Journal of Catalysis最新文献

{"title":"Pd-promoted reduction and restructuring of an In2O3-based catalyst for CO2 hydrogenation at room temperature","authors":"Xueqiang Zhang ,&nbsp;Florian Kraushofer ,&nbsp;Qi Yuan ,&nbsp;Yu-Xuan Wang ,&nbsp;Matthias Krinninger ,&nbsp;Zikang Su ,&nbsp;Haozhe Gai ,&nbsp;Kenneth Goodman ,&nbsp;Xianze Zhang ,&nbsp;Yu Wang ,&nbsp;Xiao Tong ,&nbsp;Tao Cheng ,&nbsp;Jian-Feng Wu ,&nbsp;Barbara A.J. Lechner ,&nbsp;Monika Blum","doi":"10.1016/j.jcat.2025.116618","DOIUrl":"10.1016/j.jcat.2025.116618","url":null,"abstract":"<div><div>An unconventional reaction mechanism in an In₂O₃/Pd(1<!--> <!-->1<!--> <!-->1) inverse model catalyst for the CO₂ hydrogenation reaction has been uncovered: In₂O₃ is partially reduced at room temperature in a reaction atmosphere as a result of its direct contact with Pd(1<!--> <!-->1<!--> <!-->1), which is an efficient H₂ splitter. The reduction induces changes in surface free energy, leading to a dynamical restructuring at the In₂O₃/Pd(1<!--> <!-->1<!--> <!-->1) interface <em>via</em> formation of InO_x and outward diffusion of Pd, as revealed by ambient pressure X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and density functional theory simulations. This dynamical restructuring eventually promotes the growth of 2D InPd_yO_x nanodomains as the catalytically active phase and the exclusive formation of methanol upon hydrogenation of CO₂ at room temperature. A comparable high selectivity toward CH₃OH was found in more realistic bulk catalytic systems (2 <em>wt</em>% Pd/In₂O₃ catalyst and commercial CZA catalyst). Scanning tunneling microscopy under ultrahigh vacuum and ambient pressure reaction atmospheres further reveals the structural dynamics at the InO_x/Pd(1<!--> <!-->1<!--> <!-->1) interface, where we follow <em>in situ</em> the evolution of the InO_x particles on Pd(1<!--> <!-->1<!--> <!-->1) and the mobility of the InPd_yO_x nanodomains in a CO₂ + H₂ environment. The present findings of the formation of a mixed oxide phase in a dynamically restructuring metal/reducible-oxide interface indicate further implications for other heterogeneous catalytic systems beyond the present CO₂ hydrogenation example and highlight the importance of <em>in situ</em> investigations.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116618"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145690083","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":"Catalytically activated isotope exchange in multicomponent systems gas–solid: statistical theory and its application on example of proton-conducting oxides","authors":"Dmitriy M. Zakharov","doi":"10.1016/j.jcat.2025.116582","DOIUrl":"10.1016/j.jcat.2025.116582","url":null,"abstract":"<div><div>This study aims to develop a comprehensive theory of the kinetics of catalytically activated isotope exchange in closed heterogeneous systems, grounded in the ideal statistical laws governing isotope distribution. Based on this theory, all systems exhibiting isotope exchange are categorised into three groups: one-component, two-component, and multicomponent, according to isotope behaviour. It is demonstrated that any mechanism of catalytically activated isotope exchange can be represented through subtypes of exchange characterised by atom transfer quasireactions, which mediate transitions between distinct types of isotope distribution within the components. An algorithm for describing experimental data within this theoretical framework was formulated and applied to a range of literature data concerning H/D exchange in ethylene, methane, methane–hydrogen, ethane–hydrogen, and methanol–hydrogen mixtures over metal and oxide-supported catalysts. Employing the theory, the mechanism of catalytically activated isotope exchange in pure methane and methane–hydrogen mixtures over BaCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−α, a promising proton-conducting catalyst, was investigated, revealing catalytic heterogeneity of active sites and H₂-induced kinetic isotope effects.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116582"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145611652","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 versatile one-pot strategy for the synthesis of organosilicon-functionalized polyolefins","authors":"Rafał Januszewski ,&nbsp;Bartosz Orwat ,&nbsp;Michał Dutkiewicz ,&nbsp;Ireneusz Kownacki","doi":"10.1016/j.jcat.2025.116588","DOIUrl":"10.1016/j.jcat.2025.116588","url":null,"abstract":"<div><div>We report a facile <em>one-pot</em> catalytic strategy for the synthesis of organosilicon-functionalized polyolefins — a long-standing challenge in polymer science. This streamlined approach integrates the hydrosilylation of polybutadiene with subsequent hydrogenation of the resulting silyl-functionalized intermediates, all under unified reaction conditions. The developed protocol exhibits exceptional functional group tolerance, enabling the incorporation of a broad spectrum of organic moieties that are typically incompatible with conventional copolymerization or post-polymerization methods. Remarkably, the degree of functionalization can be precisely tuned simply by adjusting the stoichiometric ratio of the organosilicon reagent to vinyl groups. This level of control, versatility, and simplicity has not been demonstrated previously in the functionalization of polyolefins. The methodology paves the way for the tailor-made design of advanced silicon-containing polyolefins with attractive functional groups, opening new avenues for applications in materials science, surface engineering, and beyond.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116588"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145599413","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":"Reductive alkylation of ketones with aldehydes using a simple catalyst and waste reductants","authors":"Evgeniya Podyacheva ,&nbsp;Zhuang Ma ,&nbsp;Alexandra I. Balalaeva ,&nbsp;Oleg I. Afanasyev ,&nbsp;Rajenahally V. Jagadeesh ,&nbsp;Matthias Beller ,&nbsp;Denis Chusov","doi":"10.1016/j.jcat.2025.116583","DOIUrl":"10.1016/j.jcat.2025.116583","url":null,"abstract":"<div><div>It is widely acknowledged that selective homogeneous catalytic reactions for advanced organic synthesis require two fundamental conditions: mild reaction conditions (low temperature/pressure) and catalysts with structurally complex ligands. In contrast, the present study demonstrates that simple metal salt (ruthenium (III) chloride) exhibit high selectivity and efficiency in catalyzing the chemo- and regioselective reductive alkylation of ketones with aldehydes. The synthetic protocol described herein is distinguished by its phosphine-free nature, a feature that facilitates the synthesis of a series of valuable organic products, encompassing heterocyclic and functionalized derivatives, as well as drug molecules. It is noteworthy that the selectivity of this Ru-based methodology is augmented by increasing the temperature. Converter gas, a byproduct of steel manufacturing, can be utilized as a reducing agent in this alkylation process.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116583"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593376","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":"Site-specific sulfur vacancies govern hydrodeoxygenation selectivity for alcohol or alkane in MoS2-catalyzed fatty acid conversion","authors":"Linjie Guan ,&nbsp;Pengwei Zhao ,&nbsp;Mingjun Cen ,&nbsp;Bin Chen ,&nbsp;Haipeng Yu ,&nbsp;Yonghao Xiao ,&nbsp;Wenchao Peng ,&nbsp;Yang Li ,&nbsp;Qicheng Zhang ,&nbsp;Danyun Xu ,&nbsp;Xiaobin Fan","doi":"10.1016/j.jcat.2025.116605","DOIUrl":"10.1016/j.jcat.2025.116605","url":null,"abstract":"<div><div>The hydrodeoxygenation (HDO) of long-chain lipids or fatty acids represents a pivotal process for synthesizing bio-based chemicals and sustainable aviation fuels, yet achieving high selectivity towards a single product remains a significant challenge. In this study, we address this limitation by engineering MoS₂ catalysts with controlled sulfur vacancy (SV) distributions through two distinct crystallization pathways. The direct crystallization-derived MoS₂(P) generates abundant in-plane SVs during thermal annealing, whereas the crystal seed-induced MoS₂(E) retains oxidized Mo⁵⁺/Mo⁶⁺ species that suppress planar sulfur depletion. These markedly different SV configurations profoundly influence catalytic performance. MoS₂(P)-A, dominated by in-plane SV, achieves near-quantitative hexadecane yield (99.5 %) in palmitic acid HDO, while edge SV-rich MoS₂ (E)-A predominantly yields hexadecanol (80.6 %). In-situ DRIFTS results show that palmitic acid adopts distinct adsorption configurations (bidentate vs. bridging) on the two SV types, leading to different reactivities. The superior alcohol dehydration efficiency of MoS₂(P)-A is attributed to its in-plane SV architecture, which not only circumvents steric hindrance effects but also provides abundant Lewis acid sites, thereby promoting efficient C–O bond cleavage. This work elucidates the structure–activity relationship for tuning the selectivity of MoS₂ catalysts through precise control of sulfur vacancy spatial distribution, providing a crucial theoretical foundation and experimental guidance for the future design of HDO catalysts with customizable product distributions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116605"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145651300","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":"Efficiency and synergy of bis-urea anions for the polymerization of cyclic esters","authors":"Riccardo Piacquadio ,&nbsp;Federica Santulli ,&nbsp;Michele Polise ,&nbsp;Filomena L. Damiani ,&nbsp;Stefano Milione ,&nbsp;Marina Lamberti ,&nbsp;Christophe M. Thomas ,&nbsp;Consiglia Tedesco ,&nbsp;Mina Mazzeo","doi":"10.1016/j.jcat.2025.116627","DOIUrl":"10.1016/j.jcat.2025.116627","url":null,"abstract":"<div><div>Organocatalytic ring-opening polymerization of lactones is a highly versatile approach to obtain well-defined, biodegradable polyesters. Despite its sustainability advantages, a major challenge remains achieving both high activity and precise control over polymerization, particularly at low catalyst loadings. Here we report that bis-urea anions, in the presence of an alcohol, are excellent catalysts for the ring-opening polymerization of lactide and various lactones. These catalytic systems exhibit “living/immortal” polymerization behavior, producing high molecular weight polymers with exceptional turnover frequencies (up to 250,000 h⁻¹) even at catalyst loadings as low as 0.06 %. Density functional theory calculations, supported by X-ray characterization, confirm the remarkable catalytic performance arises from synergistic interactions between urea moieties, which facilitate cooperative activation of the monomer. These interactions are further enhanced by metal-ion templating effects and the conformational flexibility of alkyl linkers, collectively contributing to the remarkable efficiency and control of the polymerization process.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116627"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718429","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 radical sulfonaminocyclization and sulfonylcyclization of acrylamides with N-sulfonaminopyridinium salts","authors":"Jin-Wei Yuan ,&nbsp;Wei Lian ,&nbsp;Yang Zhou ,&nbsp;Meng Yan ,&nbsp;Jian-Li Wu ,&nbsp;Liang-Ru Yang ,&nbsp;Yong-Mei Xiao ,&nbsp;Ling-Bo Qu","doi":"10.1016/j.jcat.2025.116625","DOIUrl":"10.1016/j.jcat.2025.116625","url":null,"abstract":"<div><div>A photoredox-catalyzed sulfonamination/cyclization reaction of <em>N</em>-alkyl-<em>N</em>-methacryloyl benzamides has been developed, utilizing <em>N</em>-aminopyridinium salts as sulfonamino radical precursors via N–N bond cleavage. Additionally, this reaction also enables efficient N–S bond cleavage under mild conditions, generating diverse sulfonyl radicals through electron donor–acceptor (EDA) complexes. The innovative synthetic strategy provides a broad substrate scope and mild reaction conditions, facilitating the synthesis of various 4-sulfonamino and 4-sulfonyl isoquinolinonedione derivatives. Mechanistic investigations indicate that the sulfonaminocyclization occurs via a spirocyclization and an acyl radical rearrangement pathway, while the sulfonylcyclization proceeds through a radical cyclization pathway. This process is facilitated by <em>N</em>-aminopyridinium salts in the presence of unactivated alkenes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116625"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718430","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":"Promoting the side-chain mechanism of the aromatic cycle in H-ZSM-5 zeolites by a second proximate acid site","authors":"Xin Xin ,&nbsp;Chengguang Yang ,&nbsp;Dong Fang ,&nbsp;Jia Liu ,&nbsp;Shenggang Li","doi":"10.1016/j.jcat.2025.116624","DOIUrl":"10.1016/j.jcat.2025.116624","url":null,"abstract":"<div><div>Zeolite-based catalysts found successful applications for the methanol-to-olefins (MTO) reaction, which offers a non-petroleum route for olefin production. For the small pore H-SSZ-13 zeolites, recent studies revealed cooperative effects of the active sites in that direct participation of the second acid site has a substantial influence on the side-chain mechanism of the aromatic cycle. However, it is unclear whether such cooperative effects are specific to some particular zeolites, for instance whether the double acid sites in the medium pore H-ZSM-5 zeolites will have similar effects on the side-chain mechanism. Herein, we performed periodic density functional theory (DFT) calculations to investigate the potential influence of a proximate second acid site on the side-chain mechanism of the aromatic cycle for the H-ZSM-5 zeolites. Our calculations show that the formation of the 1,1-dimethyl-4-ethylbenzenium cation (diMEB+) with an ethyl group is the key step of the side-chain mechanism for both single and double acid site models, while the elimination of the ethyl side chain is facile. Introducing a second acid site in proximity should thus greatly reduce the free energy barrier of the rate-determining step for the side-chain mechanism from 1.73 to 1.41 eV. Moreover, this mechanism occurs by indirect rather than direct participation of the second acid site. Further analysis indicates that the promoting effect of the second acid site on the side-chain mechanism results from stabilization of the transition states of the methylation reaction. Our work provides valuable atomic level insights into the MTO reaction, and should benefit the rational design of more efficient zeolite-based catalysts for product distribution regulation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116624"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718432","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":"Ni/photoredox dual catalytic 1,4-diarylation of 1,3-enynes for modular synthesis of polyaryl allenes","authors":"Bo Zhang,&nbsp;Ziyi Sheng,&nbsp;Deze Kong,&nbsp;Yu Pan,&nbsp;Pan Gao,&nbsp;Feng Chen","doi":"10.1016/j.jcat.2025.116626","DOIUrl":"10.1016/j.jcat.2025.116626","url":null,"abstract":"<div><div>We report a dual nickel and visible-light-driven dual catalytic system that enables the 1,4-diarylfunctionalization of 1,3-enynes with aryl iodides, providing access to polyaryl-substituted allenes with broad substrate scope. This method synergizes photoredox catalysis (4-CzIPN/DMAP) and nickel catalysis (Ni(DME)Br₂/1,10-phenanthroline) under mild conditions using Zn as a terminal reductant.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116626"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718433","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":"New bi-functional catalysts for a novel continuous production of propylene oxide with in-situ generated hydrogen peroxide","authors":"Christoph Schmidt ,&nbsp;Matias Alvear ,&nbsp;Francesco Sandri ,&nbsp;Seo Mandon ,&nbsp;Satu Ojala ,&nbsp;Tiina Laitinen ,&nbsp;Mika Lastusaari ,&nbsp;Ilari Angervo ,&nbsp;Tapio Salmi","doi":"10.1016/j.jcat.2025.116637","DOIUrl":"10.1016/j.jcat.2025.116637","url":null,"abstract":"<div><div>Combined direct synthesis of hydrogen peroxide (DSHP) and epoxidation of propene to propylene oxide with hydrogen peroxide (HPPO) was carried out first time in a continuous laboratory-scale trickle bed reactor operating under mild conditions of 8 bar and 10°C. The reaction was performed with bimetallic gold–palladium catalysts supported on titanium silicalite 1 (TS-1). Three series of catalysts were synthesized from two different lots of TS-1 and different calcination heating rates. The catalysts were extensively examined using XRD, SEM-EDS, TEM-SAED, STEM-EDS, ICP-OES, XPS, UV–vis DRS, nitrogen-physisorption and ammonia-TPD. The metal-modification of TS-1 containing anatase impurities was shown first time, where the preferential deposition site for the bimetallic nanoparticles was on the minor anatase phase, found in different amounts in commercial TS-1 materials. In the first catalyst series, a higher anatase content was found, which led to a decrease of the AuPd nanoparticle size compared to the second and third series. Increasing the heating rate in calcination resulted in an additional reduction of the AuPd nanoparticle size. The propylene oxide selectivity was 55.7 % using catalysts of the third series, while the propylene oxide production rate was 0.17 <!--> <!-->mol·kg_cat^-1·h⁻¹ with 19.2 % propene conversion. The use of a palladium-poor alloy was found to be crucial for this reaction system to limit the hydrogenation of hydrogen peroxide and propene. The catalyst activity was investigated in the separate processes of DSHP and epoxidation to get a deeper insight into the reaction mechanism. In the switch experiments, DSHP followed by the combined reaction of DSHP and HPPO, the competing side reactions, hydrogenation of propene and hydrogen peroxide were confirmed. In another experiment, the dismutation of hydrogen peroxide was disproved.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116637"},"PeriodicalIF":6.5,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145753012","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}