Search Results (95)

The urgent need to address the climate crisis demands a swift transition from fossil fuels to renewable energy. Clean hydrogen, produced through ethanol steam reforming (ESR), offers a viable solution. Traditional ESR operates at atmospheric pressure, requiring costly separation and compression of hydrogen. High-pressure ESR, however, improves hydrogen purification, streamlines processes like pressure swing adsorption, and reduces operational costs while enhancing energy efficiency. High-pressure ESR also enables compact reactor designs, minimizing equipment size and land use by compressing reactants into smaller volumes. This study evaluates two nickel-based commercial catalysts, AR-401 and NGPR-2, under high-pressure ESR conditions. Key parameters, including reaction temperature, steam-to-ethanol ratio, and weight hourly space velocity, were optimized. At 30 bars, 700 °C, and a steam-to-ethanol ratio of 9, both catalysts demonstrated complete ethanol conversion, with hydrogen selectivity of 65–70% and yields of 4–4.5 moles of H₂ per mole of ethanol. Raising the temperature to 850 °C improved hydrogen selectivity to 74% and yielded 5.2 moles of H₂ per mole. High-pressure ESR using renewable ethanol provides a scalable, efficient pathway for hydrogen production, supporting sustainable energy solutions. Full article

Photocatalytic water splitting for hydrogen production is an attractive renewable energy technology, but the oxygen evolution reaction (OER) at the anode is severely constrained by a high overpotential. The two-dimensional vdW ferromagnetic material Fe₃GeTe₂, with its good stability and excellent metallic conductivity, has potential as an electrocatalyst, but its sluggish surface catalytic reactivity limits its large-scale application. In this work, we adapted DFT calculations to introduce surface Te vacancies to boost OER performance of the Fe₃GeTe₂ (001) surface. Te vacancies induce the charge redistribution of active sites, optimizing the adsorption and desorption of oxygen-containing intermediates. Consequently, the overpotential of the rate-determining step in the OER process of Fe₃GeTe₂ is reduced to 0.34 V, bringing the performance close to that of the benchmark IrO₂ catalyst (0.56 V). Notably, the vacancies’ concentration and configuration significantly modify the electronic structure and thus influence OER activity. This study provides important theoretical evidence for defect engineering in OER catalysis and offers new design strategies for developing efficient and stable electrocatalysts for sustainable energy conversion. Full article

Commercial alumina and silica–alumina catalysts were investigated for propylene (PEN) production via an isopropanol (IPA) dehydration reaction between 200 and 300 °C at an atmospheric pressure and IPA partial pressure of 5136 Pa. The reaction conditions were chosen to fit with the further conversion of PEN into value-added compounds with minimal capital cost, and the conceptual process design was discussed. The textural properties, structure and chemical composition of as-received and hydrothermally treated catalysts were characterised by the adsorption–desorption of N₂, X-ray fluorescence, X-ray diffraction and Nuclear Magnetic Resonance spectroscopy. The adsorption microcalorimetry of NH₃ and SO₂ was used to determine the amount, strength and strength distribution of acid–base sites, while the nature of the acid sites was investigated by Fourier Transform Infraed spectroscopy. Surface area, pore-size distribution and pore volume were not determining factors for the catalytic performances of studied solids in the conditions used here. The best-performing catalyst combined stable textural properties and a high number of high-strength acid sites (Q_diff > 150 kJ/mol NH₃) under hydrothermal conditions. The importance of determining the number and strength of acid sites of water-aged catalysts, when considering reactions where water is present as reactive or product, is underlined. Full article

Sulfion oxidation reaction (SOR) has great potential in replacing oxygen evolution reaction (OER) and boosting highly efficient hydrogen evolution. The development of highly active and stable SOR electrocatalysts is crucial for assisting hydrogen production with low energy consumption. In this work, multiphase NiCoFe-based layered double hydroxide (namely NiCoFe-LDH) has been synthesized via a facile seed-assisted heterogeneous nucleation method. Benefiting from its unique microsized hydrangea-like structure and synergistic active phases, the catalyst delivers substantial catalytic interfaces and reactive centers for SOR. Consequently, NiCoFe-LDH electrode achieves a remarkably low potential of 0.381 V at 10 mA cm⁻² in 1 M KOH + 0.1 M Na₂S, representing a significant reduction of 0.98 V compared to conventional OER. Notably, under harsh industrial conditions (6 M KOH + 0.1 M Na₂S, 80 °C), the electrolysis system based on NiCoFe-LDH||NF pair exhibits a cell potential of only 0.71 V at 100 mA cm⁻², which shows a greater decreasing amplitude of 1.05 V compared with that of traditional OER/HER systems. Meanwhile, the NiCoFe-LDH||NF couple could maintain operational stability for 100 h without obvious potential fluctuation, as well as possessing a lower energy consumption of 1.42 kWh m⁻³ H₂. Multiphase eletrocatalysis for SOR could indeed produce hydrogen with low-energy consumption. Full article

Through the use of heterogeneous catalysts, catalytic ozone oxidation technology, an effective and eco-friendly advanced oxidation process (AOP), facilitates the breakdown of ozone into reactive oxygen species (like ·OH) and greatly increases the mineralization efficiency of pollutants. This study examines the development of heterogeneous ozone catalysts through a critical evaluation of the five primary preparation techniques: ion exchange, sol–gel, coprecipitation, impregnation, and hydrothermal synthesis. Each preparation method’s inherent qualities, benefits, drawbacks, and performance variations are methodically investigated, with an emphasis on how they affect the breakdown of different resistant organic compounds. Even though heterogeneous catalysts are more stable and reusable than homogeneous catalysts, they continue to face issues like active component leaching, restricted mass transfer, and ambiguous mechanisms. In order to determine the key paths for catalyst selection in catalytic ozone treatment going forward, the main goal of this review is to provide an overview of the accomplishments in the field of the heterogeneous ozone catalyst treatment of wastewater that is difficult to degrade. Full article

In this study, Mg-Al-Zn, MgO, Al₂O_3, and ZnO were synthesized via the co-precipitation method and evaluated as catalysts for the transesterification reaction of dimethyl carbonate (DMC) and ethanol. The crystal structure, morphological characteristics, pore structure properties, and alkaline properties of the catalysts were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, temperature-programmed desorption of CO₂ (CO₂-TPD), and Fourier transform infrared spectroscopy (FTIR). The surface alkali strength and alkalinity of the solids were determined using the Hammett indicator method and non-aqueous titration. When Al₂O₃ and ZnO are used as catalysts for this transesterification, the conversion rate of dimethyl carbonate is relatively low. When MgO and Mg-Al-Zn are used as catalysts, the conversion rate of dimethyl carbonate is higher. This indicates that the alkali strength of the catalyst for the transesterification reaction needs to be greater than 9.3. Additionally, the activity of the catalysts is also related to the amount of the alkaline sites on the solid surface. The alkali strength of MgO is greater than 11; its excessively high alkali strength will react with CO₂ and H₂O during use, resulting in a reduction in the number of alkaline sites and thus showing unsatisfactory reactivity. The alkaline strength of the Mg-Al-Zn catalyst ranges from 9.3 to 11.0. When used for the first time, the number of alkaline sites decreases, and then the alkalinity remains at a certain value. Therefore, the alkaline strength of the solid catalyst for the transesterification reaction between DMC and ethanol needs to be between 9.3 and 11.0 so that the number of alkaline sites on the catalyst surface remains unchanged and the catalytic activity remains stable. Full article

Fe-doped BiOBr nanomaterials with varying Fe concentrations were synthesized using a solvothermal method. Paracetamol (APAP) was selected as the target pollutant to evaluate the visible-light-driven peroxydisulfate (PDS) activation performance of the prepared catalysts. Among all samples, 5% Fe-doped BiOBr (5% Fe-BOB) exhibited the highest catalytic efficiency, which can completely degrade APAP in 30 min under visible light irradiation. The degradation kinetics of APAP, PDS consumption, and the dominant reactive species in the 5% Fe-BOB/PDS/visible light system were systematically investigated. Results revealed that both photocatalyst dosage and PDS concentration significantly influenced activation efficiency. The primary active species responsible for APAP degradation were identified as photogenerated holes (h⁺) and singlet oxygen (¹O₂). Furthermore, cycling tests and control experiments confirmed that the 5% Fe-BOB/PDS/visible light system maintained high stability and effectively degraded APAP across a wide pH range. This work provides an efficient and stable photocatalytic system for pharmaceutical wastewater treatment through PDS-based advanced oxidation processes. Full article

Nickel (Ni) catalysts have numerous applications in the chemical industry, but they are susceptible to sulfurization, with their sulfurized structures and underlying formation mechanisms remaining unclear. Herein, density functional theory (DFT) combined with the particle swarm optimization (PSO) algorithm is employed to investigate the low-energy structures and formation mechanisms of sulfide phases on Ni(111) surfaces, especially under high-sulfur-coverage conditions where traditional DFT calculations fail to reach convergence. Using ($\sqrt{3}\times \sqrt{3}$ ) Ni(111) slab models, we identify a sulfurization limit, finding that each pair of deposited sulfur atoms can sulfurize one layer of three Ni atoms at most (Ni:S = 3:2), with additional sulfur atoms penetrating deeper layers until saturation. Under typical reactive adsorption desulfurization conditions, the ab initio thermodynamics analysis indicates that Ni₃S₂ is the most stable sulfide phase, consistent with sulfur K-edge XANES data. Unsaturated phases, including Ni₃S, Ni₂S, and Ni₉S₅, represent intermediate states towards saturation, potentially explaining the diverse Ni sulfide compositions observed in experiments. Full article

The removal of polychlorinated dibenzo-p-dioxins (PCDDs) via advanced oxidation processes (AOPs) poses a significant challenge due to their high toxicity and chemical stability. In this study, a series of well-dispersed cobalt nanoparticles supported on carbon nitrides (xCoCNs) was synthesized to activate peroxymonosulfate (PMS) for 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) degradation under visible light. The catalysts prepared were characterized using SEM, XPS, photoluminescence (PL), and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). Among them, 2CoCN with an optimal Co content exhibited the highest photocatalytic efficiency, achieving 90.5% degradation of 2,8-DCDD within 160 min under visible light/persulfate oxidation (Vis+PMS+2CoCN system). Compared with other catalysts, 2CoCN exhibited superior optical performance and a narrower bandgap, enabling efficient excitation under visible light (Vis). Notably, all xCoCNs demonstrated pH adaptability, achieving complete degradation of 2,8-DCDD under neutral conditions (pH = 7) without additional acid/alkali adjustment. Through rigorous free radical capture experiments, it was demonstrated that SO₄^•−, ^•OH and ¹O₂ were the primary reactive oxygen species (ROS) in the Vis+PMS+2CoCN system. The catalyst exhibited excellent reusability, with stable activity retained over five cycles. Based on these findings, degradation pathways and mechanisms of 2,8-DCDD in the 2CoCN+Vis+PMS system were proposed. This study presents an effective approach for PCDD abatement in wastewater treatment applications. Full article

The auto-thermal reforming (ATR) of acetic acid is an effective hydrogen production method, but it suffers from catalyst deactivation by coking. Sm-promoted layered La₂NiO₄ perovskite catalysts were synthesized via the sol–gel method and its catalytic performance in the ATR of HAc was further evaluated. The characterization results demonstrate that the incorporation of Sm into the lattice of La₂NiO₄ perovskite led to the formation of Ni-La-Sm-O species, inducing crystal defects in the perovskite structure which could promote the gasification of coking precursors. Additionally, Sm regulated the reduction characteristics of La₂NiO₄, resulting in the formation of highly dispersed nickel nanoparticles upon the hydrogen reduction, which increased the number of active sites available for acetic acid conversion. Consequently, a stable reactivity without obvious coking was obtained over a Ni_0.42La_0.7Sm_0.36O_2.01±δ catalyst within the ATR of Hac. The hydrogen yield reached 2.53 mol-H₂/mol-HAc along with the complete conversion of acetic acid. Full article

Heterogeneous catalysis has significant applications in energy conversion, chemical production, and environmental treatment. Among them, the supported catalyst Pt/CeO₂ has attracted much attention due to its high catalytic activity and stability. While the particle size of the catalyst strongly influences its performance, the dynamic behavior and the underlying mechanism of the particle size effect under realistic reactions have not been fully clarified. Using in situ transmission electron microscopy and mass spectrometry, we systematically investigated the size-dependent surface restructuring of Pt nanoparticles supported on CeO₂ in high-temperature redox environments. Larger Pt nanoparticles exhibited significant surface fluctuations during oxidation, which could be reconstructed under reducing conditions, with a slight rotation after the reaction cycle. In contrast, smaller Pt particles demonstrated greater stability, maintaining a constant size after the reaction while their surface structures continuously restructured into low-index crystal planes during oxidation. Mass spectrometry revealed water production during the catalytic process, highlighting a correlation between surface restructuring and reactivity. These findings advance the understanding of redox dynamics in noble metal catalysts and provide a theoretical basis for the design of more efficient and stable catalytic systems. Full article

Lithium borohydride (LiBH₄) has emerged as a promising hydrogen storage material due to its exceptional theoretical hydrogen capacity (18.5 wt.%). However, its practical application is hindered by high dehydrogenation temperature (>400 °C), sluggish kinetics, and limited reversibility due to stable intermediate formation. This review critically analyzes recent advances in LiBH₄ modification through three primary strategies: catalytic enhancement, nanostructure engineering, and reactive composite design. Advanced carbon architectures and metal oxide catalysts demonstrate significant improvements in reaction kinetics and cycling stability through interface engineering and electronic modification. Sophisticated nanostructuring approaches, including mechanochemical processing and infiltration techniques, enable precise control over material architecture and phase distribution, effectively modifying thermodynamic and kinetic properties. The development of reactive hydride composites, particularly LiBH₄-MgH₂ systems, provides promising pathways for thermodynamic destabilization while maintaining high capacity. Despite these advances, challenges persist in maintaining engineered structures and suppressing intermediate phases during cycling. Future developments require integrated approaches combining multiple modification strategies while addressing practical implementation requirements. Full article

The polymerization mechanism of para-methoxystyrene catalyzed by cationic α-diimine palladium complexes with various ancillary ligands was rigorously examined using density functional theory. In the classical methyl-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(Me)-C(Me)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (A⁺), the 2,1-insertion of para-methoxystyrene is favored over the 1,2-insertion, both thermodynamically and kinetically, during the chain initiation step. The resulting thermodynamically favored η³-π-benzyl intermediates face a substantial energy barrier, yielding only trace amounts of polymer, as experimentally verified. In contrast, the dibenzobarrelene-based α-diimine palladium complex [{(2,6-ⁱPr₂C₆H₃)-N=C(R)-C(R)=N-2,6-ⁱPr₂C₆H₃)}PdMe]⁺ (R = dibenzobarrelene, B⁺) shows similar energy barriers for both 2,1- and 1,2-insertions. Continuous 2,1/2,1 or 2,1/1,2 insertions are impeded by excessive energy barriers. However, theoretical calculations reveal that the 1,2-insertion product can seamlessly transition into the chain propagation stage, producing a polymer with high 1,2-regioselectivity. The observed activity of complexes A⁺ or B⁺ towards para-methoxystyrene polymerization stems from the energy barrier differences between the 1,2- and 2,1-insertions, influenced by the steric hindrance from the ancillary ligands. Further investigation into the effects of steric hindrance on the chain initiation stage involved computational modeling of analogous complexes with increased steric bulk. These studies established a direct correlation between the energy barrier difference ∆∆G (1,2–2,1) and the van der Waals volume of the ancillary ligand. Larger van der Waals volumes correspond to reduced energy barrier differences, thus enhancing the regioselectivity for para-methoxystyrene polymerization. Moreover, the experimental inertness of complex B⁺ towards styrene polymerization is attributed to the formation of stable kinetic and thermodynamic 2,1-insertion intermediates, which obstruct further styrene monomer insertion due to an extremely high reactive energy barrier. These findings contribute to a deeper understanding of the mechanistic aspects and offer insights for designing new transition metal catalysts for the polymerization of para-alkoxystyrenes. Full article

Industrial discharge of hazardous organic and synthetic chemicals, such as antibacterials and dyes, poses severe risks to human health and the environment. This study was conducted to address the urgent need for efficient and stable zinc-oxide-based photocatalysts to degrade such pollutants. A novel approach to synthesizing silver-loaded zinc oxide (Ag@Z) catalysts was introduced by using a simple and efficient combination of hydrothermal and precipitation methods. Comprehensive characterization of Ag@Z photocatalysts was performed using XRD, XPS, Raman, UV–vis adsorption, FTIR, and SEM, revealing an enhancement of structural, optical, and morphological properties in comparison to pure zinc oxide. Notably, the 5%Ag@Z catalyst exhibited the highest degradation efficiency among the other synthesized catalysts under UV-C light irradiation, and enhanced the degradation rate of pure zinc oxide (Z) by 1.14 and 1.64 times, for Triclosan (TCS) and Methylene Blue (MB), respectively. the effect of catalyst dose and initial concentration was studied. A mechanism of degradation was proposed after investigating the effect of major reactive species. The 5%Ag@Z catalyst increased the photostability, which is a major problem of zinc oxide due to photocorrosion after reusability. We found that 50% and 74% of energy consumption for the photocatalytic degradation of TCS and MB by 5%Ag@Z, respectively, was saved in compassion with zinc oxide. The remarkable photocatalytic performance and the good recovery rate of Ag@Z photocatalysts demonstrate their high potential for photocatalytic degradation of organic contaminants in water. Full article

Catalytic dechlorination of organic chlorides by palladium (Pd) with HCOOH represents one of the most effective and promising techniques for environmental remediation. In this study, we adopted alkaline-modified porous natural sponge as support of a Pd nanocatalyst (Pd@M-Sponge) and HCOOH as a hydrogen source for the hydrodechlorination of florfenicol (FF), o-chlorophenol (o-CP), and p-chlorophenol (p-CP). Favorable conversion efficiency of FF, o-CP, and p-CP was achieved at 25 °C and atmospheric pressure attributed to the small diameter and high catalytic reactivity of the prepared Pd NPs, in addition to the slight internal mass transfer limitation of the prepared Pd@M-Sponge. High reaction rate constants were obtained even in the conditions of a low molar ratio of HCOOH to p-CP (10:1) and a high concentration of p-CP (500 mg/L). The prepared catalyst also demonstrated superior recyclability without any obvious decrease in catalytic reactivity in 20 successive p-CP dechlorination cycles. This work provides an ideal recyclable and cost-effective catalyst based on renewable and biocompatible natural material for the catalytic hydrodechlorination of chlorinated organic pollutants with formic acid and a new view for the exploration and designing of highly reactive and stable catalysts for hydrodechlorination. Full article