from 39.50 nm to 62.67 nm for ZnO and 21.24 nm to 26.15 nm for Zn2TiO4. Morphological observations using FESEM revealed the formation of dispersed cotton packet-like nanocomposites with sizes ranging from 18 to 350 nm. FTIR analysis showed peaks indicative of Ti–O and Zn–O bond formation, and EDX spectrum confirmed the presence of Ti, O, and Zn. UV spectrums and photocatalytic investigations confirmed the successful formation of ZnO/Zn2TiO4 nanocomposites with notable photocatalytic degradation efficiency for methylene blue dye under various conditions. These findings suggest the potential applicability of the synthesized nanocomposites for environmental pollutant degradation.
]]>Catalysts doi: 10.3390/catal14020155
Authors: Mengqi Tang Ahmed Gamal Arvind K. Bhakta Khouloud Jlassi Aboubakr M. Abdullah Mohamed M. Chehimi
Due to ever-increasing global warming, the scientific community is concerned with finding immediate solutions to reduce or utilize carbon dioxide (CO2) and convert it in useful compounds. In this context, the reductive process of CO2 methanation has been well-investigated and found to be attractive due to its simplicity. However, it requires the development of highly active catalysts. In this mini-review, the focus is on biochar-immobilized nanocatalysts for CO2 methanation. We summarize the recent literature on the topic, reporting strategies for designing biochar with immobilized nanocatalysts and their performance in CO2 methanation. We review the thermochemical transformation of biomass into biochar and its decoration with CO2 methanation catalysts. We also tackle direct methods of obtaining biochar nanocatalysts, in one pot, from nanocatalyst precursor-impregnated biomass. We review the effect of the initial biomass nature, as well as the conditions that permit tuning the performances of the composite catalysts. Finally, we discuss the CO2 methanation performance and how it could be improved, keeping in mind low operation costs and sustainability.
]]>Catalysts doi: 10.3390/catal14020154
Authors: Dichen Tan Zhaofei Ma Lian Chen Yuanzhu Mi Xuemin Yan
This work explores the low-temperature catalytic oxidation of heavy oil (140 °C), resulting in structural changes with reduced heavy components and increased light components. The catalytic oxidation system consists of a catalyst, an oxidant, and a proton donor. Four different complexes of iron-based catalysts were utilized: ferric oleate, iron naphthenate, EDTA–FeNa, and EDDHA–FeNa. Catalytic oxidation processes with these catalysts produced four types of oxygenated oil, which were then analyzed using group composition analysis and a viscosity test. The results show that EDDHA–FeNa is more favorable for the catalytic oxidation of heavy oil in a low-temperature environment, achieving a viscosity reduction rate of 78.57%. Furthermore, the catalytic performance of heavy oil oxidation was investigated using EDDHA–FeNa as catalyst under three conditions: the amount of catalyst, oxidant and reaction temperature. These findings may provide researchers valuable guidance and principles for the investigation and development of advanced catalytic viscosity reduction of heavy oil.
]]>Catalysts doi: 10.3390/catal14020153
Authors: Yishan Jiang Ying Xu Qichao Zhang Xin Zhao Feng Xiao Xinbo Wang Guojun Ma
Nowadays, it is highly desired to develop highly active and humidity-resistive ozone decomposition catalysts to eliminate the ozone contaminant, one of the primary pollutants in the air. In this work, a series of Cu2S hollow structured materials were rapidly synthesized using different structured Cu2O templates. The Cu2S from porous Cu2O showed the highest ozone catalytic decomposition efficiency of >95% to 400 ppm ozone with a weight hourly space velocity of 480,000 cm3·g−1·h−1 in dry air. Importantly, the conversion remained >85% in a high relative humidity of 90%. The mechanism was explored by diffusive reflectance infrared spectroscopy which showed the decomposition intermediate of O22−, and X-ray photoelectron spectroscopy revealed the dual active site of both Cu and S. The EPR and UPS characterization results also explained the superiority of porous Cu2S catalysts from the material itself. All these results show the effective decomposition of ozone by Cu2S, especially in harsh environments, promising for active ozone elimination.
]]>Catalysts doi: 10.3390/catal14020152
Authors: Jamylle Y. C. Ribeiro Gessica O. S. Santos Aline R. Dória Iñaki Requena Marcos R. V. Lanza Katlin I. B. Eguiluz Giancarlo R. Salazar-Banda Justo Lobato Manuel A. Rodrigo
In this work, a series of novel mixed metal oxide (MMO) electrodes with the composition Ti/RuO2Sb2O4Ptx (0 ≤ x ≤ 10.0) were developed, envisaging their application in a reversible electrochemical cell based on the chloralkaline process as an energy storage system. These electrodes were synthesized via the ionic liquid method. Comprehensive physical, chemical, and electrochemical characterizations were conducted to evaluate their performance. The feasibility of employing these electrodes within reversible processes was explored, using the products generated during the electrolytic operation of the system for fuel cell operation. During the electrolyzer operation, higher current densities resulted in enhanced current efficiencies for the production of oxidized chlorine species. Notably, the presence of platinum in the catalyst exhibited a negligible impact on the coulombic efficiency at low current densities where water oxidation predominates. However, at higher current densities, the presence of platinum significantly improved coulombic efficiency, approaching values of approximately 60%. Transitioning to a fuel cell operation, despite the improved kinetic performance associated with a higher platinum content, the process efficiency was predominantly governed by ohmic losses. Curiously, the MMO electrode made without platinum (Ti/(RuO2)70-(Sb2O4)30) displayed the lowest ohmic losses. This study establishes optimal conditions for future investigations into this promising possibility, which holds great potential for energy storage via chloralkaline-based reversible reactions.
]]>Catalysts doi: 10.3390/catal14020151
Authors: Xinyu Han Mengyao Bian Kaijie Liu Xin Yang Daying Zheng Xiangguang Yang Yibo Zhang
Ce-based selective catalytic reductions with an NH3 (NH3-SCR) catalyst have emerged as a focal point in denitrification catalyst research. However, the correlation between the structural characteristics of Ce-based catalysts and the influence of CeO2 nanoparticle size on SO2 resistance remains unclear. CeO2 nanospheres with different sizes of less than 10 nm were synthesized, and a series of supported CeO2/SBA-15 catalysts were prepared according to the 10 nm pore size of SBA-15. These catalysts were used to explore the influence of the size of the CeO2 nanospheres on these catalysts, specifically on their SO2 resistance in NH3-SCR reactions. With the increase in size, their SO2 resistance became stronger. The results of NH3-TPD, H2-TPR, and XPS indicated that the catalyst with the largest particle size had the lowest adsorption of SO2, which was attributed to more acid sites and a mutual effect between Si and Ce, resulting in the best SO2 resistance. It was also observed that there was less sulfate deposition on the catalyst by thermogravimetric analysis. In situ DRIFTs revealed that after SO2 poisoning, the NH3-SCR reaction on the catalyst predominantly follows the E-R mechanism. This study offers recommendations for the development of Ce-based SO2-resistant NH3-SCR catalysts, specifically focusing on the synthesis and interaction of nanomaterials.
]]>Catalysts doi: 10.3390/catal14020150
Authors: Danyu Wang Junyu Lang Zhehao Qiu Ningxujin Ding Yong Yang
The La2O3 catalyst exhibits good performance in OCM reactions for its promising C2 selectivity and yield. Previous studies have affirmed that the formation of carbonates in La2O3 impedes the catalyst’s activity as a result of poisoning from CO2 exposure. In this study, a series of Na2WO4-impregnated La2O3 catalysts were synthesized to investigate the poisoning-resistant effect. The bulk phase and kinetics of the catalysts were analyzed in reactors employed with in situ XRD-MS and online MS, focusing on the CO2 adsorption on La2O3 and the phase transition process to La2O2CO3 in temperature zone correlated to OCM light-off. In situ XRD analysis revealed that, with Na2WO4 doped, CO2 exposure at elevated temperatures formed La2O2CO3 in tetragonal crystal phases, exhibiting distinctive differences from the hexagonal phase carbonates in undoped commercial La2O3. The ability to develop tetragonal or monoclinic La2O2CO3 was suggested as a descriptor to assess the sensitivity of La2O3 catalysts to CO2 adsorption, a tunable characteristic found in this study through varying Na2WO4 doping levels. Coupled XRD-MS analysis of CO2 adsorption uptake and phase change further confirmed a positive dependence between the resistivity of La2O3 catalyst to CO2 adsorption and its low-temperature C2 selectivity. The results extended the previous CO2 poisoning effect from multiple perspectives, offering a novel modification approach for enhancing the low-temperature performance of La2O3 catalysts in OCM.
]]>Catalysts doi: 10.3390/catal14020149
Authors: Patrícia S. F. Ramalho Olívia Salomé G. P. Soares José J. M. Órfão Manuel Fernando R. Pereira
Bromate, often detected in drinking water, is associated with a significant risk of cancer. Catalytic reduction has been recognized as an effective treatment technique to remove ions by reducing them over metal catalysts in the presence of a reducing agent, usually hydrogen. This work aims to synthesize metallic magnetic nanoparticles of iron oxide (FeO) and mixed iron oxides with manganese (MnFeO), cobalt (CoFeO), and copper (CuFeO) coated with carbon via chemical vapor deposition (C-MNP) to be applied as catalysts to the reduction of bromate in water. The use of magnetic nanoparticles coated with carbon enables catalyst recovery via magnetic separation and takes advantage of the catalytic properties of the carbon materials. The iron particles proved to be the most promising catalysts for the reduction of bromate into bromide, the highest removal being obtained with the CFeO@CVD750 sample, resulting in a 99% conversion after 120 min of reaction under the conditions tested. Due to its magnetic nature, the catalytic material was easily removed after the reaction and applied in four consecutive cycles without losing its catalytic properties. These results highlight the great potential of carbon-coated magnetic nanoparticles for reducing bromate in water.
]]>Catalysts doi: 10.3390/catal14020148
Authors: Daria Armani Oreste Piccolo Antonella Petri
The use of immobilized alcohol dehydrogenases (ADHs) offers numerous advantages, especially in the reaction conditions required by industrial applications. Looking for more efficient and cost-effective methods of ADH immobilization, in this study we explored silica-based supports as an alternative to the use of functionalized polymeric resins. Three commercially available ADHs were immobilized by adsorption and covalent bond formation. The obtained supported biocatalysts were applied for the bioreduction of acetophenone and some derivatives with good yields and excellent enantioselectivity. The important intermediate (S)-1-[3,5-bis(trifluoromethyl)phenyl]ethanol was obtained with a high enantiomeric excess (>99%) by using the highest performing immobilized ADH sample. The reusability of this biocatalyst was investigated in a flow system for five consecutive runs; the experiments showed that the biocatalyst could be recycled without a loss of activity and enantioselectivity. Finally, cross-linking with the glutaraldehyde of the supported biocatalyst was also carried out to prevent the leaching of the enzyme during the catalytic reactions.
]]>Catalysts doi: 10.3390/catal14020147
Authors: Saule Mergenbayeva Zhanibek Abitayev Milana Batyrbayeva John Vakros Dionissios Mantzavinos Timur Sh. Atabaev Stavros G. Poulopoulos
Sulfamethoxazole (SMX) is a common antibiotic that is considered an emerging pollutant of water bodies, as it is toxic for various aquatic species. TiO2-based photocatalysis is a promising method for SMX degradation in water. In this work, TiO2/zeolite (Z-45 loaded with TiO2 labeled as TZ and ZSM-5 loaded with TiO2 labeled as TZSM) composites were prepared by mechanical mixing and liquid impregnation methods, and the photocatalytic performance of these composites (200 mg·L−1) was investigated toward the degradation of SMX (30 mg·L−1) in water under UV light (365 nm). The pseudo-first-order reaction rate constant of the TZSM1450 composite was 0.501 min−1, which was 2.08 times higher than that of TiO2 (k = 0.241 min−1). Complete SMX degradation was observed in 10 min using the UV/TZSM1450 system. The mineralization ability in terms of total organic carbon (TOC) removal was also assessed for all of the prepared composites. The results showed that 65% and 67% of SMX could be mineralized within 120 min of photocatalytic reaction by TZSM2600 and TZSM1450, respectively. The presence of Cl− and CO32− anions inhibited the degradation of SMX, while the presence of NO3− had almost no effect on the degradation efficiency of the UV/TZSM1450 system. The electrical energy per order estimated for the prepared composites was in the range of 68.53–946.48 kWh m−3 order−1. The results obtained revealed that the TZSM1450 composite shows promising potential as a photocatalyst for both the degradation and mineralization of SMX.
]]>Catalysts doi: 10.3390/catal14020146
Authors: Marvin Chávez-Sifontes María Ventura
Currently, many research projects are focused on the conversion of renewable raw materials into chemicals and fuels. Lignocellulosic biomass is a raw material used for the production of bio-oils and black liquors. These biomass-derived fractions offer promising paths for the production of valuable chemical products. Various catalytic methods have been investigated for upgrading the biomass-derived fractions. Researchers are interested in the hydrodeoxygenation process (HDO); in this process, the oxygen groups are eliminated by breaking the C-O bonds and water as a product. Incorporating heterogeneous catalysts (i.e., noble metals, transition metals, and metal sulfides) improves this process. Most HDO review articles describe catalytic results for model phenolic compounds. However, there is also a need to investigate the catalytic activity of real biomass-derived fractions. This paper explains research results regarding the upgrading of lignin-derived fractions (i.e., black liquors) by HDO. The paper has been organized according to the type of heterogeneous catalyst and shows compelling results based on different experimental conditions. The final sections present an analysis of the documented results and outline perspectives about integrating lignin into the biorefinery framework.
]]>Catalysts doi: 10.3390/catal14020145
Authors: Naiyuan Dong Tanglaw Roman Catherine Stampfl
Using ab initio calculations, the reaction path for methane dehydrogenation over a series of Ni-based single-atom alloys (Cu, Fe, Pt, Pd, Zn, Al) and the effect that subsurface carbon at the Ni(111) surface has on the reaction barriers are investigated. Due to the well-known problem of coking for Ni-based catalysts, the adsorption and associated physical properties of 0.25 ML, 1.0 ML, and 2 ML of carbon on the Ni(111) surface of various sites are first studied. It is found that the presence of subsurface carbon reduces the stability of the intermediates and increases the reaction barriers, thus reducing the performance of the Ni(111) catalyst. The presence of Al, Zn, and Pt is found to reduce the barriers for the CH4 → CH3 + H and CH3 → CH2 + H (Pt); and CH → C + H (Al, Zn) reactions, while Ni(111) yields the lowest barriers for the CH2 → CH + H reaction. These results thus suggest that doping the Ni surface with both Al or Zn atoms and Pt atoms, functioning as distinct active sites, may bring about an improved reactivity and/or selectivity for methane decomposition. Furthermore, the results show that there can be significant adparticle–adparticle interactions in the simulation cell, which affect the reaction energy diagram and thus highlight the importance of ensuring a common reference energy for all steps.
]]>Catalysts doi: 10.3390/catal14020144
Authors: Jingfei Luan Yichun Wang Ye Yao Liang Hao Jun Li Yu Cao
Eu2SmSbO7 and ZnBiEuO4 were synthesized for the first time using the hydrothermal method. Eu2SmSbO7/ZnBiEuO4 heterojunction photocatalyst (EZHP) was synthesized for the first time using the solvothermal method. The crystal cell parameter of Eu2SmSbO7 was 10.5547 Å. The band gap width of Eu2SmSbO7 was measured and found to be 2.881 eV. The band gap width of ZnBiEuO4 was measured and found to be 2.571 eV. EZHP efficiently degraded the pesticide chlorpyrifos under visible light irradiation (VLID). After VLID of 160 min, the conversion rate of the chlorpyrifos concentration reached 100%, while the conversion rate of the total organic carbon (TOC) concentration was 98.02% using EZHP. After VLID of 160 min, the photocatalytic degradation conversion rates of chlorpyrifos using EZHP were 1.13 times, 1.19 times, and 2.84 times those using Eu2SmSbO7, ZnBiEuO4, and nitrogen-doped titanium dioxide (N-doped TiO2), respectively. The photocatalytic activity could be ranked as follows: EZHP > Eu2SmSbO7 > ZnBiEuO4 > N-doped TiO2. The conversion rates of chlorpyrifos were 98.16%, 97.03%, 96.03%, and 95.06% for four cycles of experiments after VLID of 160 min using EZHP. This indicated that EZHP was stable and could be reused. In addition, the experiments with the addition of capture agents demonstrated that the oxidation removal ability of three oxidation free radicals for degrading chlorpyrifos obeyed the following order: hydroxyl radical > superoxide anion > holes. This study examined the intermediates of chlorpyrifos during the photocatalytic degradation of chlorpyrifos, and a degradation path was proposed, at the same time, the degradation mechanism of chlorpyrifos was revealed. This study provides a scientific basis for the development of efficient heterojunction photocatalysts.
]]>Catalysts doi: 10.3390/catal14020143
Authors: Minghui Liu Wenxin Li Chengzhuo Zheng Fei Yuan Hui Wang Chengdong Wang Qinmin Pan Garry L. Rempel
The hydrogenation of C=C bonds in styrene−butadiene rubber (SBR), catalyzed by RhH(P(i-Pr)3)3, was experimentally investigated. Tris(triisopropylphosphine)hydridorhodium(I), RhH(P(i-Pr)3)3 (i-Pr=CH(CH3)2) was prepared by using rhodium chloride (RhCl3), tetrahydrofuran (THF), triisopropylphosphine (P(i-Pr)3) and a sodium mercury amalgam. The effect of catalyst/polymer ratio, reaction temperature, and hydrogen pressure on the reactivity of the catalytic system has been studied. The optimal experimental condition was obtained. The hydrogenated styrene-butadiene rubber (HSBR) was analyzed by FT-IR and 1H-NMR. In the absence of any additives, the conversion of C=C bonds in SBR could easily reach 95% in a short period of time, and no obvious cross-linking was observed. The dynamic properties of SBR did not change after the hydrogenation of the unsaturated C=C bonds. A preliminary reaction mechanism was also proposed. This study provides a new route, not only for the chemical modification of SBR by using a rhodium complex but also for the hydrogenation of other unsaturated polymers, such as diene-based rubbers.
]]>Catalysts doi: 10.3390/catal14020142
Authors: Dengke Li Qinghao Shi Fengbing Liang Dexin Feng
Biodiesel is a non-toxic and environmentally friendly fuel that is made from renewable biological sources. It can replace petrochemical diesel and has very broad application prospects. However, the main raw materials in biodiesel are animal and plant oils, which present the problems of high costs and a lack of resources. The current research primarily emphasizes the transesterification process, with comparatively less focus on the esterification of fatty acids. In this paper, a series of phosphotungstic acid (PTA)-functionalized hydrophobic MCM–41 catalysts, OTS–PTA–MCM–41(Cx), were synthesized and used to catalyze the esterification of long-chain fatty acids with methanol in water. The experimental results show that the yield of esterification reached a maximum when catalyzed by OTS–PTA–MCM–41(Cx) and synthesized with a template agent with two carbon atoms less than the number of carbon atoms of a fatty acid. The effects of different reaction variables were investigated to optimize the reaction conditions for the maximum conversion. The stability of the catalyst was also verified. Finally, a mixed catalyst was used to catalyze in situ the esterification of fatty acids in a fermentation broth, which reached a high level (close to 90%). This paper provides references for the synthesis of a hydrophobic solid acid catalyst and green synthesis by esterification reactions in an aqueous solution and a fermentation broth system.
]]>Catalysts doi: 10.3390/catal14020141
Authors: Preeti Kashyap Magdalena Brzezińska Nicolas Keller Agnieszka Ruppert
The conversion of lignocellulosic biomass to valuable chemicals such as levulinic acid and γ-valerolactone is a promising approach for achieving a sustainable circular economy. However, the presence of impurities during the stepwise chemical processing chain of the biomass feedstock can significantly impact both the hydrolysis and hydrogenation steps implemented to convert the cellulosic feedstock to levulinic acid and further to γ-valerolactone, respectively. This review article explores the effects of those impurities by classifying them into two groups, namely endogenous and exogenous types, based on whether they originate directly from the raw lignocellulosic biomass or arise during its multi-step chemical processing. Endogenous impurities include heavy metals, alkali metals, alkaline earth metals, proteins, and side products from the downstream treatment of cellulose, while exogenous impurities are introduced during physical pre-treatments such as ball milling or during the hydrolysis step, or they might originate from the reactor setup. The specific catalyst deactivation by carbonaceous species such as humins and coke is considered. The mechanisms of impurity-induced catalyst deactivation and by-product formation are thoroughly discussed. Additionally, strategies for minimizing the detrimental effects of impurities on biomass conversion and enhancing catalytic efficiency and stability are also proposed.
]]>Catalysts doi: 10.3390/catal14020140
Authors: Sónia Alexandra Correia Carabineiro
In terms of catalysis, the exploration of novel materials and innovative methodologies continues to drive the field forward, offering solutions to pressing challenges in various industrial applications [...]
]]>Catalysts doi: 10.3390/catal14020139
Authors: Rasa Šlinkšienė Rasa Paleckienė Ieva Gaidė Violeta Makarevičienė Eglė Sendžikienė
Dolomite as a heterogeneous catalyst can be used in biodiesel synthesis. Process material costs can be reduced by regenerating and reusing the catalyst. Two methods of regeneration of dolomite were studied: (1) washing for 30 min with methanol, filtration, and washing for 30 min with hexane and (2) calcination at high temperature. Catalytic efficiency and catalyst changes after 1–6 cycles were evaluated. X-ray, FTIR, and SEM studies were performed. Calcination has been found to be a more effective method of catalyst regeneration than washing with solvents. The catalytic effectiveness of dolomite only slightly decreased over six application cycles. The results of the instrumental analysis showed that the structure and composition of the dolomite do not change during calcination after three cycles, while obvious changes in the structure of dolomite during catalyst washing were observed.
]]>Catalysts doi: 10.3390/catal14020138
Authors: Linyuan Zhou Huiru Yang Xiangze Du Changwei Hu
The hydrodeoxygenation (HDO) of renewable fats or fatty acids into alkanes is a powerful measure to address energy and environmental crises. Molybdenum carbide-based catalysts are promising due to their platinum-like noble metal electronic properties. In this paper, Mo2C catalysts were prepared by one-step carbonization of amine molybdenum oxide (AMO) precursors using diamines with different carbon chain lengths as ligands. The physical and chemical properties and the HDO catalytic activity of the catalysts were investigated. The results indicate that as the carbon chain of diamines in the precursor increases, the carbon content of the catalysts in the surface and bulk phase increases. The Mo2C-12 catalyst exhibited excellent catalytic performance, with a palmitic acid conversion rate of 100% and an alkane selectivity of 96.6%, which are attributed to the smallest particle size, largest pore size, and synergistic effect of carbon. This work provides a simple and safe method for regulating the surface properties of Mo2C catalysts.
]]>Catalysts doi: 10.3390/catal14020137
Authors: Rui G. Faria Dinis Silva Fátima Mirante Sandra Gago Luís Cunha-Silva Salete S. Balula
The removal of sulfur- and nitrogen-containing compounds present in fuels is and will be crucial to accomplish actual strict regulations to avoid environmental and humanity health adversities. The conventional hydrodesulfurization and hydrodenitrogenation processes conducted by refineries are limited due to severe operating conditions, and even more importantly, they are inefficient for simultaneously removing nitrogen- and sulfur-containing compounds in fuels. On the other hand, non-hydrogen technologies are beneficial in terms of mild operating conditions, and during the last two decades, some successful works have shown that these can be highly effective at efficiently removing both sulfur- and nitrogen-containing compounds from liquid fuels. For more than four decades, extensive research (thousands of publications since the 1980s) has been dedicated to developing remote desulfurization technologies without taking into consideration the presence of a complex fuel matrix, or even taking into account the presence of other harmful pollutant elements, such as nitrogen. Even more recently, several effective non-hydrogen denitrogenation processes have been reported without considering the presence of sulfur compounds. This review paper is a reflection on the limited work that has been successfully performed to simultaneously remove sulfur- and nitrogen-containing compounds from fuels. An evaluation of different methodologies (adsorption, extraction, oxidative (photo)catalysis, ultrasound-assisted oxidation) is presented here. Furthermore, this review intends to define new future strategies that will allow the design of more suitable and economical technologies, effectively conciliating desulfurization and denitrogenation processes to produce more sustainable fuels.
]]>Catalysts doi: 10.3390/catal14020136
Authors: Magira Zhylkybek Bolatbek Khussain Alexandr Sass Ivan Torlopov Tolkyn Baizhumanova Svetlana Tungatarova Alexandr Brodskiy Galina Xanthopoulou Kenzhegul Rakhmetova Rabiga Sarsenova Kaysar Kassymkan Yermek Aubakirov
Co–Mg catalysts for methane combustion were synthesized and studied, revealing the transformation of MgCo2O4 spinel into a CoO–MgO solid solution with oxygen release from the spinel lattice as the calcination temperature increased. Repeated heat treatment of the calcined solid solution at lower temperatures led to spinel regeneration with segregation of the solid solution phase. A TPR of the samples showed the presence of two characteristic peaks, the first of which relates to the transition of Co3+Oh spinel to the Co2+Oh structure of CoO, and the second to the reduction of CoO to Co°. The second peak was observed at 540–620 °C for samples calcined at temperatures below spinel decomposition, and for high-temperature samples at 900–1100 °C. Taking into account the identity of the structure of phases obtained in both cases, the formation of not a true CoO–MgO solid solution, but rather a mixture of ordered oxides (“pseudo-solid solution”) in the low-temperature region, was postulated. A study of the activity of the samples showed the high activity of the spinel systems and a linear relationship between the activation energy of methane oxidation and the heat treatment temperature.
]]>Catalysts doi: 10.3390/catal14020135
Authors: Baofang Jin Yuxin Liu Yue Ma Zhenguo Li Kaixiang Li Shuang Liu Rui Ran Xiaodong Wu
A series of Ag-modified manganese-mullite (SmMn2O5) catalysts with different Ag contents (1, 3, and 6 wt.%) were prepared via a citric acid sol–gel method for catalytic soot oxidation. The catalysts were characterized by powder X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Raman spectroscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy analysis (HRTEM), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). The soot oxidation activity of the mullite was significantly promoted by the addition of silver and affected by the loading amount of the metal. Herein, the influences of silver loading on the metal size distribution and its interactions with the mullite were studied. Based on these characterizations, a possible soot oxidation reaction mechanism was proposed for silver-modified SmMn2O5.
]]>Catalysts doi: 10.3390/catal14020134
Authors: Zhengqing Zhou Yinghua Zhang Zhian Huang Jia Liu Jinguo Sang Zuochun Luan Wei Tian Yukun Gao Xingyu Zhang Yucheng Ji Tao Tang
The catalytic partial oxidation of methane (CPOM) to methanol has been regarded as a promising approach for methane utilization, despite that the conversion remains a formidable challenge in the perspective of catalysts. A novel catalyst system of multi-wall carbon nanotubes (MWCNTs) that supported Fe2O3 with existing I2, consisting of non-noble metal and working in weak acid at an ambient temperature, was investigated for CPOM. MWCNTs supported the Fe2O3 catalyst, which was prepared by the impregnation method and characterized via HRTEM, XRD, XPS, FT-IR, and BET techniques. The characterization results reveal that, as a non-noble metal catalyst, the Fe2O3/MWCNTs catalyst had a good catalytic performance and stability in the CPOM. With the variation of reaction pressure and the dosage of Fe2O3/MWCNTs, the catalyst system obtained the highest methane conversion rate of 7.41% and methanol selectivity of 86.3%, which is analogous to that of the equivalently strong acid catalyst system. The I2-Fe2O3/MWCNTs catalyst system has great potential in the application of CPOM under mild, environmentally benign conditions, such as non-noble metal requirement, ambient temperature, and weak acid. The reaction mechanism was discussed.
]]>Catalysts doi: 10.3390/catal14020133
Authors: Yang Yue Qu Wu Chaofan Zheng Yongjun Sun Kinjal J. Shah
Red mud was modified by impregnation with Co element loading. The Co-RM catalyst was characterized using scanning electron microscopy (SEM), X-ray powder diffraction (XRD), X-ray fluorescence (XRF), and UV full-band scanning. The results showed that the modified Co-RM catalyst successfully loaded the Co element and formed an irregular pore structure on the surface, thereby increasing the number of active sites of the red mud catalyst and effectively improving the degradation efficiency of tetracycline. Under the optimal conditions of a catalyst dosage of 0.3 g/L, a persulfate dosage of 3 g/L, a reaction temperature of 50 °C, and a pH value of 7, a removal rate of 50 mg/L of tetracycline can be achieved: 89.5% after 90 min. The effects of common anions and humic acids in water, as well as radical quenchers (anhydrous ethanol and tert-butanol), on the degradation of tetracycline were investigated. The results showed that Cl−, CO32−, HCO3−, H2PO4−, NO32−, HPO42−, and humic acids showed inhibitory effects on the degradation of tetracycline, while SO42− showed a promoting effect on the degradation of tetracycline. The free radical quenching experiment showed that the most important free radicals that can degrade tetracycline in the system are sulfate radicals.
]]>Catalysts doi: 10.3390/catal14020132
Authors: Shenghua Zhu Jue Li Fuchang Cheng Jinghua Liang
A pellet-forming as-catalyst, CuO/Al2O3, was prepared by the precipitation–tablet molding method and characterized by the Brunner–Emmet–Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) techniques and TEM. The characterization results showed that the formed CuO/Al2O3 was in situ reduced to Cu/Al2O3 and Cu2O/ Al2O3 catalysts in the reaction system. The catalytic performance of catalyzing hydrogenation starch into glucose was investigated in an autoclave over CuO/Al2O3. The yield of glucose reached 83.16% at a temperature of 160 °C, a pressure of 1.8 MPa, a 100 g starch solution of 15 wt%, a catalyst dosage of 2.25%, a reaction time of 4 h, and a rotational speed of 630 r/min. The reusability of the catalyst was evaluated, and the glucose yield did not decrease obviously even after being reused for five consecutive cycles. Starch was converted into glucose through the synergistic action of Cu+ and Cu0 catalysis. This work is expected to provide valuable insights into the design of catalysts and the hydrogenation process for efficient starch hydrogenation.
]]>Catalysts doi: 10.3390/catal14020131
Authors: Shifei Gu Chengheng Huang Xiaorong Han Qiuju Qin Donghai Mo Chen Li Yuhua You Lihui Dong Bin Li
The physicochemical properties of active components play a key role in enhancing catalytic performance. In multi-component catalysts, different components offer a wide range of structural possibilities and catalytic potential. However, determining the role of specific components in enhancing efficiency may be blurry. This study synthetized a range of catalysts with various metal compositions on their external surfaces to investigate their catalytic activity on NH3-SCR. The V/CeMn/Ti catalysts exhibited exceptional catalytic efficiency and strong tolerance to SO2 during the SCR process. In the system, Mn and Ce facilitated electron transfer during the catalytic removal of NOx. As an assisting agent, increased the number of active species and acidic sites, playing a crucial role in oxidizing NO to NO2 and facilitating the denitrogenation reaction process at low temperatures. Further studies showed that the three ingredients exhibited unique adsorbent behaviors on the reacting gases, which provided different catalytic possibilities. This work modeled the particular catalysis of V and Ce (Mn) species, respectively, and offers experimental instruction for improving the activity and excellent tolerance to SO2 by controlling active ingredients.
]]>Catalysts doi: 10.3390/catal14020130
Authors: Xin Wen Kui Xie
The long-range ordered lattice structure and interconnected porous microstructure of porous single crystals (PSCs) provide structural regularity and connectivity in remote electron movement to stabilize oxygen vacancies and activate lattice oxygen linked to surface active sites. In this work, we prepare NiO powder, single-crystal (SC) NiO, and PSC NiO. NiO contains a significant amount of oxygen vacancies. We find that the structure of porous NiO can create more oxygen vacancies. We load Pt onto these NiO crystals by atomic layer deposition (ALD) to activate lattice oxygen on definite NiO surfaces. The results show that Pt-loaded NiO effectively exhibits CO oxidation performance, in which Pt-loaded PSC NiO completely oxidizes CO at 65 °C. With 1% CO fully adsorbed, the density of activate lattice oxygen becomes an essential factor affecting performance. PSC NiO with deposited Pt clusters exhibited stable CO oxidation catalysis when run in air at ~65 °C for 300 h.
]]>Catalysts doi: 10.3390/catal14020129
Authors: Sarah I. Othman Marwa H. Shemy Haifa E. Alfassam Haifa A. Alqhtani Ahmed A. Allam Mostafa R. Abukhadra Stefano Bellucci
Environmental organo bentonite synthesis using curcumin-derived chemicals is used as catalyst support for zinc with a Zn-pillaring structure (Zn@CU/BEN). The obtained composite was assessed as an affordable, highly effective, and multifunctional photocatalyst for enhanced oxidation of ibuprofen (IBU) residuals in water supplies. The Zn@CU/BEN composite (0.4 g/L) displayed significant catalytic activities, resulting in the complete oxidation of IBU (25 mg/L) after 80 min. Then, the complete mineralization based on the full elimination of TOC content was recognized after 160 min, with significant indications about the formed intermediates. The identified intermediates, together with the identification of hydroxyl radicals as the essential oxidizing agent, declared an oxidation pathway of IBU over Zn@CU/BEN that involved three steps: hydroxylation, decarboxylation/demethylation, and ring-opening processes. The toxic properties of raw pollutants as well as the oxidizing product at different durations were assessed based on the cell viability results of kidney (HEK293T) and liver (HepG2) cell lines. The partially oxidized sample in the initial duration displayed a higher toxicity impact than the raw IBU. However, the treated sample after 160 min reflected high biosafety and non-toxic properties (cell viability > 97%). The synergetic impact of bentonite and bentonite organo-modified by curcumin extract reflects enhancements in the adsorption as well as the oxidation performance of pillared zinc as a catalyst.
]]>Catalysts doi: 10.3390/catal14020128
Authors: Wladimir Reschetilowski
When the Swedish mineralogist Axel F [...]
]]>Catalysts doi: 10.3390/catal14020127
Authors: Alexandra A. Ioannidi Aikaterini Frigana John Vakros Zacharias Frontistis Dionissios Mantzavinos
Biochar derived from pomegranate peel at different pyrolysis temperatures (450, 600, and 850 °C) was synthesized and characterized by BET, XRD, FTIR, and SEM-EDX. Its catalytic efficiency in the degradation of the antihypertensive losartan (LOS) in the presence of sodium persulfate was examined. The biochar pyrolyzed at 850 °C exhibited higher catalytic activity, which was correlated with the greater surface area and higher concentration of minerals on its surface. Interestingly, despite adsorption being favored at alkaline pH, pH 3 showed the highest LOS degradation. LOS decomposition followed pseudo-first-order kinetics. The addition of persulfate significantly increased LOS reduction, while the presence of inorganic and organic water matrix constituents such as sodium chloride, bicarbonate, and humic acid inhibited the oxidation. Experiments conducted with radical scavengers revealed that both hydroxyl and sulfate radicals, as well as singlet oxygen, participated in LOS decomposition, with the former being the dominant species. Using a continuous flow reactor, the system exhibited a satisfactory steady-state performance of 90% LOS removal for 114 h. Afterward, a moderate decrease in performance was observed, which can be attributed to the alteration of the catalyst’s surface and mineral dissolution due to acidity.
]]>Catalysts doi: 10.3390/catal14020126
Authors: Lei Liu Ning Liu Biaohua Chen Chengna Dai Ning Wang
Hydrogen production by the electrolysis of water is a green and efficient method, which is of great significance for achieving sustainable development. Molybdenum disulfide (MoS2) is a promising electrocatalyst for hydrogen evolution reaction (HER) due to its high electrochemical activity, low cost, and abundant reserves. In comparison to the noble metal Pt, MoS2 has poorer hydrogen evolution performance in water electrolysis. Therefore, further modifications of MoS2 need to be developed aiming at improving its catalytic performance. The present work summarizes the modification strategies that have been developed in the past three years on hydrogen evolution from water electrolysis by utilizing MoS2 as the electrocatalyst and following the two aspects of internal and external modifications. The former includes the strategies of interlayer spacing, sulfur vacancy, phase transition, and element doping, while the latter includes the heterostructure and conductive substrate. If the current gap in this paper’s focus on modification strategies for electrocatalytic hydrogen evolution in water electrolysis is addressed, MoS2 will perform best in acidic or alkaline media. In addition to that, the present work also discusses the challenges and future development directions of MoS2 catalysts.
]]>Catalysts doi: 10.3390/catal14020125
Authors: Mohamed Ateia Matthew S. Johnson Bożena Czech
This Catalysts Special Issue explores cutting-edge research in the field of photocatalysis, offering a glimpse into the evolving landscape of environmental science and catalysis [...]
]]>Catalysts doi: 10.3390/catal14020124
Authors: Kess Marks Axel Erbing Lea Hohmann Tzu-En Chien Milad Ghadami Yazdi Matthias Muntwiler Tony Hansson Klas Engvall Dan J. Harding Henrik Öström Michael Odelius Mats Göthelid
Catalyst passivation through carbon poisoning is a common and costly problem as it reduces the lifetime and performance of the catalyst. Adding oxygen to the feed stream could reduce poisoning but may also affect the activity negatively. We have studied the dehydrogenation, decomposition, and desorption of naphthalene co-adsorbed with oxygen on Ni(111) by combining temperature-programmed desorption (TPD), sum frequency generation spectroscopy (SFG), photoelectron spectroscopy (PES), and density functional theory (DFT). Chemisorbed oxygen reduces the sticking of naphthalene and shifts H2 production and desorption to higher temperatures by blocking active Ni sites. Oxygen increases the production of CO and reduces carbon residues on the surface. Chemisorbed oxygen is readily removed when naphthalene is decomposed. Oxide passivates the surface and reduces the sticking coefficient. But it also increases the production of CO dramatically and reduces the carbon residues. Ni2O3 is more active than NiO.
]]>Catalysts doi: 10.3390/catal14020123
Authors: Haruna Imazu Kakeru Masaoka Saki Uike Masamichi Ogasawara
The molybdenum-catalyzed enantioselective ring-closing metathesis/kinetic resolution of a series of racemic planar-chiral 1,1′-diallylferrocene derivatives was reinvestigated utilizing the method of generating catalytically active chiral molybdenum-alkylidene species in situ, which allowed us to examine a variety of chiral molybdenum-alkylidene metathesis precatalysts in the present asymmetric reaction. With the catalyst screening experiments conducted in this study, the more practical reaction conditions, including a choice of a proper chiral molybdenum precatalyst, giving planar-chiral ferrocenes of higher enantiomeric purity and better chemoselectivity could be optimized.
]]>Catalysts doi: 10.3390/catal14020122
Authors: Chuande Huang
Chemical looping (CL) technology, initially developed as an advanced combustion method, has been widely applied in various processes, including the selective oxidation of hydrocarbons (e [...]
]]>Catalysts doi: 10.3390/catal14020121
Authors: Francisco Javier Rivas Fernando J. Beltrán Olga Gimeno
Wastewater generated in table olive manufacturing processes (WWTOMP) is a seasonal waste difficult to manage due to the high salinity content. The treatment of WWTOMP has been accomplished by including a precoagulation stage with aluminum sulfate, oxidation using the peroxymonosulfate/Fe(III) system, and a final aerobic biological stage. The optimum conditions of precoagulation led to a chemical oxygen demand removal rate of roughly 30–35% without the need for pH adjustment. The peroxymonosulfate(PMS)/Fe(III) system was thereafter applied to the effluent after coagulation. The addition of PMS lowered the initial pH to acidic conditions (pH = 1.5–2.0). Under these operating conditions, the initial PMS concentration and the initial Fe(III) dose showed optimum values. An excess of the oxidant and/or the catalyst partially inhibited the process efficiency, and pH exerted a significant influence. COD removal was substantially increased as the pH of the solution was moved toward circumneutral values in the interval 5–4. Moreover, at pH values of 5 and 7, PMS was capable of reducing COD without the need for Fe(III) presence. The direct oxidation of organics by PMS or the generation of chloride-based oxidants (Cl2 or HClO) is suggested to occur in parallel to the radical attack from PMS decomposition. An attempt to biologically reduce the final COD to discharge limits failed, mainly due to the high salinity content; however, the 1:2 dilution led to the reduction in COD from 6 to 2 g L−1. Acclimated sludges or saline content reduction should be first considered.
]]>Catalysts doi: 10.3390/catal14020120
Authors: Chiara Falcini Gonzalo de Gonzalo
Deep Eutectic Solvents (DESs) have appeared in recent years as an appealing alternative to classical organic solvents, due to their valuable environmental properties. In addition, these compounds, formed by the combination of one hydrogen bond donor with a hydrogen bond acceptor at a defined stoichiometric ratio, present other valuable activities not only as a reaction medium. DESs can also be employed as catalysts through hydrogen-bond interactions in different chemical transformations, thus substituting hazardous reagents and solvents. The search for novel and more environmentally friendly catalysts is an area of interest of pharmaceutical chemists, and therefore, the efforts made in the application of DESs as catalysts in the synthesis of APIs or its precursors are described, focusing mainly on condensations, nucleophilic additions to carbonyl moieties, and multicomponent reactions.
]]>Catalysts doi: 10.3390/catal14020119
Authors: Silvio Bellomi Davide Motta Marta Stucchi Laura Prati Nikolaos Dimitratos Alberto Villa
Herein, Ir/CeO2 catalysts were prepared using the deposition–precipitation method with NaOH or urea as the precipitating agent or using sol immobilization with tetrakis(hydroxymethyl)phosphonium chloride (THPC) as the protective and reducing agent. The effect of the preparation method on Ir catalyst activity was evaluated in the liquid-phase catalytic decomposition of hydrous hydrazine to hydrogen. Ir/CeO2 prepared using sol immobilization and DP NaOH showed the best activity (1740 h−1 and 1541 h−1, respectively) and yield of hydrogen (36.6 and 38.9%). Additionally, the effect of the support was considered, using TiO2 and NiO in addition to CeO2. For this purpose, the sol immobilization of preformed nanoparticles technique was considered because it allows the same morphology of the immobilized particles to be maintained, regardless of the support. Ir deposited on NiO resulted in the most selective catalyst with a H2 yield of 83.9%, showing good stability during recycling tests. The catalysts were characterized using different techniques: X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) equipped with an X-ray detector (EDX) and inductively coupled plasma–mass spectroscopy (ICP-MS).
]]>Catalysts doi: 10.3390/catal14020118
Authors: Elena Ionata Emilia Caputo Luigi Mandrich Loredana Marcolongo
Phytoremediation is an eco-friendly technology that utilizes plants and plant–microbe interactions to remove a wide spectrum of organic and inorganic pollutants from contaminated environments such as soils, waters and sediments. This low-impact, environmentally sustainable and cost-effective methodology represents a valuable alternative to expensive physical and chemical approaches, characterized by secondary pollution risks, and is gaining increasing attention from researchers and popular acceptance. In this review, the main mechanisms underlying the decontamination activity of plants have been clarified, highlighting the environmental remediation in fertility and soil health. Studies have illustrated the high potential of phytoremediation coupled with green and sustainable biocatalytic processes, which together represent a non-polluting alternative for the conversion of plant biomass into renewable resources. The convenience of this technology also lies in the valorization of the bio-wastes towards biofuels, energy purposes and value-added products, contributing to an effective and sustainable circular approach to phyto-management. The strategy proposed in this work allows, with the use of totally green technologies, the recovery and valorization of contaminated soil and, at the same time, the production of bioenergy with high efficiency, within the framework of international programs for the development of the circular economy and the reduction of greenhouse carbon emissions.
]]>Catalysts doi: 10.3390/catal14020117
Authors: Dominik Soukup-Carne Felipe Sanchez Bragagnolo Cristiano Soleo Funari Jesús Esteban
As fossil-based resource depletion intensifies and the use of lignocellulosic biomass gains more and more momentum for the development of biorefineries, the production of furans has received a great deal of attention considering their outstanding synthetic possibilities. The production of 5-hydroxymethylfurfural (HMF) is quite established in the recent scientific literature, with a large number of studies having been published in the last few years. Lately, there has been a growing interest in the synthesis of 5-chloromethylfurfural (CMF) as a novel building block of similar molecular structure to that of HMF. CMF has some advantages, such as its production taking place at milder reaction conditions, a lower polarity that enables easier separation with the aid of organic media, and the presence of chlorine as a better leaving group in synthesis. Precisely the latter aspect has given rise to several interesting products to be obtained therefrom, including 2,5-dimethylfuran, 2,5-furandicarboxylic acid, and 5-methylfurfural, to name a few. This work covers the most relevant aspects related to the production of CMF and an array of synthetic possibilities. Through varied catalysts and reaction conditions, value-added products can be obtained from this chemical, thus highlighting the advances in the production and use of this chemical in recent years.
]]>Catalysts doi: 10.3390/catal14020116
Authors: Dalsan Yoo Munjeong Kim Seung Kyo Oh Seoyeon Hwang Sohee Kim Wooram Kim Yoonja Kwon Youngmin Jo Jong-Ki Jeon
The objectives of this study were to prepare a high-purity hydroxylammonium nitrate (HAN) solution and evaluate the performance of various types of metal oxide/honeycomb catalysts during the catalytic decomposition of the HAN solution. Hydroxylammonium nitrate was prepared via a neutralization reaction of hydroxylamine and nitric acid. FT-IR was used to analyze the chemical composition, chemical structure, and functional groups of the HAN. The aqueous HAN solution obtained from pH 7.06 showed the highest concentration of HAN of 60% and a density of 1.39 g/mL. The concentration of HAN solution that could be obtained when the solvent was evaporated to the maximum level could not exceed 80%. In this study, catalysts were prepared using a honeycomb structure made of cordierite (5SiO2-2MgO-2Al2O3) as a support, with Mn, Co, Cu, Pt, or Ir impregnated as active metals. The pore structure of the metal oxide/honeycomb catalysts did not significantly depend on the type of metal loaded. The Cu/honeycomb catalyst showed the strongest effect of lowering the decomposition onset temperature in the decomposition of the HAN solution likely due to the intrinsic activity of the Cu metal being superior to that of the other metals. It was confirmed that the effect of the catalyst on the decomposition mechanism of the aqueous HAN solution was negligible. Through a repetitive cycle of HAN decomposition, it was confirmed that the Cu/honeycomb catalyst could be recovered and reused as a catalyst for the decomposition of an aqueous HAN solution.
]]>Catalysts doi: 10.3390/catal14020115
Authors: Oumaima Cherni Diego Carballares El Hocine Siar Pedro Abellanas-Perez Diandra de Andrades Javier Rocha-Martin Sellema Bahri Roberto Fernandez-Lafuente
The lipase from Prunus dulcis almonds has been immobilized for the first time. For this purpose, two different supports, an octadecyl methacrylate particulate support, and aminated agarose (monoaminoethyl-N-aminoethyl) have been utilized. Both immobilized biocatalysts show improved enzyme stability, but great changes in enzyme specificity were detected. The enzyme immobilized via ion exchange maintained its activity intact versus p-nitrophenyl butyrate, while the enzyme immobilized on the hydrophobic support fully lost its activity versus this substrate, which was confirmed to be due to substrate adsorption on the support. However, this biocatalyst was much more active versus triacetin (more than 10-fold), R- or S- methyl mandelate at pH 7. At pH 9, a strong effect of using phosphate or bicarbonate as reaction buffers was detected. Using bicarbonate, the interfacially immobilized enzyme presented no activity versus R-isomer, but it was very active versus the S-isomer and triacetin. Using a phosphate buffer during the reaction, all compounds were recognized as substrates. The enzyme immobilized via ion exchange was significantly more active using phosphate; in fact, using bicarbonate, the enzyme was inactive versus both methyl mandelate isomers. This paper shows for the first time a great interaction between the effects of the immobilization protocol and buffer used during reaction on the enantiospecificity of lipases.
]]>Catalysts doi: 10.3390/catal14020114
Authors: Moloko G. Mathipa-Mdakane Lucia Steenkamp
The utilization of chemical reactions is crucial in various industrial processes, including pharmaceutical synthesis and the production of fine chemicals. However, traditional chemical catalysts often lack selectivity, require harsh reaction conditions, and lead to the generation of hazardous waste. In response, biocatalysis has emerged as a promising approach within green chemistry, employing enzymes as catalysts. Among these enzymes, aldolases have gained attention for their efficiency and selectivity in catalyzing C-C bond formation, making them versatile biocatalysts for diverse biotechnological applications. Despite their potential, challenges exist in aldolase-based biocatalysis, such as limited availability of natural aldolases with desired catalytic properties. This review explores strategies to address these challenges, including immobilization techniques, recombinant expression, and protein engineering approaches. By providing valuable insights into the suitability of aldolases as biocatalysts, this review lays the groundwork for future research and the exploration of innovative strategies to fully harness the potential of aldolases in biotechnology. This comprehensive review aims to attract readers by providing a comprehensive overview of aldolase-based biocatalysis, addressing challenges, and proposing avenues for future research and development.
]]>Catalysts doi: 10.3390/catal14020113
Authors: Hongzhi Ding Chenyu Yang Congyan Jiang Wei Luo Qiuyue Wang Xuefeng Guo
The use of eco-friendly biomass as a resource is an efficient way to address the problems of fossil fuel depletion and climate change. In biomass conversion, versatile γ-valerolactone (GVL) is generally obtained from levulinic acid (LA) hydrogenation via a multimetallic catalyst system. Despite conversion efficiency being enhanced in mild conditions due to metal interactions, maintaining high catalyst stability is still a challenge. In this study, we synthesized a surrounded Co0.52Ni0.48@Al2O3-IE catalyst that exhibited excellent alloying and synergistic interaction between the metal constituents. Under relatively mild reaction conditions, the GVL yield over the catalyst exceeded 99% in LA hydrogenation. The catalyst showed no deactivation in a test of five cycles, displaying superiority in stability, possibly due to reasons of the physical isolation of the shell and the alumina retention on the Co-Ni alloys surface caused by the reversibility of exchange equilibrium. The present work demonstrated that a surrounded structured catalyst fabricated by ion exchange (IE) with active metals physically enclosed can lead to high catalytic activity and superior stability.
]]>Catalysts doi: 10.3390/catal14020112
Authors: Maria Antonopoulou Anna Tzamaria Kleopatra Miserli Christos Lykos Ioannis Konstantinou
In the present study, the photocatalytic oxidation and detoxification of aqueous matrices contaminated with boscalid using g-C3N4 catalyst and UV-A light was investigated. The UV-A/g-C3N4 process was found to achieve higher than 83% removal of boscalid in both matrices, with h+ and O2•− being the main species. UHPLC-HRMS analysis allowed the identification of five TPs, while the main degradation pathways involved hydroxylation, cyclization, and dechlorination. Scenedesmus rubescens microalgae species was exposed to boscalid solutions and lake water spiked with the fungicide before the photocatalytic treatment and inhibition in the growth rate was observed. An increase in the toxicity was also observed during the first stages of the treatment. The results from the in silico study correlate with the observed evolution of ecotoxicity during the application of the process, as some of the identified TPs were found to be toxic or very toxic for aquatic organisms. However, prolonged application of the process can lead to detoxification. It was also observed that the g-C3N4 catalyst can retain its photochemical stability and activity after at least three cycles. However, a slight decrease in the activity was observed when repeated another two times. This study demonstrated that the suggested photocatalytic process can both decrease the harmful effects of boscalid as well as effectively lower its concentration in water.
]]>Catalysts doi: 10.3390/catal14020111
Authors: Sónia Alexandra Correia Carabineiro
The catalytic oxidation of hydrocarbons stands at the forefront of sustainable chemical transformations, offering pathways to selectively convert aliphatic and aromatic compounds into valuable oxygenated products [...]
]]>Catalysts doi: 10.3390/catal14020110
Authors: Nickolas D. Polychronopoulos Angeliki Brouzgou
Three-dimensional printed electrodes seem to overcome many structural and operational limitations compared to ones fabricated with conventional methods. Compared to other 3D printing techniques, direct ink writing (DIW), as a sub-category of extrusion-based 3D printing techniques, allows for easier fabrication, the utilization of various materials, and high flexibility in electrode architectures with low costs. Despite the conveniences in fabrication procedures that are facilitated by DIW, what qualifies an ink as 3D printable has become challenging to discern. Probing rheological ink properties such as viscoelastic moduli and yield stress appears to be a promising approach to determine 3D printability. Yet, issues arise regarding standardization protocols. It is essential for the ink filament to be extruded easily and continuously to maintain dimensional accuracy, even after post-processing methods related to electrode fabrication. Additives frequently present in the inks need to be removed, and this procedure affects the electrical and electrochemical properties of the 3D-printed electrodes. In this context, the aim of the current review was to analyze various energy devices, highlighting the type of inks synthesized and their measured rheological properties. This review fills a gap in the existing literature. Thus, according to the inks that have been formulated, we identified two categories of DIW electrode architectures that have been manufactured: supported and free-standing architectures.
]]>Catalysts doi: 10.3390/catal14020109
Authors: Juan C. Aldana Marta Pedrosa Adrián M. T. Silva Joaquim L. Faria Juan L. Acero Pedro M. Álvarez
In this study, a mixed-matrix method was used to prepare PVDF polymeric membranes with different amounts of TiO2 P25 photocatalyst embedded, which were employed in filtration processes in the presence of UV radiation (LED, peak emission at 375 nm) to eliminate two aqueous micropollutants (MPs) used as model compounds (venlafaxine and metoprolol). The obtained membranes were characterized to gain insights into their texture, morphology, composition, and other catalyst-related properties that could affect the photocatalytic filtration process. For that purpose, N2 adsorption–desorption, contact angle, SEM-EDX, thermal analysis, FTIR, XPS, UV-vis DRS, and PL spectroscopy were used. Filtration tests were carried out in continuous mode using a dead-end filtration cell to evaluate the performance of the prepared membranes in removing the selected MPs. Experiments were performed both in ultrapure water and a secondary effluent from a municipal wastewater treatment plant. It was found that the synthesized membranes could effectively remove the target MPs in ultrapure water, achieving up to 99% elimination. Such process performance decreased drastically in the secondary effluent with removals below 35%. Carbonate/bicarbonate ions in the secondary effluent were identified as the main scavenging substances. Thus, after the partial removal of carbonate/bicarbonate ions from the secondary effluent, the removal of MPs achieved was above 60%.
]]>Catalysts doi: 10.3390/catal14020108
Authors: Sergey A. Smirnov Ruslan M. Mensharapov Dmitry D. Spasov Nataliya A. Ivanova Sergey A. Grigoriev
Platinum electrocatalysts on graphene-like supports have recently attracted research interest as components of electrochemical devices based on hydrogen oxidation reactions in acid media due to their improved electrochemical properties, high stability, and conductivity. Within the current work, hydrogen adsorption and the recombination effects of a proton and hydroxonium on a graphene-based electrocatalyst were investigated using density functional theory. The interaction between ions and the platinum surface was simulated for various configurations, including different initial ion distances and angles relative to the surface of the graphene sheet as well as different adsorptions on various Pt atoms (vertices or faces for Pt13 and Pt14 nanoclusters). Then, the geometry optimization was performed. Changes in the density of states during the reactions were studied to analyze the occurrences and alterations of the interactions. A comparative analysis of the obtained adsorption energies of H+ and H3O+ with experimental data was conducted. The energy was calculated to be less in absolute value, and intermediates were more stable in adsorption models with the H–Pt–Gr angle of 90° than in models with the angle of 180°. Strong chemical bonding for models with H–Pt distances less than 2 Å was observed from the DOS.
]]>Catalysts doi: 10.3390/catal14020107
Authors: Mohd Quasim Khan Khursheed Ahmad Waseem Raza Rais Ahmad Khan Manas Sutradhar Anup Paul
In this work we reported the hydrothermal preparation of molybdenum disulfide (MoS2). The phase purity and crystalline nature of the synthesized MoS2 were examined via the powder X-ray diffraction method. The surface morphological structure of the MoS2 was examined using scanning electron microscopy and transmission electron microscopy. The specific surface area of the MoS2 was calculated using the Brunauer-Emmett-Teller method. The elemental composition and distribution of the Mo and S elements were determined using energy-dispersive X-ray spectroscopy. The oxidation states of the Mo and S elements were studied through employing X-ray photoelectron spectroscopy. In further studies, we modified the active surface area (3 mm) of the glassy carbon (GC) electrode using MoS2 as an electrocatalyst. The MoS2 modified GC electrode (MSGC) was used as an electrochemical sensor for the detection of thiabendazole (TBZ). Linear sweep voltammetry (LSV) was used as the electrochemical sensing technique. The MSGC exhibited good performance in the detection of TBZ. A limit of detection of 0.1 µM with a sensitivity of 7.47 µA/µM.cm2 was obtained for the detection of TBZ using the LSV method. The MSGC also showed good selectivity for the detection of TBZ in the presence of various interfering compounds. The obtained results showed that MoS2 has good electrocatalytic properties. This motivated us to explore the catalytic properties of MoS2 in dye sensitized solar cells (DSSCs). Thus, we have fabricated DSSCs using MoS2 as a platinum-free counter electrode material. The MoS2 counter electrode-based DSSCs showed good power conversion efficiency of more than 5%. We believe that the present work is beneficial for the scientific community, and especially for research surrounding the design and fabrication of catalysts for electrochemical sensing and DSSC applications.
]]>Catalysts doi: 10.3390/catal14020106
Authors: Jerzy Podobiński Jerzy Datka
In our previous study, we elaborated a method of determination of concentrations of the basic sites O2− and OH− in a quantitative IR study of CO2 adsorption. Previous adsorption studies or TPD experiments only provided the total basicity without distinguishing between O2− and OH−. In this study, we determined the concentration of O2− and OH− on ZnO, Ga2O3, and MgO surfaces. The basicity of ZnO and MgO was found to be significantly higher than that of Ga2O3. The surface of ZnO was rich in O2−, the contribution of OH− was very small, and the Ga2O3 surface contained mainly OH−. For MgO, the contribution of O2− and OH− was comparable. According to the IR results, only a small fraction of all surface hydroxyls were sufficiently basic to react with CO2. The partial dehydroxylation changed the proportion of the concentrations of O2− and OH− on the oxides. We also elaborated upon a new method to determine the total concentration of basic sites via CO2 desorption monitored using IR. For all the oxides, we studied the sum of the concentrations of O2− and OH−, as determined in our quantitative IR studies, to find whether they were comparable with the total basicity determined in the desorption experiments.
]]>Catalysts doi: 10.3390/catal14020105
Authors: Pedro Abellanas-Perez Diego Carballares Javier Rocha-Martin Roberto Fernandez-Lafuente
The lipases from Thermomyces lanuginosus (TLL) and Candida antarctica (B) (CALB) were immobilized on octyl-agarose beads at 1 mg/g (a loading under the capacity of the support) and by overloading the support with the enzymes. These biocatalysts were compared in their stabilities in 10 mM of sodium phosphate, HEPES, and Tris-HCl at pH 7. Lowly loaded CALB was more stable than highly loaded CALB preparation, while with TLL this effect was smaller. Phosphate was very negative for the stability of the CALB biocatalyst and moderately negative using TLL at both loadings. The stability of the enzymes in HEPES and Tris-HCl presented a different response as a function of the enzyme loading (e.g., using lowly loaded CALB, the stabilities were similar in both buffers, but it was clearly smaller in HEPES using the highly loaded biocatalysts). Moreover, the specific activity of the immobilized enzymes versus p-nitrophenol butyrate, triacetin and R- or S-methyl mandelate depended on the buffer, enzyme loading, and interaction between them. In some cases, almost twice the expected activity could be obtained using highly loaded octyl-CALB, depending on the buffer. A co-interaction between the effects on enzyme activity and the specificity of support enzyme loading and buffer nature was detected.
]]>Catalysts doi: 10.3390/catal14020104
Authors: Tobias Weissenberger Ralf Zapf Helmut Pennemann Gunther Kolb
We report an investigation of catalyst performance for the decomposition of ammonia under industrially relevant conditions (high temperatures of up to 800 °C and an elevated pressure of 5 bar) with further emphasis on their stability at high reaction temperatures. The catalysts were applied and tested as coatings in 500 µm wide channels of microreactors. Nickel-based catalysts were studied and compared to a ruthenium-based catalyst supported on SiO2. The effect of the support on the catalytic performance was investigated, and CeO2-supported nickel catalysts were found to exhibit the highest activity. Promoters were applied to increase the NH3 decomposition activity of the Ni/CeO2 catalysts. The addition of cesium led to a slight reduction in activity, while lanthanum, calcium, and barium doping resulted in increased activity. In particular, the barium-doped Ni/CeO2 catalyst showed very high ammonia conversion and closed the activity gap with respect to ruthenium catalysts at reactor temperatures of 650 °C and higher. The hydrogen production rates achieved in this work were compared to values in the literature and were shown to exceed values found earlier for both nickel- and ruthenium-based catalysts. Furthermore, the ruthenium-based catalysts under investigation were rapidly deactivated at 700 °C, while the nickel-based catalysts did not show deactivation after 220 h on time on stream at 700 °C.
]]>Catalysts doi: 10.3390/catal14020103
Authors: Yinhai Zhang Xiaoxue Liu Ruyu Zhao Jingwei Zhang Lanfen Zhang Wei Zhang Jian Hu Hao Li
Recently, supported WO3-based catalysts have been widely used in oxidative desulfurization (ODS) due to their advantages of easy separation, high activity, and being environment-friendly. In this work, supported mesoporous WO3/SiO2 catalysts have been prepared using an incipient-wetness impregnation method with agricultural waste rice husks as both a silicon source and mesoporous template, and phosphotungstic acid as a tungsten source. The effects of different calcination temperatures and WO3 loadings on the ODS performance of samples are studied, and the appropriate calcination temperature and WO3 loading are 923 K and 15.0 wt.%, respectively. The relevant characterization results show that, compared with pure WO3, the specific surface area and mesopore volume of WO3/SiO2 samples are greatly increased. Due to (a) high WO3 loading, (b) high specific surface area, and (c) nanoscale WO3 grains uniformly dispersed on the surface of the mesoporous SiO2 carrier, active sites of WO3/SiO2 catalysts are greatly increased, and their catalytic activities are improved. After the sixth and eighth runs in the ODS of dibenzothiophene and 4,6-dimethyldibenzothiophene, respectively, the WO3/SiO2 catalyst still maintains high catalytic activity (>99.0%) despite the presence of a partial loss of WO3. In addition, with the aid of the UV-Vis technique, the tungsten-peroxo species, the active intermediates in the ODS reaction catalyzed by the WO3/SiO2 catalyst, are captured. Finally, a possible mechanism for the ODS of bulky organic sulfides using the WO3/SiO2 catalyst is proposed.
]]>Catalysts doi: 10.3390/catal14020102
Authors: Georgios Bampos Athanasia Petala Zacharias Frontistis
The need for low-cost and environmentally friendly energy is greater than ever nowadays due to the global population growth as well as the modern lifestyle [...]
]]>Catalysts doi: 10.3390/catal14020101
Authors: Serena Todaro Giuseppe Bonura Alessandro Cajumi Mariarita Santoro Fabrizio Randazzo Giosuè Giacoppo Francesco Frusteri Catia Cannilla
In this work, a 3D printing methodology based on the robocasting of catalytic ink pastes was applied to obtain structured matrix-like cylinders as innovative materials for an effective utilization of carbon dioxide. The influence of three different binders (i.e., PEI, HPMC and MC) on the physio-chemical, mechanical and catalytic properties of multi-channel monoliths was studied against a reference binder-free powdered system in order to envisage the effectiveness of the printing procedure in realizing hybrid advanced materials at a higher control and reproducibility than from traditional preparation techniques. In terms of textural and structural properties, the micro-extruded 3D cylinders only evidenced a slight difference in terms of relative crystallinity, with minor effects on the surface area exposure in relation to the specific binder used during the direct ink writing process. More importantly, the typology of binder significantly affected the rheological properties of the catalytic ink, with the need of a controlled viscosity to ensure a suitable thixotropic behaviour of the extrudable pastes, finally determining an optimal mechanical resistance of the final 3D monolith. The experimental validation of the hybrid multi-channel cylinders under conditions of CO2 hydrogenation demonstrated the great potential of additive manufacturing in the realization of catalyst architectures characterized by unique features and fidelity scarcely reproducible via conventional synthetic techniques.
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