Editor’s Choice Articles

Research into the incorporation of cerium into a diverse range of catalyst systems for a wide spectrum of process chemistries has expanded rapidly. This has been evidenced since about 1980 in the increasing number of both scientific research journals and patent publications that address the application of cerium as a component of a multi-metal oxide system and as a support material for metal catalysts. This review chronicles both the applied and fundamental research into cerium-containing oxide catalysts where cerium’s redox activity confers enhanced and new catalytic functionality. Application areas of cerium-containing catalysts include selective oxidation, combustion, NO_x remediation, and the production of sustainable chemicals and materials via bio-based feedstocks, among others. The newfound interest in cerium-containing catalysts stems from the benefits achieved by cerium’s inclusion, which include selectivity, activity, and stability. These benefits arise because of cerium’s unique combination of chemical and thermal stability, its redox active properties, its ability to stabilize defect structures in multicomponent oxides, and its propensity to stabilize catalytically optimal oxidation states of other multivalent elements. This review surveys the origins and some of the current directions in the research and application of cerium oxide-based catalysts. Full article

Due to increasingly stringent environmental regulations imposed by governments throughout the world, the manufacture of low-sulfur fuels has received considerable assiduity in the petroleum industry. In this investigation, mesoporous V₂O₅-decorated two-dimensional ZnO nanocrystals were manufactured using a simple surfactant-assisted sol–gel method for thiophene photocatalytic oxidative desulfurization (TPOD) at ambient temperature applying visible illumination. When correlated to pure ZnO NCs, V₂O₅-added ZnO nanocomposites dramatically improved the photocatalytic desulfurization of thiophene, and the reaction was shown to follow the pseudo-first-order model. The photocatalytic effectiveness of the 3.0 wt.% V₂O₅-ZnO photocatalyst was the greatest among all the other samples, with a rate constant of 0.0166 min⁻¹, which was 30.7 significantly greater than that of pure ZnO NCs (0.00054 min⁻¹). Compared with ZnO NCs, and owing to their synergetic effects, substantial creation of hydroxyl radical levels, lesser light scattering action, quick transport of thiophene species to the active recenters, and efficient visible-light gathering, V₂O₅-ZnO nanocomposites were found to have enhanced photocatalytic efficiency. V₂O₅-ZnO nanocomposites demonstrated outstanding stability during TPOD. Using mesoporous V₂O₅-ZnO nanocomposites, the mechanism of the charge separation process was postulated. Full article

High-temperature oxidation of NH₃ on Pt alloy gauzes to NO is widely employed in industry for the production of HNO₃, which is used to obtain agricultural fertilizers. Particular attention is paid now to the investigation of the chemical composition of gauzes used in NH₃ oxidation. X-ray photoelectron and energy-dispersive X-ray spectroscopies with the depth of analysis ca. 5 nm and ca. 500 nm were applied to investigate the chemical composition of surface and subsurface layers of the new and used in NH₃ oxidation with air at T = 1133 K Pt–Pd–Rh–Ru catalytic gauzes (81, 15, 3.5, 0.5 wt.%, respectively). For all the gauzes, adsorption (OH_ad, CO_ad), graphitic (C_gr) and oxide (Rh₂O₃) films were found on the surface of the metallic alloy. Under these films, C_ab, N_ab and O_ab atoms absorbed in the subsurface layers were detected on the gauzes used in NH₃ oxidation. The obtained data testify to the penetration of O_ab and N_ab atoms into deeper layers of the alloy during etching with elevation of the catalyst temperature. O_ab atoms were accumulated predominantly on dislocations, etch pits and grain boundaries, whereas N_ab atoms intercalated mostly into interstitial sites of the alloy lattice. Full article

Diesel soot particles are of concern for both the environment and health. To catalytically remove them, it is important to know their structure and composition. There is little described in the literature on how catalysts favor the combustion of different soot fractions. In this work, programmed temperature oxidation (TPO) experiments were carried out using Co,Ce or Co,Ba,K catalysts supported on ceramic papers. Soot particles were obtained by burning diesel fuel in a vessel (LabSoot) or by filtering exhaust gases from a turbo diesel engine in a DPF filter (BenchSoot), and compared with a commercial diesel soot: Printex U. Various characterization techniques were useful to relate the characteristics of both the soot particles and the catalysts with the TPO results. The maximum catalytic soot burn rate (T_M) temperatures were in the range of diesel exhaust temperatures that would facilitate in-situ regeneration of the DPF. The Co,Ba,K catalyst showed a higher catalytic effect in LabSoot, as the latter exhibited the largest primary particles and the higher order of graphene layers, for which the potassium-containing catalyst improves the contact between soot and catalyst and favors the combustion of soot, while the Co,Ce catalyst preferentially enhanced the combustion of commercial soot by supplying active oxygen. Full article

The two-electron oxygen reduction reaction (2e⁻ORR) pathway electrochemical synthesis to H₂O₂ has the advantages of low investment and environmental protection and is considered to be a promising green method. Herein, the oxidized Mo₂TiC₂ MXene (O-Mo₂TiC₂) was successfully synthesized by a facile hydrothermal method as an electrocatalyst in electrocatalytic H₂O₂ production. The O-Mo₂TiC₂ achieved the 90% of H₂O₂ selectivity and 0.72 V vs. RHE of the onset potential. Moreover, O-Mo₂TiC₂ showed high charge transfer ability and long-term stable working ability of 40 h. This significantly enhanced electrocatalytic H₂O₂ production capacity is assigned the oxidation treatment of Mo₂TiC₂ MXene to generate more oxygen-containing groups in O-Mo₂TiC₂. This work provides a promising catalyst candidate for the electrochemical synthesis of H₂O₂. Full article

The activity of emission control catalysts must be improved in urban mode at low temperatures. One possible way is to tailor the metal-support interaction between platinum group metals (PGMs) and ceria to stabilize small clusters or single atoms, optimizing the utilization of costly PGMs. In this study, a small loading of Pd (<0.2 wt.%) was dispersed on Pr-rich cerium–zirconium–praseodymium mixed oxides (CZP45: Ce_0.45Zr_0.10Pr_0.45O_2−x). After the initial calcination at 800 °C, Pd was mainly in the form of dispersed isolated cations which were found to be efficient for low-temperature CO oxidation but inactive for propane combustion. Nevertheless, a pre-reduction step can trigger the formation of Pd nanoparticles and promote the propane oxidation. Pd nanoparticles, formed during the reduction step, coupled with the high oxygen mobility of CZP45, lead to outstanding catalytic activity for propane oxidation starting from 250 °C. However, the re-oxidation of Pd nanoparticles and their partial re-dispersion, promoted by the fast oxygen mobility of the mixed oxide, rapidly deactivate the catalysts in lean conditions. Full article

Detailed studies of the electrochemical oxygen reduction reaction (ORR) on catalyst materials are crucial to improving the performance of different electrochemical energy conversion and storage systems (e.g., fuel cells and batteries), as well as numerous chemical synthesis processes. In the effort to reduce the loading of expensive platinum group metal (PGM)-based catalysts for ORR in the electrochemical systems, many carbon-based catalysts have already shown promising results and numerous investigations on those catalysts are in progress. Most of these studies show the catalyst materials’ ORR performance as current density data obtained through the rotating disk electrode (RDE), rotating ring-disk electrode (RRDE) experiments taking cyclic voltammograms (CV) or linear sweep voltammograms (LSV) approaches. However, the provided descriptions or interpretations of those data curves are often ambiguous and recondite which can lead to an erroneous understanding of the ORR phenomenon in those specific systems and inaccurate characterization of the catalyst materials. In this paper, we presented a study of ORR on a newly developed carbon-based catalyst, the nitrogen-doped graphene/metal-organic framework (N-G/MOF), through RDE and RRDE experiments in both alkaline and acidic mediums, taking the LSV approach. The functions and crucial considerations for the different parts of the RDE/RRDE experiment such as the working electrode, reference electrode, counter electrode, electrolyte, and overall RDE/RRDE process are delineated which can serve as guidelines for the new researchers in this field. Experimentally obtained LSV curves’ shapes and their correlations with the possible ORR reaction pathways within the applied potential range are discussed in depth. We also demonstrated how the presence of hydrogen peroxide (H₂O₂), a possible intermediate of ORR, in the alkaline electrolyte and the concentration of acid in the acidic electrolyte can maneuver the ORR current density output in compliance with the possible ORR pathways. Full article

In this work, we investigated the catalytic effects of a Sharpless dimeric titanium (IV)–tartrate–diester catalyst on the epoxidation of allylalcohol with methyl–hydroperoxide considering four different orientations of the reacting species coordinated at the titanium atom (reactions R1–R4) as well as a model for the non-catalyzed reaction (reaction R0). As major analysis tools, we applied the URVA (Unified Reaction Valley Approach) and LMA (Local Mode Analysis), both being based on vibrational spectroscopy and complemented by a QTAIM analysis of the electron density calculated at the DFT level of theory. The energetics of each reaction were recalculated at the DLPNO-CCSD(T) level of theory. The URVA curvature profiles identified the important chemical events of all five reactions as peroxide OO bond cleavage taking place before the TS (i.e., accounting for the energy barrier) and epoxide CO bond formation together with rehybridization of the carbon atoms of the targeted CC double bond after the TS. The energy decomposition into reaction phase contribution phases showed that the major effect of the catalyst is the weakening of the OO bond to be broken and replacement of OH bond breakage in the non-catalyzed reaction by an energetically more favorable TiO bond breakage. LMA performed at all stationary points rounded up the investigation (i) quantifying OO bond weakening of the oxidizing peroxide upon coordination at the metal atom, (ii) showing that a more synchronous formation of the new CO epoxide bonds correlates with smaller bond strength differences between these bonds, and (iii) elucidating the different roles of the three TiO bonds formed between catalyst and reactants and their interplay as orchestrated by the Sharpless catalyst. We hope that this article will inspire the computational community to use URVA complemented with LMA in the future as an efficient mechanistic tool for the optimization and fine-tuning of current Sharpless catalysts and for the design new of catalysts for epoxidation reactions. Full article

The hydroaminomethylation of the long-chain olefin 1-decene and diethylamine with a homogeneous Rh(acac)(cod)/SulfoXantphos catalyst complex as a one-pot synthesis was investigated. The influence of reaction conditions such as temperature and synthesis gas pressure was determined, as well as the effects of the initial concentrations of catalyst precursor, ligand, and reactants on the yield of fatty amine. Hydroaminomethylation was successfully carried out in an aqueous microemulsion system using a non-ionic surfactant with a reaction time of 2 h. A maximum yield of 34%, high regioselectivities >97%, and chemoselectivities >85% were achieved. Full article

Due to the complexity of heterogeneous reactions and heterogeneities of individual catalyst particles in size, morphology, and the surrounding medium, it is very important to characterize the structure of nanocatalysts and measure the reaction process of nanocatalysis at the single-particle level. Traditional ensemble measurements, however, only provide averaged results of billions of nanoparticles (NPs), which do not help reveal structure–activity relationships and may overlook a few NPs with high activity. The advent of dark-field microscopy (DFM) combined with plasmonic resonance Rayleigh scattering (PRRS) spectroscopy provides a powerful means for directly recording the localized surface plasmon resonance (LSPR) spectrum of single plasmonic nanoparticles (PNPs), which also enables quantitative measurements. In recent years, DFM has developed rapidly for a series of single-particle catalytic reactions such as redox reactions, electrocatalytic reactions, and DNAzyme catalysis, with the ability to monitor the catalytic reaction process in real time and reveal the catalytic mechanism. This review provides a comprehensive overview of the fundamental principles and practical applications of DFM in measuring various kinds of catalysis (including chemocatalysis, electrocatalysis, photocatalysis, and biocatalysis) at the single-particle level. Perspectives on the remaining challenges and future trends in this field are also proposed. Full article

Using organic-base tetramethylammonium hydroxide (TMAH) is a viable, cheap, and fast option for the synthesis of MgZnAl-LDH-type materials by both co-precipitation and mechano-chemical methods. TMAH presents several advantages, such as the smaller quantity of water required in the washing step compared to the use of inorganic alkalis, the prevention of LDH contamination with alkali cations, and its action as a template molecule in texture tailoring. It also has disadvantages, such as its presence in small quantities in the resulting layered materials. Regardless of the use of organic/inorganic bases and co-precipitation/mechano-chemical methods, zincite stable phase was found in all the synthesized solids. The basicity of catalysts followed the trend: mixed oxides > reconstructed > parent LDH. The memory effect of LDH was supported only by the presence of Mg and Al cations, while Zn remained as a zincite stable phase. The catalytic activities for Claisen-Schmidt condensation of benzaldehyde with cyclohexanone provided values higher than 90% after 2 h, with a total selectivity toward 2,6-dibenzylidenecyclohexanone, while self-condensation of cyclohexanone yielded no more than 7.29% after 5 h. These behaviors depended on catalyst basicity as well as on the planar rigidity of the compound. Full article

Advanced oxidation processes are promising techniques for water remediation and degradation of micropollutants in aqueous systems. Since single processes such as sonolysis and photocatalysis exhibit limitations, combined AOP systems can enhance degradation efficiency. The present work addresses the synergistic intensification potential of an ultrasound-assisted photocatalysis (sonophotocatalysis) for bisphenol A degradation with a low-frequency sonotrode (f = 20 kHz) in a batch-system. The effects of energy input and suspended photocatalyst dosage (TiO₂-nanoparticle, m = 0–0.5 g/L) were investigated. To understand the synergistic effects, the sonication characteristics were investigated by bubble-field analysis, hydrophone measurements, and chemiluminescence of luminol to identify cavitation areas due to the generation of hydroxyl radicals. Comparing the sonophotocatalysis with sonolysis and photocatalysis (incl. mechanical stirring), synergies up to 295% and degradation rates of up to 1.35 min⁻¹ were achieved. Besides the proof of synergistic intensification, the investigation of energy efficiency for a degradation degree of 80% shows that a process optimization can be realized. Thus, it could be demonstrated that there is an effective limit of energy input depending on the TiO₂ dosage. Full article

Nickel (Ni)-promoted Molybdenum (Mo)-based catalysts are used for hydrotreatment processes in the chemical industry where the catalysts are exposed to high-pressure H₂ at elevated temperature. In this environment, the catalyst transforms into the active phase, which involves the reduction of the oxide. Here, we report on the first in situ study on the reduction of alumina supported Ni- and Mo-based catalysts in 1 mbar H₂ using ambient-pressure X-ray photoelectron spectroscopy (APXPS). The study confirms that mixing Ni and Mo lowers the reduction temperature of both Ni- and Mo-oxide as compared to the monometallic catalysts and shows that the MoO₃ reduction starts at a lower temperature than the reduction of NiO in NiMo/Al₂O₃ catalysts. Additionally, the reduction of Ni and Mo foil was directly compared to the reduction of the Al₂O₃-supported catalysts and it was observed that the reduction of the supported catalysts is more gradual than the reduction of the foils, indicating a strong interaction between the Ni/Mo and the alumina support. Full article

Water plays a fundamental role in meeting the basic needs of society. Surface waters contain numerous organic pollutants, such as pesticides, drugs, and surfactants. The use of photolysis processes in organic matter degradation not only has practical applications in wastewater treatment but is also of major importance in the pretreatment of samples prior to the trace analysis of numerous analytes. The heterogeneous degradation is simple to implement prior to ultra-traces determination and is the only one allowed before the speciation analysis. Speciation analysis is currently the most important environmental challenge. The analysis of water, including tests associated with wastewater pretreatment and the monitoring of aqueous ecosystems, is the largest segment of environmental analysis. In the trace analysis of water, organic compounds are the principal interfering compounds reducing the quality of the obtained results or even preventing the determination of the examined analytes altogether. Some analytical techniques do not perform well in the presence, for example, of surfactants, so mineralization is sometimes required. Advanced oxidation processes are used to remove interfering organic compounds. The oxidation can be performed using homogenous photolysis (UV mineralization with hydrogen peroxide addition), while heterogenous photolysis using semiconductors helps to increase the removal efficiency of interferents dissolved in water. Utilizing semiconductor nanostructured materials as photocatalysts has been shown to be effective for the adequate removal of a wide spectrum of pollutants in water. Several semiconductor systems are used in the degradation of organic compounds, e.g., TiO₂, Fe₃O₄, WO₃, Fe₂O₃, ZnO, and mixtures of these oxides enriched with various precious metals, such as silver or gold. It is very challenging to manage the selectivity and reduction power so that organic compounds can be degraded but without disturbing the speciation of As, Cr, or Tl. Chemical modification of samples and the selection of semiconductor layers, light wavelength, and pH allow for the targeted degradation of specific compounds but may also indirectly affect the analysis of water samples. This review is a presentation of the state of the art of photocatalysis as a simple and effective technique for sample pretreatment in ultra-trace and speciation analysis and its critical as well as unpublished data related to this topic. Full article

The depletion of fossil energy sources and the legislation regarding emission control demand the use of alternative fuels and rapid progression of aftertreatment technologies. The study of dimethyl ether (DME) catalytic oxidation is important in this respect, as DME is a promising clean fuel and at the same time a VOC pollutant present in the tail gases of industrial processes. In the present work, copper ferrite catalysts synthesized via the citrate complexation method have been evaluated in DME oxidation. N₂-physisorption, XRD, H₂-TPR, and XPS were employed for the characterization of the mixed oxide catalysts. The copper ferrite spinel phase was detected in all samples accompanied by a gradual decrease in the bulk CuO phase upon increase in iron content, with the latter never vanishing completely. The Fe_0.67Cu_0.33 catalyst exhibited the highest catalytic activity in DME oxidation, attaining approximately a 4-fold higher oxidation rate compared to the respective pure copper and iron oxides. The enhanced catalytic performance was attributed to the higher specific surface area of the catalyst and its enhanced redox properties. Highly dispersed copper species were developed owing to the formation of the spinel phase. DME-TPD/TPSR experiments showed that the surface lattice oxygen of the Fe_0.67Cu_0.33 catalyst can oxidize preadsorbed DME at a lower temperature than all other catalysts which is in agreement with the H₂-TPR findings. Full article

The development of high-performance non-noble metal-based oxygen electrocatalysts is crucial for the practical application of zinc–air batteries. Most of them suffer from low intrinsic activity and poor stability, failing to meet the needs of practical applications. Here, we report an efficient and durable bifunctional oxygen electrocatalyst of Fe@Fe-SAC composite (SAC stands for single atoms on carbon). A facile and ease-to-scale-up process synthesizes it. Fe single-atom and Fe nanoparticles are anchored on nitrogen-doped porous carbon, with the latter encapsulated by the graphitic shell. It exhibits appealing activity and durability in a basic electrolyte, requiring a half-wave potential of 0.805 V for oxygen reduction reaction (ORR) and an overpotential of only 348 mV to deliver a current density of 10 mA cm⁻² for oxygen evolution reaction (OER). Both activities are comparable to the corresponding benchmarking electrocatalyst of Pt/C for ORR and IrO₂ for OER. The superior activities are attributed to the strong electronic interaction between metal single-atom and nanoparticles. The favorable stability is ascribed to the physical encapsulation of carbon coatings on nanoparticles. This work presents a feasible scheme for designing and large-scale preparation of high-performance non-noble metal-based bifunctional oxygen electrocatalysts. Full article

Hydrogen fuel cell technology is an essential component of a green economy. However, it is limited in practicality and affordability by the oxygen reduction reaction (ORR). Nanoscale silver particles have been proposed as a cost-effective solution to this problem. However, previous computational studies focused on clean and flat surfaces. High-index surfaces can be used to model active steps presented in nanoparticles. Here, we used the stable stepped Ag(322) surface as a model to understand the ORR performance of steps on Ag nanoparticles. Our density functional theory (DFT) results demonstrate a small dissociation energy barrier for O₂ molecules on the Ag(322) surface, which can be ascribed to the existence of low-coordination number surface atoms. Consequently, the adsorption of OOH* led to the associative pathway becoming ineffective. Alternatively, the unusual dissociative mechanism is energetically favored on Ag(322) for ORR. Our findings reveal the importance of the coordination numbers of active sites for catalytic performance, which can further guide electrocatalysts’ design. Full article

A large signal of gas-phase CO overlapping with those of adsorbates is often present when investigating catalysts by operando diffuse reflectance FT-IR spectroscopy. Physically removing CO(g) from the IR cell may lead to a fast decay of adsorbate signals. Our work shows that carbonyls adsorbed on metallic Pt sites fully vanished in less than 10 min at 30 °C upon removing CO(g) when redox supports were used. In contrast, a broad band assigned to CO adsorbed on oxidized Pt sites was stable. It was concluded that physically removing CO(g) at room temperature during IR analyses will most likely lead to changes in the distribution of CO(ads) and a misrepresentation of the Pt site speciation, misguiding the development of efficient low-temperature CO oxidation catalysts. A tentative representation of the nature of the Pt phases present depending on the feed composition is also proposed. Full article

Nowadays, the oxidation activity at the low-temperature regime for Co₃O₄ catalysts needs to be improved to meet the stringent regulation of multi-pollutant diesel exhaust. Herein, nanoflower-like Co₃O₄ diesel oxide catalysts (DOCs) were fabricated with the addition of a low-content Pt to trigger better catalytic activities for oxidizing multi-pollutants (CO, C₃H₆, and NO) emissions by taking advantage of the strong-metal supporting interaction. Compared to the conventional DOCs based on Pt/Al₂O₃, the as-synthesized Pt/Co₃O₄ catalysts not only exhibited better multi-pollutants oxidation activities at the low temperature but also obtained better resistance toward NO inhibition. Moreover, Pt/Co₃O₄ catalysts showed exceptional hydrothermal durability throughout long-term tests in the presence of water vapor. According to the XPS and H₂-TPR results, Pt promoted low-temperature catalytic activity by increasing the active surface oxygen species and reducibility due to the robust synergistic interaction between metallic Pt and supporting Co₃O₄. Meanwhile, TGA curves confirmed the Pt atoms that facilitated the desorption of surface-active oxygen and hydroxyl radicals in a low-temperature regime. Furthermore, instead of probing the intermediates during CO and C₃H₆ oxidation for Pt/Co₃O₄ catalysts, which included carbonates, formate, and acetate species, in situ DRIFTs experiments also revealed C₃H₆ oxidation mainly took place over metallic Pt sites. Full article

A functionally structured catalyst was explored for ethanol steam reforming (ESR) to generate H₂. Aluminum lathe waste strips were employed as the structured catalytic framework. The mixed metal oxide (Li-Al-O) was formed on the surface of Al lathe waste strips through calcination of the Li-Al-CO₃ layered double hydroxide (LDH), working as the support for the formation of Ni catalyst nanoparticles. NaOH and NaHCO₃ titration solutions were, respectively, used for adjusting the pH of the NiCl₂ aqueous solutions at 50 °C when developing the precursors of the Ni-based catalysts forming in-situ on the Li-Al-O oxide support. The Ni precursor on the Al structured framework was reduced in a H₂ atmosphere at 500 °C for 3 h, changing the hydroxide precursor into Ni nanoparticles. The titration agent (NaOH or NaHCO₃) effectively affected the physical and chemical characterizations of the catalyst obtained by the different titrations. The ESR reaction catalyzed by the structured catalysts at a relatively low temperature of 500 °C was studied. The catalyst using NaHCO₃ titration presented good stability for generating H₂ during ESR, achieving a high rate of H₂ volume of about 122.9 L/(g_cat·h). It also had a relatively low acidity on the surface of the Li-Al-O oxide support, leading to low activity for the dehydration of ethanol and high activity to H₂ yield. The interactions of catalysts between the Ni precursors and the Li-Al-O oxide supports were discussed in the processes of the H₂ reduction and the ESR reaction. Mechanisms of carbon formation during the ESR were proposed by the catalysts using NaOH and NaHCO₃ titration agents. Full article

Global warming and rising waste content collectively accelerate the development of renewable-derived ‘low-carbon’ chemical technologies. Among all abundant renewables, marine-/food-waste-derived chitin, the only nitrogen-containing sustainable biomass, contains the unique N-acetylglucosamine units, which could be synthetically manipulated to a plethora of organonitrogen chemicals. Herein, we report the efficient one-step catalytic valorization of chitin to N-acylethanolamine over cost-effective Ni/CeO₂-based materials, which interestingly demonstrate shape-based reactivity based on CeO₂ supports. In general, all three catalysts (Ni on cubic-, rod-, and polyhedral-shaped CeO₂ supports) were active for this reaction, but they differed in their catalytic efficiency and time-monitored reaction profiles. Herein, Ni on cubic-shaped CeO₂ delivered relatively better and stable catalytic performance, along with its rod-shaped counterpart, while the polyhedral CeO₂-based material also delivered decent performance. Such interesting catalytic behavior has been corroborated by their physicochemical properties, as revealed by their characterization studies. Herein, to establish an appropriate structure-property-reactivity relationship, multimodal characterization techniques and control mechanistic experiments have been performed. This work demonstrates a concept to reduce the consumption of primary carbon resources and increase the utilization of secondary waste materials to facilitate a smooth transition from a linear economy (cf. cradle-to-grave model) to a circular economy (cf. cradle-to-cradle model). Full article

Polyphenolic esters (PEs) are valuable chemical compounds that display a wide spectrum of activities (e.g., anti-oxidative effects). As a result, their production through catalytic routes is an attractive field of research. The present review aims to discuss recent studies from the literature regarding the catalytic production of PEs from biomass feedstocks, namely, naturally occurred polyphenolic compounds. Several synthetic approaches are reported in the literature, mainly bio-catalysis and to a lesser extent acid catalysis. Immobilized lipases (e.g., Novozym 435) are the preferred enzymes thanks to their high reactivity, selectivity and reusability. Acid catalysis is principally investigated for the esterification of polyphenolic acids with fatty alcohols and/or glycerol, using both homogeneous (p-toluensulfonic acid, sulfonic acid and ionic liquids) and heterogeneous (strongly acidic cation exchange resins) catalysts. Based on the reviewed publications, we propose some suggestions to improve the synthesis of PEs with the aim of increasing the greenness of the overall production process. In fact, much more attention should be paid to the use of new and efficient acid catalysts and their reuse for multiple reaction cycles. Full article

Biogas, with its high carbon dioxide content (30–50 vol%), is an attractive feed for catalytic methanation with green hydrogen, and is suitable for establishing a closed carbon cycle with methane as energy carrier. The most important questions for direct biogas methanation are how the high methane content influences the methanation reaction and overall efficiency on one hand, and to what extent the methanation catalysts can be made more resistant to various sulfur-containing compounds in biogas on the other hand. Ni-based catalysts are the most favored for economic reasons. The interplay of active compounds, supports, and promoters is discussed regarding the potential for improving sulfur resistance. Several strategies are addressed and experimental studies are evaluated, to identify catalysts which might be suitable for these challenges. As several catalyst functionalities must be combined, materials with two active metals and binary oxide support seem to be the best approach to technically applicable solutions. The high methane content in biogas appears to have a measurable impact on equilibrium and therefore CO₂ conversion. Depending on the initial CH₄/CO₂ ratio, this might lead to a product with higher methane content, and, after work-up, to a drop in-option for existing natural gas grids. Full article

We report on the synthesis of a novel class of functionalized thia[6]helicenes and a thia[5]helicene, containing a benzothiophene unit and a second heteroatom embedded in the helix (i.e., nitrogen and oxygen) or a pyrene or a spirobifluorene moiety. These systems are obtained through straightforward and general procedures that involve: (i) palladium-catalyzed annulation of iodo-atropoisomers with internal alkynes and (ii) Suzuki coupling of iodo-atropoisomers with phenyl boronic acid followed by a Mallory-type reaction. Both experimental and theoretical studies on the configurational stability of some selected thia[6]helicenes confirmed their stability toward racemization at room temperature, while the pyrene-based thia[5]helicene was found to be unstable. Moreover, the configuration assignment for one representative thiahelicene was established through the comparison between experimental and theoretical circular dichroism (CD) spectra. A systematic study of the photophysical properties of both thiahelicenes and the corresponding atropoisomers has been carried out to provide a complete overview on the new molecules proposed in this work. The obtained data showed regular trends in all the thiahelicene series with spectroscopic traits in line with those previously observed for similar heterohelicenes. Full article

In this study, a set of CuCeO_x catalysts was prepared via the coprecipitation method using a Multi-Inlet Vortex Reactor: the Cu wt.% content is 5, 10, 20, 30 and 60. Moreover, pure CeO₂ and CuO were synthesized for comparison purposes. The physico-chemical properties of this set of samples were investigated by complementary techniques, e.g., XRD, N₂ physisorption at −196 °C, Scanning Electron Microscopy, XPS, FT-IR, Raman spectroscopy and H₂-TPR. Then, the CuCeO_x catalysts were tested for the CO and ethene oxidation reactions. As a whole, all the prepared samples presented good catalytic performances towards the CO oxidation reaction (1000 ppm CO, 10 vol.% O₂/N₂): the most promising catalyst was the 20%CuCeO_x (complete CO conversion at 125 °C), which exhibited a long-term thermal stability. Similarly, the oxidative activity of the catalysts were evaluated using a gaseous mixture containing 500 ppm C₂H₄, 10 vol.% O₂/N₂. Accordingly, for the ethene oxidation reaction, the 20%CuCeO_x catalyst evidenced the best catalytic properties. The elevated catalytic activity towards CO and ethene oxidation was mainly ascribed to synergistic interactions between CeO₂ and CuO phases, as well as to the high amount of surface-chemisorbed oxygen species and structural defects. Full article

Environmental issues related to greenhouse gases (GHG) emissions have pushed the development of new technologies that will allow the economic production of low-carbon energy vectors, such as hydrogen (H₂), methane (CH₄) and liquid fuels. Dry reforming of methane (DRM) has gained increased attention since it uses CH₄ and carbon dioxide (CO₂), which are two main greenhouse gases (GHG), as feedstock for the production of syngas, which is a mixture of H₂ and carbon monoxide (CO) and can be used as a building block for the production of fuels. Since H₂ has been identified as a key enabler of the energy transition, a lot of studies have aimed to benefit from the environmental advantages of DRM and to use it as a pathway for a sustainable H₂ production. However, there are several challenges related to this process and to its use for H₂ production, such as catalyst deactivation and the low H₂/CO ratio of the syngas produced, which is usually below 1.0. This paper presents the recent advances in the catalyst development for H₂ production via DRM, the processes that could be combined with DRM to overcome these challenges and the current industrial processes using DRM. The objective is to assess in which conditions DRM could be used for H₂ production and the gaps in literature data preventing better evaluation of the environmental and economic potential of this process. Full article

In this study, the temperature-dependent activity of Au/AC nanocatalysts in redox catalytic reactions was investigated. To this end, a series of colloidal gold catalysts supported on activated carbon and titania were prepared by the sol immobilization method employing polyvinyl alcohol as a polymeric stabilizer at different hydrolysis degrees. The as-synthesized materials were widely characterized by spectroscopic analysis (XPS, XRD, and ATR-IR) as well as TEM microscopy and DLS/ELS measurements. Furthermore, 5-hydroxymethylfurfural (HMF) oxidation and 4-nitrophenol (4-NP) reduction were chosen to investigate the catalytic activity as a model reaction for biomass valorization and wastewater remediation. In particular, by fitting the hydrolysis degree with the kinetic data, volcano plots were obtained for both reactions, in which the maximum of the curves was represented relative to hydrolysis intermediate values. However, a comparison of the catalytic performance of the sample Au/AC_PVA-99 (hydrolysis degree of the polymer is 99%) in the two reactions showed a different catalytic behavior, probably due to the detachment of polymer derived from the different reaction temperature chosen between the two reactions. For this reason, several tests were carried out to investigate deeper the observed catalytic trend, focusing on studying the effect of the reaction temperature as well as the effect of support (metal–support interaction) by immobilizing Au colloidal nanoparticles on commercial titania. The kinetic data, combined with the characterization carried out on the catalysts, confirmed that changing the reaction conditions, the PVA behavior on the surface of the catalysts, and, therefore, the reaction outcome, is modified. Full article

Organic carbonates are considered the chemicals of the future. In particular, propylene carbonate is widely used as a non-reactive solvent, plasticizer, fuel additive, and reagent, especially in the production of environmentally friendly polymers that are not harmful to human health. This paper reviews recent literature findings regarding the development of propylene carbonate synthetic methods starting from propane-1,2-diol and urea. The ammonia formed during the synthesis is recycled to obtain urea from carbon dioxide. Full article

The preparation of Ru nanoparticles supported on γ-Al₂O₃ followed by chemical reduction using RuCl₃ as a precursor is demonstrated, and their properties are compared to Ru nanoparticles supported on γ-Al₂O₃ prepared by impregnation of γ-Al₂O₃ with Ru₃(CO)₁₂ and subsequent thermal decomposition. The Ru nanoparticles resulting from chemical reduction of RuCl₃ are slightly larger (1.2 vs. 0.8 nm). In addition, Ru nanoparticles were deposited on Stöber SiO₂ using both deposition techniques. These particles were larger than the ones deposited on γ-Al₂O₃ (2.5 and 3.4 nm for chemical reduction and thermal decomposition, respectively). Taking into account the size differences between the Ru nanoparticles, all catalysts display similar activity (0.14–0.63 mol·g_Ru⁻¹·h⁻¹) and selectivity (≥99%) in the sunlight-powered Sabatier reaction. Ergo, the use of toxic and volatile Ru₃(CO)₁₂ can be avoided, since catalysts prepared by chemical reduction of RuCl₃ display similar catalytic performance. Full article

Biochar (BCH) is a carbon-based bio-material produced from thermochemical conversion of biomass. Several activation or functionalization methods are usually used to improve physicochemical and functional properties of BCHs. In the context of green and sustainable future development, activated and functionalized biochars with abundant surface functional groups and large surface area can act as effective catalysts or catalyst supports for chemical transformation of a range of bioproducts in biorefineries. Above the well-known BCH applications, their use as adsorbents to remove pollutants are the mostly discussed, although their potential as catalysts or catalyst supports for advanced (electro)catalytic processes has not been comprehensively explored. In this review, the production/activation/functionalization of metal-supported biochar (M-BCH) are scrutinized, giving special emphasis to the metal-functionalized biochar-based (electro)catalysts as promising catalysts for bioenergy and bioproducts production. Their performance in the fields of biorefinery processes, and energy storage and conversion as electrode materials for oxygen and hydrogen evolutions, oxygen reduction, and supercapacitors, are also reviewed and discussed. Full article

Being the major renewable source of bio-aromatics, lignin possesses considerable potential for the chemical industry as raw material. Kraft lignin is a couple product of paper industry with an annual production of 55,000,000 ton/y and is considered the largest share of available lignin. Here we report a facile approach of Kraft lignin depolymerization to defined oligomeric units with yields of up to 70 wt.%. The process implies utilization of an aqueous base in combination with a metal containing catalyst and an alcohol under non-oxidative atmosphere at 300 °C. An advantage of the developed approach is the facile separation of the oligomer product that precipitates from the reaction mixture. In addition, the process proceeds without char formation; both factors make it attractive for industrialization. The suppression of the repolymerization processes that lead to char formation is possible when the combination of metal containing catalyst in the presence of an alcohol is used. It was found that the oligomer units have structural features found in phenol-acetaldehyde resins. These features result from the base catalyzed condensation of lignin fragments with in situ formed aldehydes. Catalytic dehydrogenation of the alcohol provides the latter. This reaction pathway is confirmed by the presence condensation products of Guerbet type reactions. Full article

Dye-containing pollutants are currently a threat to the environment, and it is highly challenging to eliminate these dyes photocatalytically under visible light. Herein, we designed and prepared a ZnO/CuO/g-C₃N₄ (ZCG) heterostructure nanocomposite by a co-crystallization procedure and applied it to eliminate pollutants from wastewater via a photocatalytic scheme. The structural and morphological features of the composite confirmed the formation of a ZCG nanocomposite. The photocatalytic capability of the ZCG photocatalyst was investigated via the decomposition of methylene blue dye. The outstanding activity level of 97.46% was reached within 50 min. In addition, the proficiency of the ZCG composite was 753%, 392%, 156%, and 130% higher than photolysis, g-C₃N₄, CuO, and ZnO, respectively. Furthermore, the photodeterioration activity on Congo red was also evaluated and found to be excellent. The enhanced catalytic achievement is attributed to the construction of heterojunctions among the constituent compounds. These properties boost the charge transfer and decrease the recombination rate. Moreover, the reusability of the ZCG product was explored and a negligible photoactivity decline was detected after six successful runs. The outcomes suggest the as-prepared nanocomposite can be applied to remove pollutants, which opens a new door to practical implementation. Full article

Plasmonic CO₂ methanation using γ-Al₂O₃-supported Ru nanorods was carried out under continuous-flow conditions without conventional heating, using mildly concentrated sunlight as the sole and sustainable energy source (AM 1.5, irradiance 5.5–14.4 kW·m⁻² = 5.5–14.4 suns). Under 12.5 suns, a CO₂ conversion exceeding 97% was achieved with complete selectivity towards CH₄ and a stable production rate (261.9 $\mathrm{mmol}·{\mathrm{g}}_{\mathrm{Ru}}^{-1}·{\mathrm{h}}^{-1}$) for at least 12 h. The CH₄ production rate showed an exponential increase with increasing light intensity, suggesting that the process was mainly promoted by photothermal heating. This was confirmed by the apparent activation energy of 64.3 kJ·mol⁻¹, which is very similar to the activation energy obtained for reference experiments in dark (67.3 kJ·mol⁻¹). The flow rate influence was studied under 14.4 suns, achieving a CH₄ production plateau of 264 µmol min⁻¹ (792 $\mathrm{mmol}·{\mathrm{g}}_{\mathrm{Ru}}^{-1}·{\mathrm{h}}^{-1}$) with a constant catalyst bed temperature of approximately 204 °C. Full article

Composite catalysts of mixed metal oxides were prepared by mixing a phase-pure M1 MoVNbTeO_x with anatase-phase TiO₂. Two methods were used to prepare the composite catalysts (the simple physically mixed or sol-gel method) for the improvement of the catalytic performance in the oxidative dehydrogenation of ethane (ODHE) process. The results showed that TiO₂ particles with a smaller particle size were well dispersed on the M1 surface for the sol-gel method, which presented an excellent activity for ODHE. At the same operating condition (i.e., the contact time of 7.55 g_cat·h/mol_C2H6 and the reaction temperature of 400 °C), the M1-TiO₂-SM and M1-TiO₂-PM achieved the space time yields of 0.67 and 0.52 kg_C2H4/kg_cat/h, respectively, which were about ~76% and ~35% more than that of M1 catalyst (0.38 kg_C2H4/kg_cat/h), respectively. The BET, ICP, XRD, TEM, SEM, H₂-TPR, C₂H₆-TPSR, and XPS techniques were applied to characterize the catalysts. It was noted that the introduction of TiO₂ raised the V⁵⁺ abundance on the catalyst surface as well as the reactivity of active oxygen species, which made contribution to the promotion of the catalytic performance. The surface morphology and crystal structure of used catalysts of either M1-TiO₂-SM or M1-TiO₂-PM remained stable as each fresh catalyst after 24 h time-on-stream tests. Full article

CO₂ hydrogenation is an effective way to convert CO₂ to value-added chemicals (e.g., CH₄ and CH₃OH). As a thermal catalytic process, it suffers from dissatisfactory catalytic performances (low conversion/selectivity and poor stability) and high energy input. By utilizing the dielectric barrier discharge (DBD) technology, the catalyst and plasma could generate a synergy, activating the whole process in a mild condition, and enhancing the conversion efficiency of CO₂ and selectivity of targeted product. In this review, a comprehensive summary of the applications of DBD plasma in catalytic CO₂ hydrogenation is provided in detail. Moreover, the state-of-the-art design of the reactor and optimization of reaction parameters are discussed. Furthermore, several mechanisms based on simulations and experiments are provided. In the end, the existing challenges of this hybrid system and corresponding solutions are proposed. Full article

A supported gold nanoparticle-catalyzed strategy has been utilized to promote a click chemistry reaction for the synthesis of 1,2,3-triazoles via the azide-alkyne cycloaddition (AAC) reaction. While the advent of effective non-copper catalysts (i.e., Ru, Ag, Ir) has demonstrated the catalysis of the AAC reaction, additional robust catalytic systems complementary to the copper catalyzed AAC remain in high demand. Herein, Au nanoparticles supported on Al₂O₃, Fe₂O₃, TiO₂ and ZnO, along with gold reference catalysts (gold on carbon and gold on titania supplied by the World Gold Council) were used as catalysts for the AAC reaction. The supported Au nanoparticles with metal loadings of 0.7–1.6% (w/w relative to support) were able to selectively obtain 1,4-disubstituted-1,2,3-triazoles in moderate yields up to 79% after 15 min, under microwave irradiation at 150 °C using a 0.5–1.0 mol% catalyst loading through a one-pot three-component (terminal alkyne, organohalide and sodium azide) procedure according to the “click” rules. Among the supported Au catalysts, Au/TiO₂ gave the best results. Full article

The rapid development of science, technology, and engineering in the 21st century has offered a remarkable rise in our living standards. However, at the same time, serious environmental issues have emerged, such as acid rain and the greenhouse effect, which are associated with the ever-increasing need for energy consumption, 85% of which comes from fossil fuels combustion. From this combustion process, except for energy, the main greenhouse gases-carbon dioxide and steam-are produced. Moreover, during industrial processes, many hazardous gases are emitted. For this reason, gas-detecting devices, such as electrochemical gas sensors able to analyze the composition of a target atmosphere in real time, are important for further improving our living quality. Such devices can help address environmental issues and inform us about the presence of dangerous gases. Furthermore, as non-renewable energy sources run out, there is a need for energy saving. By analyzing the composition of combustion emissions of automobiles or industries, combustion processes can be optimized. This review deals with electrochemical gas sensors based on solid oxide electrolytes, which are employed for the detection of hazardous gasses at high temperatures and aggressive environments. The fundamentals, the principle of operation, and the configuration of potentiometric, amperometric, combined (amperometric-potentiometric), and mixed-potential gas sensors are presented. Moreover, the results of previous studies on carbon oxides (CO_x), nitrogen oxides (NO_x), hydrogen (H₂), oxygen (O₂), ammonia (NH₃), and humidity (steam) electrochemical sensors are reported and discussed. Emphasis is given to sensors based on oxygen ion and proton-conducting electrolytes. Full article

This review summarizes recent applications of nickel as a nonprecious metal catalyst in hydrodehalogenation (HDH) reactions of halogenated aromatic compounds (Ar–Xs). Nickel-based HDH catalysts were developed for reductive treatment of both waste containing concentrated Ar–Xs (mainly polychlorinated benzenes) and for wastewater contaminated with Ar–Xs. Ni-catalyzed HDH enables the production of corresponding nonhalogenated aromatic products (Ar–Hs), which are principally further applicable/recyclable and/or Ar–Hs, which are much more biodegradable and can be mineralized during aerobic wastewater treatment. Developed HDH methods enable the utilization of both gaseous hydrogen via the direct HDH process or other chemical reductants as a source of hydrogen utilized in the transfer of the hydrodehalogenation process. This review highlights recent and major developments in Ni-catalyzed hydrodehalogenation topic since 1990. Full article

In this study the catalytic activity of different gold and bimetallic nanoparticle solutions towards the reduction of methylene blue by sodium borohydride as a model reaction is investigated. By utilizing differently shaped gold nanoparticles, i.e., spheres, cubes, prisms and rods as well as bimetallic gold–palladium and gold–platinum core-shell nanorods, we evaluate the effect of the catalyst surface area as available gold surface area, the shape of the nanoparticles and the impact of added secondary metals in case of bimetallic nanorods. We track the reaction by UV/Vis measurements in the range of 190–850 nm every 60 s. It is assumed that the gold nanoparticles do not only act as a unit transferring electrons from sodium borohydride towards methylene blue but can promote the electron transfer upon plasmonic excitation. By testing different particle shapes, we could indeed demonstrate an effect of the particle shape by excluding the impact of surface area and/or surface ligands. All nanoparticle solutions showed a higher methylene blue turnover than their reference, whereby gold nanoprisms exhibited 100% turnover as no further methylene blue absorption peak was detected. The reaction rate constant k was also determined and revealed overall quicker reactions when gold or bimetallic nanoparticles were added as a catalyst, and again these were highest for nanoprisms. Furthermore, when comparing gold and bimetallic nanorods, it could be shown that through the addition of the catalytically active second metal platinum or palladium, the dye turnover was accelerated and degradation rate constants were higher compared to those of pure gold nanorods. The results explore the catalytic activity of nanoparticles, and assist in exploring further catalytic applications. Full article

Industries such as mining, cokemaking, (petro)chemical and electroplating produce effluents that contain free cyanide (fCN = HCN + CN⁻). Currently, fCN is mainly removed by (physico)chemical methods or by biotreatment with activated sludge. Cyanide hydratases (CynHs) (EC 4.2.1.66), which convert fCN to the much less toxic formamide, have been considered for a mild approach to wastewater decyanation. However, few data are available to evaluate the application potential of CynHs. In this study, we used a new CynH from Exidia glandulosa (protein KZV92691.1 designated NitEg by us), which was overproduced in Escherichia coli. The purified NitEg was highly active for fCN with 784 U/mg protein, k_cat 927/s and k_cat/K_M 42/s/mM. It exhibited optimal activities at pH approximately 6–9 and 40–45 °C. It was quite stable in this pH range, and retained approximately 40% activity at 37 °C after 1 day. Silver and copper ions (1 mM) decreased its activity by 30–40%. The removal of 98–100% fCN was achieved for 0.6–100 mM fCN. Moreover, thiocyanate, sulfide, ammonia or phenol added in amounts typical of industrial effluents did not significantly reduce the fCN conversion, while electroplating effluents may need to be diluted due to high fCN and metal content. The ease of preparation of NitEg, its high specific activity, robustness and long shelf life make it a promising biocatalyst for the detoxification of fCN. Full article

Half-titanocenes are well known to show high activity for ethylene polymerization and good capability for copolymerization of ethylene with other olefins, and the ancillary ligands can crucially affect the catalytic performance. In this paper, the mechanisms of ethylene polymerization catalyzed by three half-metallocenes, (η⁵-C₅Me₅)TiCl₂(O-2,6-ⁱPr₂C₆H₃) (1), (η⁵-C₅Me₅)TiCl₂(N=C^tBu₂) (2) and [Me₂Si(η⁵-C₅Me₄)(N^tBu)]TiCl₂ (3), have been investigated by density functional theory (DFT) method. At the initiation stage, a higher free energy barrier was determined for complex 1, probably due to the presence of electronegative O atom in phenoxy ligand. At the propagation stage, front-side insertion of the second ethylene is kinetically more favorable than back-side insertion for complexes 1 and 2, while both side insertion orientations are comparable for complex 3. The energy decomposition showed that the bridged cyclopentadienyl amide ligand could enhance the rigidity of the active species as suggested by the lowest deformation energy derived from 3. At the chain termination stage, β-H transfer was calculated to be a dominant chain termination route over β-H elimination, presumably owing to the thermodynamic perspective. Full article

Potassium (K) is a notorious villain among the ash components found in the biomass, being the cause of bed agglomeration and contributing to fouling and corrosion. At the same time, K is known to have catalytic properties towards fuel conversion in combustion and gasification environments. Olivine (MgFe silicate) used as gasifier bed material has a higher propensity to form catalytically active K species than traditional silica sand beds, which tend to react with K to form stable and inactive silicates. In a dual fluidized bed (DFB) gasifier, many of those catalytic effects are expected to be relevant, given that the bed material becomes naturally enriched with ash elements from the fuel. However, a comprehensive overview of how enrichment of the bed with alkali affects fuel conversion in both parts of the DFB system is lacking. In this work, the effects of ash-enriched olivine on fuel conversion in the gasification and combustion parts of the process are mapped. The work is based on a dedicated experimental campaign in a Chalmers DFB gasifier, wherein enrichment of the bed material with K is promoted by the addition of a reaction partner, i.e., sulfur, which ensures K retention in the bed in forms other than inactive silicates. The choice of sulfur is based on its affinity for K under combustion conditions. The addition of sulfur proved to be an efficient strategy for capturing catalytic K in olivine particles. In the gasification part, K-loaded olivine enhanced the char gasification rate, decreased the tar concentration, and promoted the WGS equilibrium. In the combustion part, K prevented full oxidation of CO, which could be mitigated by the addition of sulfur to the cyclone outlet. Full article

The selective oxidation of methanol to formaldehyde is a growing million-dollar industry, and has been commercial for close to a century. The Formox process, which is the largest production process today, utilizes an iron molybdate catalyst, which is highly selective, but has a short lifetime of 6 months due to volatilization of the active molybdenum oxide. Improvements of the process’s lifetime is, thus, desirable. This paper provides an overview of the efforts reported in the scientific literature to find alternative catalysts for the Formox process and critically assess these alternatives for their industrial potential. The catalysts can be grouped into three main categories: Mo containing, V containing, and those not containing Mo or V. Furthermore, selected interesting catalysts were synthesized, tested for their performance in the title reaction, and the results critically compared with previously published results. Lastly, an outlook on the progress for finding new catalytic materials is provided as well as suggestions for the future focus of Formox catalyst research. Full article

Cutaneotrichosporon oleaginosus is an oleaginous yeast with several favourable qualities: It is fast growing, accumulates high amounts of lipids and has a very broad substrate spectrum. Its resistance to hydrolysis by-products makes it a promising biocatalyst for custom tailored microbial oils. C. oleaginosus can accumulate up to 60 wt.% of its biomass as lipids. This species is able to grow by using several compounds as a substrate, such as acetic acid, biodiesel-derived glycerol, N-acetylglucosamine, lignocellulosic hydrolysates, wastepaper and other agro-industrial wastes. This review is focused on state-of-the-art innovative and sustainable biorefinery schemes involving this promising yeast and second- and third-generation biomasses. Moreover, this review offers a comprehensive and updated summary of process strategies, biomass pretreatments and fermentation conditions for enhancing lipid production by C. oleaginosus as a whole-cell biocatalyst. Finally, an overview of the main industrial applications of single-cell oil is reported together with future perspectives. Full article

The thickness of transition metal dichalcogenides (TMDs) plays a key role in enhancing their photocatalytic CO₂ reduction activity. However, the optimum thickness of the layered TMDs that is required to achieve sufficient light absorption and excellent crystallinity has still not been definitively determined. In this work, ultra-thin molybdenum disulfide films (MoS₂TF) with 25 nm thickness presented remarkable photocatalytic activity, and the product yield increased by about 2.3 times. The photocatalytic mechanism corresponding to the TMDs’ thickness was also proposed. This work demonstrates that the thickness optimization of TMDs provides a cogent direction for the design of high-performance photocatalysts. Full article

For a long time, the organic chemistry of sulfur dioxide (SO₂) consisted of sulfinates that react with carbon electrophiles to generate sulfones. With alkenes and other unsaturated compounds, SO₂ generates polymeric materials such as polysulfones. More recently, H-ene, sila-ene and hetero-Diels–Alder reactions of SO₂ have been realized under conditions that avoid polymer formation. Sultines resulting from the hetero-Diels–Alder reactions of conjugated dienes and SO₂ are formed more rapidly than the corresponding more stable sulfolenes resulting from the cheletropic additions. In the presence of a protic or Lewis acid catalyst, the sultines derived from 1-alkoxydienes are ionized into zwitterionic intermediates bearing 1-alkoxyallylic cation moieties which react with electro-rich alkenes such as enol silyl ethers and allylsilanes with high stereoselectivity. (C–C-bond formation through Umpolung induced by SO₂). This produces silyl sulfinates that react with carbon electrophiles to give sulfones (one-pot four component asymmetric synthesis of sulfones), or with Cl₂, generating the corresponding sulfonamides that can be reacted in situ with primary and secondary amines (one-pot four component asymmetric synthesis of sulfonamides). Alternatively, Pd-catalyzed desulfinylation generates enantiomerically pure polypropionate stereotriads in one-pot operations. The chirons so obtained are flanked by an ethyl ketone moiety on one side and by a prop-1-en-1-yl carboxylate group on the other. They are ready for two-directional chain elongations, realizing expeditious synthesis of long-chain polypropionates and polyketides. The stereotriads have also been converted into simpler polypropionates such as the cyclohexanone moiety of baconipyrone A and B, Kishi’s stereoheptad unit of rifamycin S, Nicolaou’s C₁–C₁₁-fragment and Koert’s C₁₆–C_I fragment of apoptolidin A. This has also permitted the first total synthesis of (-)-dolabriferol. Full article

Bismuth vanadate (BiVO₄), which has attractive applicability as a photoactive material, presents applications that range from catalysis to water treatment upon visible light irradiation. In this study, we develop a simple synthesis of < 200 nm monoclinic BiVO₄ nanoparticles, which were further deposited on transparent conductive substrates by spin coating and calcination, obtaining nanostructured films. The obtained nanostructured BiVO₄ photoanodes were tested for water oxidation, leading to promising photocurrents exhibiting competitive onset potentials (~0.3 V vs. RHE). These nanoparticulate BiVO₄ photoanodes represent a novel class of highly potential materials for the design of efficient photoelectrochemical devices. Full article

Multifunctional electrocatalysts are vastly sought for their applications in water splitting electrolyzers, metal-air batteries, and regenerative fuel cells because of their ability to catalyze multiple reactions such as hydrogen evolution, oxygen evolution, and oxygen reduction reactions. More specifically, the application of single-atom electrocatalyst in multifunctional catalysis is a promising approach to ensure good atomic efficiency, tunability and additionally benefits simple theoretical treatment. In this review, we provide insights into the variety of single-site metal catalysts and their identification. We also summarize the recent advancements in computational modeling of multifunctional electrocatalysis on single-site catalysts. Furthermore, we explain each modeling step with open-source-based working examples of a standard computational approach. Full article

The chemo-selective hydrogenolysis of secondary hydroxyls is an important reaction for the production of biomass-derived α,ω-diols. This is the case for 1,3-propanediol production from glycerol. Supported Pt-WO_x materials are effective catalysts for this transformation, and their activity is often related to the tungsten surface density and Brönsted acidity, although there are discrepancies in this regard. In this work, a series of Pt-WO_x/γ-Al₂O₃ catalysts were prepared by modifying the pH of the solutions used in the active metal impregnation step. The activity–structure relationships, together with the results from the addition of in situ titrants, i.e., 2,6-di-tert-butyl-pyridine or pyridine, helped in elucidating the nature of the bifunctional active sites for the selective production of 1,3-propanediol. Full article

The industrial use of enzymes generally necessitates their immobilization onto solid supports. The well-known high affinity of enzymes for metal-organic framework (MOF) materials, together with the great versatility of MOFs in terms of structure, composition, functionalization and synthetic approaches, has led the scientific community to develop very different strategies for the immobilization of enzymes in/on MOFs. This review focuses on one of these strategies, namely, the one-pot enzyme immobilization within sustainable MOFs, which is particularly enticing as the resultant biocomposite Enzyme@MOFs have the potential to be: (i) prepared in situ, that is, in just one step; (ii) may be synthesized under sustainable conditions: with water as the sole solvent at room temperature with moderate pHs, etc.; (iii) are able to retain high enzyme loading; (iv) have negligible protein leaching; and (v) give enzymatic activities approaching that given by the corresponding free enzymes. Moreover, this methodology seems to be near-universal, as success has been achieved with different MOFs, with different enzymes and for different applications. So far, the metal ions forming the MOF materials have been chosen according to their low price, low toxicity and, of course, their possibility for generating MOFs at room temperature in water, in order to close the cycle of economic, environmental and energy sustainability in the synthesis, application and disposal life cycle. Full article