Journal of Catalysis最新文献

{"title":"Protonation dynamics of confined ethanol–water mixtures in H-ZSM-5 from machine learning-driven metadynamics","authors":"Princy Jarngal ,&nbsp;Benjamin A. Jackson ,&nbsp;Simuck F. Yuk ,&nbsp;Difan Zhang ,&nbsp;Mal-Soon Lee ,&nbsp;Maria Cristina Menziani ,&nbsp;Vassiliki-Alexandra Glezakou ,&nbsp;Roger Rousseau ,&nbsp;GiovanniMaria Piccini","doi":"10.1016/j.jcat.2025.116658","DOIUrl":"10.1016/j.jcat.2025.116658","url":null,"abstract":"<div><div>Zeolites are indispensable heterogeneous catalysts in industrial chemical processes, valued for their strong Brønsted acidity, well-defined microporous frameworks, and tunable pore structures. Their catalytic activity arises primarily from Brønsted acid sites (BAS), typically present as bridging hydroxyl groups (Si–OH–Al). Under aqueous reaction conditions, these protons interact dynamically with water and alcohol molecules, leading to complex solvation and protonation behavior within confined pores. In this study, we investigate the protonation equilibrium occurring between ethanol and water at the BAS of acidic zeolites under varying hydration levels, i.e., C₂H₅OH–(H₂O)<em>_n</em>, <em>n</em> = 1–4. Local structure was analyzed through an adaptive-learning global optimization algorithm, while enhanced sampling molecular dynamics simulations with Well-Tempered Metadynamics (WTMetaD) and machine learning interatomic potentials (MLPs) provide free-energy surfaces (FES) at variable hydration levels. The results reveal a strong dependence of proton localization on the degree of hydration. In presence of just 1 water molecule, the proton resides predominantly on ethanol; with 2 water molecules, it shifts toward water, and starting at 3, it becomes delocalized over the water cluster. These findings underscore the critical role of solvation in modulating acid site behavior and suggest that a minimum of three water molecules is necessary to fully stabilize the proton on water within the zeolite framework. This solvation threshold has significant implications for catalytic processes, particularly in biomass conversion reactions where alcohol protonation is a key step in dehydration mechanisms.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116658"},"PeriodicalIF":6.5,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"H2 production at positive potentials with a stable and bifunctional Ru0-RuO2Cy electrocatalyst","authors":"Francisco Gonell ,&nbsp;Carmen Tébar-Soler ,&nbsp;Sergio Díaz-Coello ,&nbsp;Elena Pastor ,&nbsp;Avelino Corma ,&nbsp;Patricia Concepción","doi":"10.1016/j.jcat.2025.116654","DOIUrl":"10.1016/j.jcat.2025.116654","url":null,"abstract":"<div><div>Developing highly efficient and earth-abundant catalysts for the hydrogen evolution reaction (HER) is essential to produce hydrogen (H₂) as a sustainable energy vector, providing an alternative to fossil fuels. Promoting HER in basic media remains challenging due to the lower proton availability compared to acidic conditions. Herein, we report the synthesis of partially carbon-coated, ruthenium-based materials with carefully controlled synthesis parameters that modulate the concentrations of metallic Ru⁰ and ruthenium oxycarbonate (RuO₂C_y). These materials exhibit impressive electrocatalytic performance in HER, with overpotentials required to reach a current density of 10 mA cm⁻² (versus RHE) as low as 37 mV in acidic and 7 mV in basic media. The high efficiency observed in basic media was further characterized using differential electrochemical mass spectrometry (DEMS) and in situ Raman spectroscopy, revealing H₂ production at positive potentials. This phenomenon may result from local pH changes facilitated by efficient water deprotonation on ruthenium species with intermediate oxidation states. In addition to high activity, the most efficient material demonstrated excellent stability, with no significant deactivation during chronopotentiometry experiments at 10 mA cm⁻² for 40 h. This work underscores the importance of precise material design in developing effective electrocatalysts for HER.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116654"},"PeriodicalIF":6.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co-induced copper clusters formation on Cu(1 0 0) and its application in the water–gas shift reaction: First-principles based kinetic simulation","authors":"Zi-Qiao Xue ,&nbsp;Yingqi Wang ,&nbsp;Gui-Chang Wang","doi":"10.1016/j.jcat.2025.116655","DOIUrl":"10.1016/j.jcat.2025.116655","url":null,"abstract":"<div><div>Recently surface science studies have demonstrated that reactant atmospheres such as CO can significantly induce the formation of nanoclusters on catalyst surfaces. As a key reaction for regulating the CO/H₂ ratio to achieve hydrogen production and purification, the active sites of the water–gas shift reaction (WGSR) are likely located within these dynamically formed clusters. To investigate the role of nanoclusters as potential active sites in low-temperature catalytic reactions, our study employs density functional theory combined with kinetic Monte Carlo simulations to systematically examine the dynamic formation of CO-induced copper clusters on Cu(1<!--> <!-->0<!--> <!-->0) surfaces and their impact on WGSR. The CO-induced copper nanocluster formation on Cu(1<!--> <!-->0<!--> <!-->0) was assumed into three steps: the detachment of copper atoms, diffusion of copper atom and the aggregation of copper atoms. The kinetic Monte Carlo simulations successfully reproduce the experimentally observed <strong><em>three-atom-wide copper nanorod structures(</em>i.e.<em>,Cu_3n/</em></strong>Cu(1<!--> <!-->0<!--> <!-->0)<strong><em>)</em></strong> at rom temperature, and reveal that high-density copper clusters tend to aggregate under WGSR conditions, leading to a reduction in the number of low-coordination copper atoms. By constructing Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) and Zn-doped Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) models and employing mean-field microkinetic modeling, we demonstrate that, compared to Cu(1<!--> <!-->0<!--> <!-->0), both Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) and Zn-doped Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) exhibit significantly enhanced OH adsorption while maintaining comparable CO adsorption energies. Moreover, the activation energy for water dissociation on these cluster-modified surfaces is lower than that on Cu(1<!--> <!-->0<!--> <!-->0). Further microkinetic analysis reveals that the WGSR activity follows the order: Zn-doped Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) &gt; Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) &gt; Cu(1<!--> <!-->0<!--> <!-->0), with the turnover frequency (TOF) of Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) showing good agreement with experimental results. The high activity of activity Zn-doped Cu_3n/Cu(1<!--> <!-->0<!--> <!-->0) is attributed to the reduced activation energy for water dissociation due to the stable <strong><em>Zn-Cu interface</em></strong>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116655"},"PeriodicalIF":6.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polymethylated aromatics deactivate intracrystalline acid sites in MFI zeolites during low-temperature toluene methylation","authors":"Sopuruchukwu Ezenwa,&nbsp;Andrew T. Norfleet,&nbsp;David Hibbitts,&nbsp;Rajamani Gounder","doi":"10.1016/j.jcat.2025.116653","DOIUrl":"10.1016/j.jcat.2025.116653","url":null,"abstract":"<div><div>Toluene methylation on Brønsted acidic aluminosilicates at low temperatures (&lt;433 K) and conversions (&lt;1%) show initial rates and selectivities dictated by the stabilities of transition states confined within voids of molecular dimensions, but deactivation leads to decreases in rates and shifts in selectivity according to mechanisms that remain incompletely understood. Here, we elucidate the predominant mechanism by which MFI zeolites deactivate and provide insights into the identity and location of deactivating species. Gas-phase aromatic product distributions formed on aluminosilicates of varying pore size (MFI, BEA, FAU, MCM-41) during toluene methylation (403 K, 4 kPa toluene, 66 kPa dimethyl ether) indicate that methylbenzenes larger than xylenes and 1,2,4-trimethylbenzene form, but are unable to egress from medium-pore (∼0.55 nm diameter) MFI zeolites. Co-feeding a selective poison of extracrystalline H⁺ sites (e.g., 2,6-di-<em>tert</em>-butylpyridine) reveals that intracrystalline H⁺ sites in MFI zeolites dominate observed deactivation behavior; as a result, deactivation-induced changes to xylene selectivity reflect disproportionate decreases in the numbers of intracrystalline H⁺ sites that remain active, relative to extracrystalline H⁺ sites. Post-reaction thermal treatments (up to 853 K) of deactivated MFI zeolites result in the concomitant formation of C_6‒10 monocyclic aromatic hydrocarbons and C_2‒3 aliphatic hydrocarbons, and are able to fully regenerate MFI zeolites. These results implicate bulky polymethylbenzenes (on average, C₁₁) as predominant deactivating species that cannot egress from crystallites, and only dealkylate at higher temperatures. These findings provide clarity on how zeolites deactivate and engender changes in selectivity during low-temperature toluene methylation, and provide guidance for zeolite catalyst design and regeneration.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116653"},"PeriodicalIF":6.5,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unravel key factors in α,β-unsaturated carboxylic acid salts one-pot synthesis from CO2 and alkenes: parameterization of bidentate ligands in transition-metal complexes","authors":"Youcai Zhu ,&nbsp;Yue Mu ,&nbsp;Changmu Kang ,&nbsp;Li Sun ,&nbsp;Zuoxiang Zeng ,&nbsp;Sukwon Hong ,&nbsp;Zhen Liu","doi":"10.1016/j.jcat.2025.116656","DOIUrl":"10.1016/j.jcat.2025.116656","url":null,"abstract":"<div><div>Transition metal-catalyzed CO₂ conversion to value-added chemicals faces the challenge of balancing selectivity and activity. Here, we integrate multivariate linear regression (MLR) with density functional theory (DFT) to establish a predictive framework to optimize catalytic systems for CO₂/C₂H₄ coupling. The classical steric descriptors percent buried volume (%V_bur) and bite angle were shown to be non-equivalent, and their interplay is explained by an “interaction term transformation strategy”. By rationally tuning the electronic, steric and geometric properties of the catalyst, we design a high performance PPh₂-ImPy-Ni(0) catalyst for CO₂/C₂H₄ coupling, achieving a record TON of 570 with 82 % yield. A novel buried volume of octants (V_BO) descriptor is proposed that can be extended to identify thresholds separating high-active/low-active regions in the CO₂/alkene coupling, analogous to previous ligand classification systems. Most importantly, our stepwise energy decomposition approach – from DFT-computed Gibbs free energy (ΔG) to electronic energy (ΔE), interaction energy (ΔE_int), and ultimately to the PIO-based bond index (PBI) – provides a generalizable framework for mechanistically interpreting reaction reactivity. These studies illuminate the broad applicability of hypotheses concerning the structural impact of various classes of bidentate ligands on reaction mechanisms, offering a robust methodology likely to be instrumental in advancing future ligand research.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116656"},"PeriodicalIF":6.5,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145814071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydrodeoxygenation of cottonseed oil to alkanes using effective and stable Mo-Ni-based bifunctional catalysts with optimized support","authors":"Wenyao Gu ,&nbsp;Mengjiao Xing ,&nbsp;Jiamian Chen ,&nbsp;Le Li ,&nbsp;Zimin Peng ,&nbsp;Meiqi Sun ,&nbsp;Jiaxin Xie ,&nbsp;Jianyu Tang ,&nbsp;Mintong Chen ,&nbsp;Borun Chen ,&nbsp;Tianfu Zhang ,&nbsp;Yiwen Fang ,&nbsp;Suyao Liu","doi":"10.1016/j.jcat.2025.116648","DOIUrl":"10.1016/j.jcat.2025.116648","url":null,"abstract":"<div><div>The development of high-performance hydrodeoxygenation (HDO) catalysts for the hydroprocessed esters and fatty acids (HEFA) pathway is crucial for producing sustainable aviation fuel (SAF), with a focus on promoting C–O bond cleavage while preserving C–C bonds. Herein, the present study reports a rational design of a series of Mo-Ni-based bifunctional catalysts (20 wt% Mo, 5 wt% Ni) supported on SiO₂–Al₂O₃, where precise modulation of the support composition regulates the metal-support interaction to overcome this challenge. The systematic investigation reveals that incorporating SiO₂ enhances the surface area and facilitates the formation of Brønsted acid sites through Si–O–Al interactions. Consequently, the preferred catalyst (MN/SA-70, with a SiO₂/Al₂O₃ weight ratio of 70:30) maximizes the surface density of active Mo^IV and Mo^V species while maintaining highly dispersed Ni⁰ sites. This optimized Ni⁰-MoO_x architecture enables a distinct reaction mechanism, encouraging the heterolytic cleavage of hydrogen and effectively producing proton species (H⁺) to propel the selective HDO pathway. Conversely, the high dispersion of Ni⁰ particles substantially inhibits the hydrogenolysis side reactions commonly associated with aggregated metal ensembles. Guided by these mechanistic insights, further validated by a robust linear correlation linking the surface density of Mo^IV and Mo^V species to both the intrinsic reaction rate and the HDO/DCO ratio within the kinetic control regime, the MN/SA-70 catalyst exhibits the lowest activation energy (E_a) and exceptional efficacy in the hydrotreatment of cottonseed oil. It attains complete deoxygenation with a yield exceeding 99 % of C₁₅–C₁₈ alkanes and an elevated HDO/DCO ratio of 7.1, markedly surpassing traditional formulations. The catalyst additionally exhibits exceptional stability over a period of 100 h, thereby establishing a robust foundation for the industrial-scale production of SAF.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116648"},"PeriodicalIF":6.5,"publicationDate":"2025-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoparticle size and composition of PdAu catalysts govern the structure and kinetics of H2O2 formation through O2 reduction","authors":"Sucharita Vijayaraghavan ,&nbsp;Conor Waldt ,&nbsp;Rajeev Kumar ,&nbsp;Nishchay Rathi ,&nbsp;David Hibbitts ,&nbsp;David W. Flaherty","doi":"10.1016/j.jcat.2025.116649","DOIUrl":"10.1016/j.jcat.2025.116649","url":null,"abstract":"<div><div>The identities and distribution of active site motifs on bimetallic nanoparticle surfaces depend upon their composition and size, and these factors impact rates and selectivities of surface catalyzed reactions. We combine steady-state rate measurements of O₂-H₂ reactions to form H₂O₂ and H₂O, <em>ex situ</em> spectroscopy, and density functional theory (DFT) calculations to elucidate the structure-performance relationships of silica-supported PdχAu catalysts (1.8 and 11.8 nm diameters, where <span><math><mrow><mi>χ</mi></mrow></math></span> describes the Pd mole fraction). Smaller (1.8 nm) PdχAu nanoparticles display greater H₂O₂ selectivities and rates relative to larger (11.8 nm) particles regardless of bulk composition, which suggests the number and coordination of exposed Pd atoms dictates these trends. <em>Ex situ</em> infrared spectra of adsorbed CO (CO*) and mixed ¹²CO*-¹³CO* adlayers combined with DFT-calculated structures and vibrational frequencies reveal greater Pd isolation on smaller nanoparticles. This is evidenced by weaker dipole coupling interactions between CO* species, likely due to differences in particle curvature and greater fractions of surface sites with stable binding upon nanoparticles of smaller diameters (but equivalent bulk composition). Molecular interpretations of measured apparent activation enthalpies (<span><math><mrow><mi>Δ</mi><msubsup><mi>H</mi><mrow><msub><mi>H</mi><mn>2</mn></msub><msub><mi>O</mi><mn>2</mn></msub></mrow><mo>‡</mo></msubsup><mo>,</mo><mi>Δ</mi><msubsup><mi>H</mi><mrow><msub><mi>H</mi><mn>2</mn></msub><mi>O</mi></mrow><mo>‡</mo></msubsup></mrow></math></span>) further confirm Pd active site structure differences with nanoparticle size given the same Pd content, reflecting changes in H₂O₂ selectivities. H₂O₂ selectivities remain largely constant with reactant pressures on 11.8 nm PdχAu catalysts but vary significantly with H₂ to O₂ pressure ratios on 1.8 nm PdχAu catalysts. These differences show the coordination of Pd atoms in smaller nanoparticles respond more sensitively to reactant coverages, and high O₂ chemical potentials stabilize Pd atoms at the surfaces. Collectively, these results demonstrate how nanoparticle size affects the location, size, and spatial distributions of Pd ensembles, and nanoparticle surface restructuring in response to changes in reaction conditions—ultimately governing intrinsic kinetics and selectivity to H₂O₂.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116649"},"PeriodicalIF":6.5,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic regulation of charge dynamics and reaction pathways for selective photocatalytic NO oxidation to nitrate via oxygen vacancies and plasmonic Ag nanoparticles","authors":"Dengyu Jiao ,&nbsp;Peng Chen ,&nbsp;Xing’an Dong ,&nbsp;Jiazhen Liao ,&nbsp;Wenjie He ,&nbsp;Wendong Zhang","doi":"10.1016/j.jcat.2025.116650","DOIUrl":"10.1016/j.jcat.2025.116650","url":null,"abstract":"<div><div>Selective photocatalytic oxidation of NO to nitrate (NO₃^–), rather than toxic NO₂, remains highly challenging due to uncontrollable reaction intermediates and extremely low charge migration efficiency. Herein, we design a photocatalyst (BiSbO₄/AgCl-Ag-70) that integrates a BiSbO₄/AgCl heterojunction with spatially correlated Ag nanoparticles (NPs) and oxygen vacancies (OVs) to synergistically regulated charge dynamics and reaction pathways. The formation of a heterojunction establishes a built-in electric field, which facilitates directional electron transfer. Meanwhile, Ag NPs and abundant OVs induce localized electron redistribution, promoting the generation of reactive oxygen species (ROS), and enhancing the selectivity toward nitrate. The BiSbO₄/AgCl-Ag-70 photocatalyst immobilized on ceramic foam achieved 90.0 % NO removal efficiency with excellent stability, maintaining 79.0 % removal after 720 min, while generating only 22 ppb (4.2 %) of toxic NO₂. Furthermore, the BiSbO₄/AgCl-Ag-70 catalyst demonstrated a high nitrate selectivity of 89.2 %. Mechanistic studies combining <em>in situ</em> DRIFTS and DFT calculations reveal that the introduction of OVs activates O₂/H₂O molecules, thereby promoting a reactive oxygen species-dominated pathway for the conversion of NO to NO₃^–, rather than the route involving the formation of the toxic intermediate NO₂. This work provides a strategy for the selective removal of NO by designing a material with rapid interface charge transfer and abundant surface active sites, thereby achieving precise regulation of the photocatalytic oxidation pathways.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116650"},"PeriodicalIF":6.5,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813457","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photo-generated hole mediated dynamic acid-base regulation in g-C3N4/Cr-MF/Cr2O3 composite for enhanced glucose photo-thermal conversion","authors":"Min Li,&nbsp;Juanjuan Geng,&nbsp;Bing Feng,&nbsp;Tianyu Luan,&nbsp;Xumei Tao,&nbsp;Liang Huang","doi":"10.1016/j.jcat.2025.116647","DOIUrl":"10.1016/j.jcat.2025.116647","url":null,"abstract":"<div><div>The selective conversion of glucose to 5-hydroxymethylfurfural (HMF) is crucial for sustainable biorefineries. The g-C₃N₄/Cr-MF/Cr₂O₃ composite was engineered by integrating photocatalytic and thermocatalytic functions, which synergistically balanced the Brønsted-to-Lewis acid ratio and enhanced charge carrier dynamics. Under 500 W Xe lamp irradiation and mild heat (150 °C, N₂), thermal energy served as the primary driving force, while photoexcitation selectively enhanced the catalysis by dual mechanisms. The catalyst established a spatiotemporal match between Lewis-acid-dominated glucose isomerization and Brønsted-acid-dominated dehydration at the bifunctional interface. Photo-generated holes potentiated Brønsted acidity via hole-proton synergy. This electronic and protonic-level modulation of the reaction pathway optimized the process, achieving exceptional glucose conversion (98.4 %) and HMF yield (52.8 %). This work established a generalizable framework for energy-coupled catalytic systems where light selectively accelerated specific steps within thermal reaction networks.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116647"},"PeriodicalIF":6.5,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145784417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanism of Fe modulating NO/H2 reduction selectivity in Pd/Al2O3 catalyst for passive SCR","authors":"Peng Cheng ,&nbsp;Meiqing Shen ,&nbsp;Wei Li ,&nbsp;Xinhua Li ,&nbsp;Liwei Jia ,&nbsp;Gurong Shen","doi":"10.1016/j.jcat.2025.116652","DOIUrl":"10.1016/j.jcat.2025.116652","url":null,"abstract":"<div><div>Passive selective catalytic reduction (SCR) for hydrogen engine NO_x aftertreatment requires efficient NO-to-NH₃ conversion over three-way catalysts (TWC). However, conventional TWC formulations aim to maximize NO conversion to N₂, hence it is necessary to modify catalyst formulation and tailor the NO reduction selectivity towards NH₃. In this study, we examine the effect of surface coverage on NO reduction selectivity by comparing PdFe/Al₂O₃ and Pd/Al₂O₃. Through kinetic analysis combined with characterizations, we demonstrate that Fe enhances surface H* coverage by providing additional H₂ adsorption, and these H* species participate in NO reduction through spillover effect. Meanwhile Fe reduces the NO* coverage through reducing the electron density of Pd. Collectively, these changes regulate the relative surface coverage of NO* and H* (<span><math><mrow><msub><mi>θ</mi><mrow><mi>NO</mi></mrow></msub><mo>/</mo><msub><mi>θ</mi><mi>H</mi></msub></mrow></math></span>) during the reaction, leading to significant changes in reaction kinetics, inhibiting N₂O generation while improving NH₃ selectivity. This provides important insights for optimizing passive SCR catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116652"},"PeriodicalIF":6.5,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145784418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}