Journal of Catalysis最新文献

{"title":"Upgrading of glycerol to solketal over mesoporous gallosilicates with tuned hydrophobicity","authors":"Hussein Hussein ,&nbsp;Luca Fusaro ,&nbsp;Michel Devillers ,&nbsp;Carmela Aprile","doi":"10.1016/j.jcat.2025.116409","DOIUrl":"10.1016/j.jcat.2025.116409","url":null,"abstract":"<div><div>Novel mesoporous gallosilicates with tuned hydrophobicity were synthesized through methylation of extra small XS-SiO₂ silica particle via condensation with trimethoxymethylsilane CH₃Si(OCH₃)₃ followed by impregnation with gallium (III) precursors. The structural and textural properties of the solids obtained were extensively characterized by different techniques. The synthesized catalysts displayed excellent catalytic activity in the acetalization of acetone with glycerol to produce solketal. Among all the studied catalysts, the most active catalyst, XS-10 %Me-GaLac, displayed high turnover number and significantly improved glycerol conversion which is attributed to the relatively hydrophobic surface and high amount of accessible active acid sites. The high acidity and enhanced hydrophobicity of this catalyst was generated by the incorporation of the methyl groups which allowed a homogeneous dispersion of highly active gallium species on the silica matrix before calcination. The effect of reaction time, temperature, catalyst loading and acetone to glycerol molar ratio was investigated. Furthermore, the mesoporous gallosilicate materials were truly heterogeneous without leaching gallium active sites and can be efficiently reused in successive catalytic cycles.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116409"},"PeriodicalIF":6.5,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009355","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":"A synthesis-structure-catalytic activity map for CO oxidation on dealloyed Au-Ag nanoparticles derived using multiscale simulations","authors":"Prajwal Kumar Ayadathil,&nbsp;Abhijit Chatterjee","doi":"10.1016/j.jcat.2025.116406","DOIUrl":"10.1016/j.jcat.2025.116406","url":null,"abstract":"<div><div>Dealloyed gold nanoparticles can be synthesized by selectively dissolving Ag from gold-silver alloy nanoparticles through the well-known process of dealloying. These nanoparticles exhibit remarkable catalytic activity towards the CO oxidation reaction owing to their large specific surface area, presence of rough surfaces that contain a high density of catalytically-active sites, and synergistic effects arising from the residual Ag leftover from the dealloying process. We introduce a computational framework aimed at determining the optimal dealloying conditions that can yield dealloyed nanoparticles with the highest CO oxidation specific activity. This is accomplished by establishing comprehensive synthesis-structure–activity relations for dealloyed nanoparticles. Through such an approach, we elucidate the link between the key catalyst attributes (active site density, reaction kinetics, and synergistic effects) and dealloying parameters (initial nanoparticle size, composition, dissolution condition, and dissolution time). Our methodology combines multiscale simulations to explore a vast synthesis-parameter space. The resulting size-dependent synthesis-structure–activity map reveals the optimal residual Ag for efficient CO oxidation catalysis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116406"},"PeriodicalIF":6.5,"publicationDate":"2025-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144995538","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":"Selective hydrodeoxygenation of lignins into cyclohexanols over Ni/CeO2 via hydrogen transfer","authors":"Lang Zhou ,&nbsp;Tong Xu ,&nbsp;En Zhao ,&nbsp;Dongsheng Huang ,&nbsp;Lin Dong ,&nbsp;Zupeng Chen","doi":"10.1016/j.jcat.2025.116396","DOIUrl":"10.1016/j.jcat.2025.116396","url":null,"abstract":"<div><div>The production of high-value cyclohexanols from renewable lignins under hydrogen-free conditions is highly attractive but notoriously challenging. Here, we report an efficient strategy for converting various lignin-derived phenolic monomers and lignin oils into cyclohexanols using a Ni/CeO₂ catalyst with isopropanol as the hydrogen donor. This approach achieves an impressive yield of 90.1 % from 2-methoxy-4-propylphenol, demonstrating selective hydrogenation of aromatic rings and cleavage of Ar-OCH₃ bonds while retaining the desired hydroxyl functionalities. Mechanistic investigations reveal that the interplay between Ni and CeO₂ enhances the reduction of Ni species and the creation of oxygen vacancies. Additionally, the charge transfer between Ni and CeO₂ facilitates the formation of Ni<em>^δ</em>⁺, which promotes the adsorption and activation of aromatic rings. Notably, the Ni/CeO₂ catalyst exhibits excellent stability and broad applicability, delivering a cyclohexanol yield of 66.6% from real lignin oil. This work presents a robust strategy for the high-selectivity conversion of renewable lignin into cyclohexanols via catalytic hydrogen transfer reactions, paving the way for sustainable lignin utilization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116396"},"PeriodicalIF":6.5,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144983287","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":"Key role of yttrium doping on Cu/CeO2 (111) in water–gas shift reaction: Promotion of cluster dispersity","authors":"Yu-Xuan Zhu ,&nbsp;Yingqi Wang ,&nbsp;Gui-Chang Wang","doi":"10.1016/j.jcat.2025.116405","DOIUrl":"10.1016/j.jcat.2025.116405","url":null,"abstract":"<div><div>Conventional theoretical models of electronic metal-support interaction (EMSI) often assume <strong><em>uniform metal dispersion</em></strong>, leading to conclusions conflicting with experimental observations. It highlights the critical need to incorporate <strong><em>metal dispersion effects</em></strong> in EMSI studies. Here, we investigate how Y³⁺ doping regulates Cu cluster dispersion on CeO₂(1 1 1) for the water–gas shift reaction (WGSR) using density functional theory (DFT), mean-field microkinetic modeling (MF-MKM), and kinetic Monte Carlo (kMC) simulations. Cohesion energy analysis reveals that on undoped ceria, bilayer clusters predominate. However, Y³⁺ (compared to Ce⁴⁺) possesses a smaller radius and lower redox capability, which differentiates loading sites but obstructs EMSI. Excessive doping even restricts the formation of spillover oxygen (O_sp), thereby favoring 3D clusters. The presence of surface spillover oxygen partially compensates for the EMSI weakening. This compensation effect causes the cohesive energy difference between bilayer and O_sp planar-type clusters to become positive, resulting in the advantage of O_sp planar-type clusters at lightly doping level. Kinetic simulations identify O_sp-type planar copper clusters as functional active phases for undoped/lightly doped ceria, while heavily doped systems are regular planar clusters without O_sp. O_sp-type planar clusters exhibit extraordinary catalytic activity due to O_sp-mediated adsorption and reactivity promotion, whereas bilayer clusters manifest low activity. Comprehensive analysis of cluster dispersion and structure–activity relationships discloses non-monotonic WGSR activity dependence on Y-doping: activity of sub-nanometer copper clusters peaks at low doping amount before declining at higher doping levels, aligning with experiments This work highlights the necessity of identifying both dispersion and activity of clusters for specific doping levels. These findings provide critical insights for the design of doped-supported catalysts and establish a theoretical framework for optimizing EMSI in heterogeneous catalysis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116405"},"PeriodicalIF":6.5,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924408","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":"A comprehensive theoretical study on CuOx/Cu(110) catalyzed water–gas shift reaction","authors":"Yu-Bi Huang ,&nbsp;Yingqi Wang ,&nbsp;Gui-Chang Wang","doi":"10.1016/j.jcat.2025.116404","DOIUrl":"10.1016/j.jcat.2025.116404","url":null,"abstract":"<div><div>In recent years, theoretical studies on Cu-based catalysts for the water–gas shift reaction (WGSR) have been conducted extensively. However, the issues concerning the oxidation state of copper atoms under reaction conditions and their roles in catalyzing WGSR remain unresolved. Surface science experiments have demonstrated that clean Cu(110) exhibits higher catalytic activity than clean Cu(111), and a previous study has theoretically indicated that the oxidation can enhance the intrinsic activity of Cu(111). Therefore, determining the surface oxides on Cu(110) and their catalytic activity is fundamental and will provide valuable insights for rational catalyst design. In this paper, ab initio atomistic thermodynamics was performed to reveal the potential phase transitions from clean Cu(110) to Cu₂O (110), including added row-(4 × 1) (AR-41), added row-(2 × 1) (AR-21), as well as added strand-c(6 × 2) (AS-c62) structures. The WGSR mechanisms were systematically investigated on these distinct surfaces by density functional theory (DFT) calculations. Additionally, we identified a volcano-type relationship between the catalytic performance and the oxidation degree of Cu(110), with the mildly oxidized AR-41 structure exhibiting optimal activity, as determined by mean-field microkinetic modeling (MF-MKM) and kinetic Monte Carlo (kMC) simulations. Moreover, the degree of rate control (DRC) analysis revealed that water dissociation is no longer the rate-determining step for oxidized structures compared to clean Cu(110). Instead, the direct oxidation of CO and the production of H₂ may play a more critical role in CuO_x/Cu(110)-catalyzed WGSR. Meanwhile, it was found that the redox and carboxyl mechanisms compete with each other. The carboxyl mechanism predominantly operates at low levels of oxidation, while the redox mechanism takes precedence at high levels of oxidation. Consequently, the appropriate oxidation state will enhance catalytic activity on Cu(110). Additionally, doping with other metal atoms was used as a strategy to improve catalyst performance, and it was found that doping with Pd or Zn may slightly promote the catalytic performance. Furthermore, a comparison between CuO_x/Cu(110) and CuO_x/Cu(111) was conducted, and it was found that they show different catalytic activity due to their unique interfaces of CuO_x and metallic subsurface.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116404"},"PeriodicalIF":6.5,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928589","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":"Visible-light-driven aerobic oxidation via a dual ROS-generating manganese(II)-organic framework photocatalyst","authors":"Hui Chen ,&nbsp;Jiahui He ,&nbsp;Zhen Zhou ,&nbsp;Bin Wang ,&nbsp;Xiong-Feng Ma ,&nbsp;Maojun Deng ,&nbsp;Yuanzhen Zhou ,&nbsp;Pascal Van Der Voort","doi":"10.1016/j.jcat.2025.116403","DOIUrl":"10.1016/j.jcat.2025.116403","url":null,"abstract":"<div><div>Developing sustainable and efficient photocatalytic systems for aerobic oxidation remains a pivotal challenge in green chemistry. Herein, we report the rational design and synthesis of a novel manganese(II)-organic framework (An-MnMOF) by integrating anthracene-based photoactive ligands with Mn(II)-oxo clusters. The framework exhibits broad visible-light absorption extending up to 650 nm, efficient charge separation, and dual reactive oxygen species (ROS) generation capabilities. Structural characterization confirms a crystalline 2D lamellar architecture with hierarchical porosity, while mechanistic studies reveal a synergistic interplay between anthracene-mediated light harvesting and Mn(II)-driven redox processes. Under visible-light irradiation, An-MnMOF achieves exceptional catalytic performance in aerobic oxidation reactions, including hydroxylation of arylboronic acids (＞95 % yield) and benzylic C(<em>sp</em>³)-H bond activation (＞85 % yield), outperforming the homogeneous Mn catalyst. The framework’s microporous channels stabilize reactive intermediates, suppressing overoxidation, while its robust chemical and thermal stability enables five consecutive recycling cycles without activity loss. This work establishes a paradigm for noble-metal-free photocatalysis by leveraging MOF-confined dual-function sites for solar-driven organic transformations, advancing sustainable synthesis methodologies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116403"},"PeriodicalIF":6.5,"publicationDate":"2025-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924405","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":"Ir-catalyzed transfer hydrogenation and N-alkylation of alkynyl/alkenyl arylamines with carbonyls in water","authors":"Jianhua Liao,&nbsp;Huajie Zhu,&nbsp;Shilin Guo,&nbsp;Jinhui Li,&nbsp;Lu Ouyang,&nbsp;Renshi Luo","doi":"10.1016/j.jcat.2025.116402","DOIUrl":"10.1016/j.jcat.2025.116402","url":null,"abstract":"<div><div>Herein, we advance a novel and efficient iridium-catalyzed transfer hydrogenation and <em>N</em>-alkylation of alkynyl/alkenyl arylamines with carbonyls to facilitate the streamlined synthesis of diverse amines. The reaction could be achieved direct hydrogenation and alkylation of alkynyl/alkenyl arylamines with carbonyls using H₂O as reaction media and HCO₂H as hydrogen donor, providing a variety of arylamine derivatives in moderate to excellent yields. Control experiments indicated the <em>N</em>-alkylation of alkynyl/alkenyl arylamines contributed to the reduction of alkynes/alkenes. The practicality of this sustainable process was evidenced by large-scale, catalyst recycling experiments and derivatization of biologically active molecules.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116402"},"PeriodicalIF":6.5,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919085","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":"Unraveling B, N Co-doping synergy in graphitic carbon nitride for efficient CO2 cycloaddition with styrene oxide","authors":"Hafila S. Khairun ,&nbsp;Gazala Parveen ,&nbsp;Ripsa Rani Nayak ,&nbsp;Jogeswar Chhatria ,&nbsp;Sooraj Kunnikuruvan ,&nbsp;Navneet Kumar Gupta","doi":"10.1016/j.jcat.2025.116399","DOIUrl":"10.1016/j.jcat.2025.116399","url":null,"abstract":"<div><div>The cycloaddition of CO₂ and styrene oxide to produce styrene carbonate under solvent-free conditions offers an eco-friendly, atom-efficient, and highly effective approach to CO₂ utilization. This study presents a highly active and selective catalytic system based on boron and nitrogen co-doped graphitic carbon nitride (BN-GCN) for the efficient production of styrene carbonate. Unlike many conventional catalysts, the BN-GCN system operates without needing solvents or metals, functioning as a metal-free heterogeneous catalyst for the cycloaddition of CO₂ with styrene oxide. It outperforms other heteroatom-doped graphitic carbon nitride (X-GCN) catalysts, with the enhanced activity attributed to the synergistic interaction of reactants with B and N sites. XPS analysis reveals that the N moiety and the B atom are critical active sites for cooperative catalysis. The BN-GCN catalyst achieves 75 % conversion and &gt; 90% selectivity for styrene carbonate (SC) formation under mild conditions (353 K, 2 bar CO₂) within 3 h. Comprehensive material characterization, kinetic studies, and reaction data confirm that B and N co-doping facilitates the co-activation of CO₂ and epoxide. Based on density functional theory (DFT) calculations, and experiments, a convenient mechanism has been proposed for this unique method. The B–N bond duality in BN-GCN offers a cost-effective, sustainable, and efficient catalytic pathway for CO₂ utilization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116399"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915847","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":"Construction of visible light-driven ternary S-scheme melamine sponge MS/TpTt/ZIS heterojunction photocatalysts for enhanced photocatalytic pollutant removal and hydrogen evolution","authors":"Qingmei Tang ,&nbsp;Yuqi Wan ,&nbsp;Yuzhuo Wan ,&nbsp;Zhiquan Pan ,&nbsp;Qingrong Cheng","doi":"10.1016/j.jcat.2025.116388","DOIUrl":"10.1016/j.jcat.2025.116388","url":null,"abstract":"<div><div>Charge separation critical for improving photocatalytic performance. But single semiconductor cannot realize efficient charge separation and transport. Little research has been reported on using melamine foam (MS) as a carrier. Herein, we have successfully synthesized a heterojunction MS/TpTt/ZnIn₂S₄-x% (MTZIS-x%) photocatalysis with MS as the carrier by solvothermal method. It was found the degradation rate of MO over MTZIS-3 % could reach almost 100 %, and the biotoxicity tests showed that degraded residual liquid of MO was almost non-biological toxicity. Moreover, the ptotocatalytic H₂ evolution rate of MTZIS-3 % reached to 11523.64 µmol g⁻¹h⁻¹, which was 7.02, 11.91 and 13.19 times than that of ZIS, MS/TpTt and COF-TpTt. And the evolution rate of photoreduction CO₂ to CO was 501.55 µmol g⁻¹ h⁻¹. The excellent photocatalytic property was owing to the S-scheme band structure facilitated the separation of electron-hole efficiently and retained the highly reducing electrons. This work provided a theoretical reference for the construction of efficient new heterojunction photocatalysts using MS as a carrier.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116388"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919124","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":"Solventless and low-temperature ring-opening polymerization using deep eutectic solvents of ε-caprolactone and their depolymerization cycles for biodegradable polyesters","authors":"Puracheth Rithchumpon ,&nbsp;Wanich Limwanich ,&nbsp;Kraikrit Utama ,&nbsp;Nathaporn Cheechana ,&nbsp;Natthapol Akkravijitrkul ,&nbsp;Padchanee Sangthong ,&nbsp;Winita Punyodom ,&nbsp;Puttinan Meepowpan","doi":"10.1016/j.jcat.2025.116400","DOIUrl":"10.1016/j.jcat.2025.116400","url":null,"abstract":"<div><div>The catalytic performance of deep eutectic solvents (DESs) between choline chloride (ChCl) and organic acids was investigated for the ring-opening polymerization (ROP) of <em>ε</em>-caprolactone (CL). These organic acids act as hydrogen bond donors (HBDs), while choline chloride serves as the hydrogen bond acceptor (HBA). Among fifteen acids, (–)-camphorsulfonic acid (CSA), diphenyl phosphate (DPP), 2,5-dimethylbenzenesulfonic acid (DSA), and <em>p</em>-toluenesulfonic acid (PTSA) with ChCl at 100:1:1 M ratio could effectively poly(<em>ε</em>-caprolactone) (PCL) with the molecular weight ranging from 8,000 to 10,000 g/mol and a low dispersity (<em>Ð</em>) (1.2–1.5). The ROP kinetics was powerfully investigated differential scanning calorimetry (DSC) technique. PTSA in combination with ChCl exhibited the fastest reaction and the lowest activation energy (<em>E_a</em>). Additionally, the depolymerization processes of PCL back to its CL monomer was studied by thermogravimetric analysis (TGA). Notably, phosphotungstic acid (PTA) demonstrated the highest depolymerization activity achieving a 100 % yield of CL at 160 °C for 1 h under vacuum distillation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116400"},"PeriodicalIF":6.5,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144919132","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}