Search Results (354)

Chemical recycling of plastic waste, especially polyolefins, into valuable liquid fuels is of considerable significance to address the serious issues raised by their threat on environmental and human health. Nevertheless, the construction of efficient and economically viable catalytic systems remains a significant hurdle. Herein, we developed an efficient bifunctional catalyst system comprising γ-Al₂O₃-supported ruthenium nanoparticles (Ru/γ-Al₂O₃) and β-zeolite for the conversion of polyolefins into gasoline-range hydrocarbons. A yield of C_5–12 paraffins up to 73.4% can be obtained with polyethene as the reactant at 250 °C in hydrogen. The Ru sites primarily activate the initial cleavage of C–H bonds of polymer towards the formation of olefin intermediates, which subsequently go through further cracking and isomerization over the acid sites in β-zeolite. Employing in situ infrared spectroscopy and probe–molecule model reactions, our investigation reveals that the optimized proportion and spatial distribution of the dual catalytic sites are pivotal in the tandem conversion process. This optimization synergistically regulates the cracking kinetics and accelerates intermediate transfer, thereby minimizing the production of side C_1–4 hydrocarbons resulting from over-cracking at the Ru sites and enhancing the yield of liquid fuels. This research contributes novel insights into catalyst design for the chemical upgrading of polyolefins into valuable chemicals, advancing the field of plastic waste recycling and sustainable chemical production. Full article

This paper elucidates the consecutive chain transfer reaction, initially to (p-vinylphenyl) methyl dichlorosilane (or (p-vinylbenzyl) methyl dichlorosilane), followed by hydrogen, during metallocene-catalyzed propylene polymerization by an isospecific metallocene catalyst (i.e., rac-dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride, I)/ activated with methylaluminoxane (MAO), rendering a catalytic access styryldichlorosilane capped isotactic polypropylenes (iPP). The PP molecular weight is inversely related to the molar ratio of [(p-vinylphenyl) methyl dichlorosilane]/[propylene] and [(p-vinylbenzyl) methyl dichlorosilane]/[propylene]. Every polypropylene chain formed presents a terminal (p-vinylphenyl) methyl dichlorosilane (or (p-vinylbenzyl) methyl dichlorosilane) unit. Hydrogen enhances the concentration of the starting arm polymer for the subsequent synthesis of the star polymer by increasing the incorporation of the chain terminal group. In order to create star polymers with isotactic polypropylene(iPP) as the arm and a siloxane cross-linking structure as the core, the terminal dichlorosilane iPP unit can work up (with water) to create cyclic siloxane oligomer interlinkages between iPP chains. Full article

Electrochemical water splitting is a feasible and effective method for attaining hydrogen, offering a mechanism for renewable energy solutions to combat the world’s energy crises due to the scarcity of fossil fuels. Evidently, the viability and stability of the electrocatalysts are fundamental to the electrochemical water-splitting process. However, the net efficiency of this process is noticeably hindered by the kinetic drawbacks related to the OER. Hence, NiFe LDH has been widely used as a highly efficient OER and HER catalyst material due to its unique nanostructure, tunable composition, and favorable electronic structure. This review offers a systematic analysis of the latest progress in the fabrication of functional NiFe LDH catalysts and associated fabrication strategies, structure optimizations, and performance improvements. Special emphasis is given to understanding the role of nanostructure engineering in increasing active site accessibility, enhancing the effectiveness of subsequent electron transfer, and boosting the intrinsic catalytic activity for HER and OER. Moreover, we discuss the influence of doping, defects, and the formation of heterostructures with other materials on the OER and HER activities of NiFe LDHs. Additional accounts of basic structures and the OER and HER catalytic activities are provided, along with an enhanced theoretical understanding based on DFT studies on the NiFe LDH. Moreover, the limitations and potential developments of the work focus on the need for existing synthesis approaches, the stability of the NiFe LDH catalysts, and their insertion into working electrochemical processes. This review is a comprehensive analysis of the current state of research and developments in the use of NiFe LDH catalysts for the electrochemical water-splitting process to foster improved development of sustainable hydrogen sources in the future. Full article

The development of advanced electrocatalysts plays a pivotal role in enhancing hydrogen production through water electrolysis. In this study, we employed a two-step electrodeposition method to fabricate a 3D porous Cu-Co-Ni alloy with superior catalytic properties and long-term stability for hydrogen evolution reaction (HER). The resulting trimetallic alloy, Cu@Cu-Ni-Co, demonstrated significant improvements in structural integrity and catalytic performance. A comparative analysis of electrocatalysts, including Cu, Cu@Ni-Co, and Cu@Cu-Ni-Co, revealed that Cu@Cu-Ni-Co achieved the best results in alkaline media. Electrochemical tests conducted in 1.0 M NaOH showed that Cu@Cu-Ni-Co reached a current density of 10 mA cm⁻² at a low overpotential of 125 mV, along with a low Tafel slope of 79.1 mV dec⁻¹. The catalyst showed exceptional durability, retaining ~95% of its initial current density after 120 h of continuous operation at high current densities. Structural analysis confirmed that the enhanced catalytic performance arises from the synergistic interaction between Cu, Ni, and Co within the well-integrated trimetallic framework. This integration results in a large electrochemical active surface area (ECSA) of 380 cm² and a low charge transfer resistance (15.76 Ω), facilitating efficient electron transfer and promoting superior HER activity. These findings position Cu@Cu-Ni-Co as a highly efficient and stable electrocatalyst for alkaline HER in alkaline conditions. Full article

In this study, a sulfur-doped cobalt–iron catalyst (CoFeS/NF) was synthesized on a nickel foam (NF) substrate via a facile one-step electrodeposition method, and its performance in urea electrolysis for hydrogen production was systematically investigated. Sulfur doping induced significant morphology optimization, forming a highly dispersed nanosheet structure, which enhanced the specific surface area increase by 1.9 times compared with the undoped sample, exposing abundant active sites. Meanwhile, the introduction of sulfur facilitated electron redistribution at the surface modulated the valence states of nickel and cobalt, promoted the formation of high-valence Ni³⁺/Co³⁺, optimized the adsorption energy of the reaction intermediates, and reduced the charge transfer resistance. Electrochemical evaluations revealed that CoFeS/NF achieves a current density of 10 mA cm⁻² at a remarkably low potential of 1.18 V for the urea oxidation reaction (UOR), outperforming both the undoped catalyst (1.24 V) and commercial RuO₂ (1.35 V). In addition, the catalyst also exhibited excellent catalytic activity and long-term stability in the total urea decomposition process, which was attributed to the amorphous structure and the synergistic enhancement of corrosion resistance by sulfur doping. This study provides a new idea for the application of sulfur doping strategy in the design of multifunctional electrocatalysts, which promotes the coupled development of urea wastewater treatment and efficient hydrogen production technology. Full article

Polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant, are of global concern due to their environmental persistence, bioaccumulation, toxicity, and resistance to conventional remediation methods. In this study, the electrochemical reduction of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) with Pd/Metal foam electrodes (Ni, Cu, and Ag) was investigated. The effect of Pd loadings was explored, and the results show that Pd loading enhances the debromination performance, with 15.16%Pd/Ni foam exhibiting the best efficiency, followed by 9.37%Pd/Cu and 10.26%Pd/Ag. The degradation mechanisms for Pd/Ni and Pd/Ag are primarily hydrogen atom transfer, while for Pd/Cu, electron transfer dominates. Among the reduction products, Pd/Ni foam shows the highest debromination capability. The impact of electrolytes, current intensity, and bromination degrees of PBDEs was evaluated for 15.16%Pd/Ni. The results reveal that the presence of electrolytes inhibits BDE-47 degradation; the degradation rate of BDE-47 increases with current density, peaks at 4 mA, and decreases as current rises; and 15.16%Pd/Ni foam can effectively degrade PBDEs with varying bromination levels. Additionally, cycling tests show a decrease in efficiency from 94.3% (first cycle) to 56.58% (fourth cycle), attributed to Pd loss and structural damage. The findings offer valuable insights for developing efficient, sustainable catalytic materials for the electrochemical degradation of PBDEs and other persistent organic pollutants. Full article

Materials with high electron transfer performance remain a key focus in photocatalytic research, as they can effectively promote the separation of photogenerated carriers and enhance the utilization efficiency of photogenerated electrons. To enhance the effective utilization of photogenerated electrons, the MSIG material was prepared by incorporating the iodine clusters and magnetic Fe₃O₄ into the as-synthesized crumpled graphene oxide (CGO) to construct Möbius-like electronic transmission pathways. The introduction of magnetic groups optimized the spin orientation of electrons, facilitating directional electron transport and thereby enhancing the photocatalytic efficiency of the material. Experimental results reveal that, in visible light-driven hydrogen production reactions, the eosin Y (EY)-sensitized Pt-Fe₃O₄-MSIG catalyst exhibits outstanding catalytic performance, with a hydrogen production rate of 1.48 mL/h, which is 15 times higher than that of the Pt-Fe₃O₄ catalyst. Photoelectrochemical analyses show a significant increase in the catalyst’s fluorescence lifetime, attributed to the Möbius strip-like electron transport channels within the material. Theoretical calculations further support this by demonstrating that the bandgap widening of the CGO reduces the recombination probability of photogenerated carriers, thereby improving their average lifetime. This study offers a novel approach for the design of visible-light-driven photocatalytic materials. Full article

This work aims to explore the influence of crystal phase engineering on the photocatalytic hydrogen evolution activity of Ru/C₃N₄ systems. By precisely tuning the combination of Ru precursors and reducing solvents, we successfully synthesized Ru co-catalysts with distinct crystal phases (hcp and fcc) and integrated them with C₃N₄. The photocatalytic hydrogen evolution experiments demonstrated that hcp-Ru/C₃N₄ achieved a significantly higher hydrogen evolution rate (24.23 μmol h⁻¹) compared to fcc-Ru/C₃N₄ (7.44 μmol h⁻¹), with activity reaching approximately 42% of Pt/C₃N₄ under the same conditions. Photocurrent and electrochemical impedance spectroscopy analyses revealed that hcp-Ru/C₃N₄ exhibited superior charge separation and transfer efficiency. Moreover, Gibbs free energy calculations indicated that the hydrogen adsorption energy of hcp-Ru (ΔG_H* = −0.14 eV) was closer to optimal compared to fcc-Ru (−0.32 eV), enhancing the hydrogen generation process. These findings highlight that crystal-phase engineering plays a critical role in tuning the electronic structure and catalytic properties of Ru-based systems, offering insights for the design of highly efficient noble metal catalysts for photocatalysis. Full article

Selective catalytic reduction of NO_x with H₂ (H₂-SCR) is crucial for eliminating NO_x emissions from hydrogen internal combustion engines (H₂-ICE). Although 1 wt.% Pt/SSZ-13 (Pt/SZ) is a promising H₂-SCR catalyst, it faces challenges such as a narrow operating window and low N₂ selectivity. Herein, the effects of WO₃ on improving the H₂-SCR performance of Pt/SZ was investigated. Results showed that incorporating 5 wt.% WO₃ significantly widened the temperature window for 80% NO_x conversion and enhanced N₂ selectivity at 90–180 °C. Several characterizations revealed that electrons transfer from W to Pt, so more active Pt⁰ species were formed on 1 wt.% Pt-5 wt.% W/SZ (Pt-5W/SZ). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis indicated that more active monodentate nitrates, nitrites, and NH₄⁺ species were generated on Pt-5W/SZ, which are key intermediates for N₂ formation. Consequently, the temperature windows for NO_x conversion (over 80%) and N₂ selectivity (over 70%) were widened by 65 °C and 66 °C, respectively. This work provides insights into the developing H₂-SCR catalysts with broader operating windows and higher N₂ selectivity. Full article

The growing demand for sustainable energy solutions requires the development of safe and efficient systems for hydrogen utilization. Hydrogen, with its high energy density and clean combustion characteristics, has become a promising alternative for heating applications. However, conventional combustion technologies often suffer from inefficiencies and safety concerns, such as NO_x emissions and explosion risks. To address these challenges, this study aimed to design and evaluate a catalytic heat generator utilizing hydrogen–air mixtures under controlled conditions to eliminate the need for pure oxygen and mitigate associated risks. A single-bed catalytic system was developed using palladium-based catalysts supported on ceramic fibers, followed by its heating, activation, and further characterization using the SEM-EDS technique. A multi-bed generator was later constructed to enhance scalability and performance. Thermal imaging and temperature monitoring were employed to optimize activation processes and assess system performance under varying hydrogen flow rates. The experimental results demonstrated efficient heat transfer and operational stability. Full article

This study employs DFT at the APFD/def2-TZVP level, with SMD solvation in THF, to investigate the catalytic activation of methane by [(κ³-CNC)Fe(N₂O)]²⁺ cation complexes. The catalytic mechanism encompasses three key steps: oxygen atom transfer (OAT), hydrogen atom abstraction (HAA), and oxygen radical rebound (ORR). The computational results identify OAT as the rate-determining step, with activation barriers of −10.2 kcal/mol and 5.0 kcal/mol for κ¹-O- and κ¹-N-bound intermediates in the gas and solvent phases, respectively. Methane activation proceeds via HAA, with energy barriers of 16.0–25.2 kcal/mol depending on the spin state and solvation, followed by ORR, which occurs efficiently with barriers as low as 6.4 kcal/mol. The triplet (S = 1) and quintet (S = 2) spin states exhibit critical roles in the catalytic pathway, with intersystem crossing facilitating optimal reactivity. Spin density analysis highlights the oxyl radical character of the Fe^IV=O intermediate as being essential for activating methane’s strong C–H bond. These findings underscore the catalytic potential of CNC-ligated iron complexes for methane functionalization and demonstrate their dual environmental benefits by utilizing methane and reducing nitrous oxide, a potent greenhouse gas. Full article

The electrocatalytic reduction of nitric oxide and nitrogen dioxide (NOx) remains a significant challenge due to the need for stable, efficient, and cost-effective materials. This study presents a novel support system for NOx reduction in alkaline media, composed of ZrO₂-WO₃-C (ZWC), synthesized via coprecipitation. Platinum nanoparticles (10 wt.%) were loaded onto ZWC and Vulcan carbon support, using similar methods for comparison. Comprehensive physicochemical and electrochemical analyses (N₂ physisorption, XRD, XPS, SEM, TEM, and cyclic and linear voltammetry) revealed that PtZWC outperformed PtC and commercial PtEtek in NOx electrocatalysis. Notably, PtZWC exhibited the highest total electric charge for NOx reduction. At the same time, the hydrogen evolution reaction (HER) was shifted to more negative cathodic potentials, indicating reduced hydrogen coverage and a modified dissociative Tafel mechanism on platinum. Additionally, the combination of WO₃ and ZrO₂ in ZWC enhanced electron transfer and suppressed HER by reducing NO and hydrogen atom adsorption competition. While the incorporation of WO₃ and ZrO₂ lowered the surface area to 96 m²/g, it significantly improved pore properties, facilitating better Pt nanoparticle dispersion (3.06 ± 0.85 nm, as confirmed by SEM and TEM). XRD analysis identified graphite and Pt phases, with monoclinic WO₃ broadening PtZWC peaks (20–25°). At the same time, XPS confirmed oxidation states of Pt, W, and Zr and tungsten-related oxygen vacancies, ensuring chemical stability and enhanced catalytic activity. Full article

A challenge for the oil refinement industry is the production of high-octane gasoline with a low benzene content. This work reports the calculation of the atmospheric benzene emissions generated from gasoline storage, transfer, and transport operations in Mexico, estimating 1.48 KBPD of environmental release. The aim was to estimate the minimum benzene emissions through operative improvements in refineries, initially by performing simulations of the Naphtha Catalytic Reforming (NCR) process using ASPEN HYSYS^® ver. 8.8 (34.0.08909) and then by optimizing the operative conditions to improve the reformate quality while reducing the benzene content. The operative ranges comprised hydrogen/hydrocarbon (H₂/HC) feedstock molar ratios from 2.0 to 6.0 and reaction temperatures from 450 to 525 °C, which were used as independent variables to assess the benzene content and the Research Octane Number (RON) of the produced gasoline. The Surface Response Method (SRM) and multi-objective optimization analysis were applied. The improved operative conditions were 491 °C and a H₂/HC ratio of 2.0, which allowed us to obtain a RON value of 89.87, an aromatics value of 37.39% (v/v), and a benzene value of 1.48% (v/v), with an estimated 16.44% drop in atmospheric benzene emissions, meaning a reduction in greenhouse gas emissions and climate change, thus favorably impacting public health by improving refinery operations. The simulation outcomes were compared with industrial-scale data and the experimental results, with significant similitudes being observed. Full article

Developing stable and effective catalysts for the hydrogen evolution reaction (HER) has been a long-standing pursuit. In this work, we propose a series of single-atom catalysts (SACs) by importing transition-metal atoms into the carbon and vanadium vacancies of tetragonal V₂C₂ and V₃C₃ slabs, where the transition-metal atoms refer to Ti, V, Cr, Mn, Fe, Co, Ni, and Cu. By means of first-principles computations, the possibility of applying these SACs in HER catalysis was investigated. All the SACs are conductive, which is favorable to charge transfer during HER. The Gibbs free energy change (ΔG_H*) during hydrogen adsorption was adopted to assess their catalytic ability. For the V₂C₂-based SACs with V, Cr, Mn, Fe, Ni, and Cu located at the carbon vacancy, excellent HER catalytic performance was achieved, with a |ΔG_H*| smaller than 0.2 eV. Among the V₃C₃-based SACs, apart from the SAC with Mn located at the carbon vacancy, all the SACs can act as outstanding HER catalysts. According to the ΔG_H*, these excellent V₂C₂- and V₃C₃-based SACs are comparable to the best-known Pt-based HER catalysts. However, it should be noted that the V₂C₂ and V₃C₃ slabs have not been successfully synthesized in the laboratory, leading to a pure investigation without practical application in this work. Full article

Hydrogen plays a vital role in the global shift toward cleaner energy solutions, with water electrolysis standing out as one of the most promising techniques for generating hydrogen. Despite its potential, the oxygen evolution reaction (OER) involved in this process faces significant challenges, including high overpotentials and slow reaction rates, which underscore the need for advanced electrocatalytic materials to enhance efficiency. Noble metal catalysts are effective but expensive, so transition-metal-based electrocatalysts like nickel–cobalt layered double hydroxides (NiCo LDHs) have become promising alternatives. In this research, a series of NiCo LDH catalysts doped with Fe, Mn, Cu, and Zn were effectively produced using a one-step hydrothermal technique. Among the catalysts, the Fe-doped NiCo LDH exhibited OER activity, achieving a lower overpotential (289 mV) at a current density of 50 mA/cm², which was far better than the 450 mV of the undoped NiCo LDH. The Mn-, Cu-, and Zn-NiCo LDHs also exhibited lower overpotentials of 414 mV, 403 mV, and 357 mV, respectively, at this current density. The Fe-doped NiCo LDH had a 3D layered nanoflower structure, increasing the surface area for reactant adsorption. The electrochemically active surface area (ECSA), as indicated by the double-layer capacitance (C_dl), was larger in the doped samples. The C_dl value of the Fe-doped NiCo LDH was 3.72 mF/cm², significantly surpassing the 0.82 mF/cm² of the undoped NiCo LDH. These changes improved charge transfer and optimized reaction kinetics, enhancing the overall OER performance. This study offers significant contributions to the development of efficient electrocatalysts for the OER, advancing the understanding of key design principles for enhanced catalytic performance. Full article