Journal of Catalysis最新文献

{"title":"Efficient catalytic upcycling of polyester and polycarbonate plastics using an NNN-based iron catalyst","authors":"Xiaoxiao Chu ,&nbsp;Guoren Zhou ,&nbsp;Chongyan Ren ,&nbsp;Xiaoshi Zhang ,&nbsp;Maofu Pang ,&nbsp;Nuoyan Zhao ,&nbsp;Hongwu Zhang","doi":"10.1016/j.jcat.2025.116358","DOIUrl":"10.1016/j.jcat.2025.116358","url":null,"abstract":"<div><div>The development of efficient, eco-friendly recycling methods for mitigating the environmental impact of polyester waste remains a significant challenge. Herein, we establish an efficient catalytic system based on an NNN-based iron pincer catalyst, which can facilitate the hydrogenative depolymerization of polyester plastics using two methods. The first method is to depolymerize the polyester into ester monomers via methanolysis and facilitate subsequent transfer hydrogenation using ammonia borane as a hydrogen source to obtain diol products under mild conditions. The second method is to use molecular hydrogen as a hydrogen source for the direct catalytic hydrogenolysis of the plastic to obtain diol products. The catalyst [Fe(NNHN)Cl₂] demonstrates high catalytic efficiency in the degradation of polyester and polycarbonate plastics, including when using plastic waste from daily life as raw materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116358"},"PeriodicalIF":6.5,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840330","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":"Design and synthesis of nickel-containing covalent organic frameworks for visible light induced directed ortho-trifluoromethylation of aromatic amides","authors":"Mengqi Zou,&nbsp;Houhai Fan,&nbsp;Feiyang Xie,&nbsp;Jing Xu,&nbsp;Hongbo Zhao,&nbsp;Wenyi Chu","doi":"10.1016/j.jcat.2025.116367","DOIUrl":"10.1016/j.jcat.2025.116367","url":null,"abstract":"<div><div>A nickel based covalent organic framework (Ni(II)@TFPA-COF) was designed and synthesized by bonding the double bonds of olefins and imines formed through orthogonal Schiff base reaction and Knoevenagel condensation using 4-aminobenzyl cyanide and tris-(4-formylphenyl) amine as starting materials, and its structure and optical properties were characterized. Ni(II)@TFPA-COF was used as a recyclable catalyst to develop a visible-light-induced reaction strategy for the directed <em>ortho</em>-trifluoromethylation of aromatic amide, and a series of <em>ortho</em>-trifluoromethylated aromatic amides were synthesized with good yields under mild and green conditions. Ni(II)@TFPA-COF exhibited good dual-functionality in photocatalysis and transition metal catalysis in the reaction. Based on the control experiments and literatures, a possible reaction mechanism for visible-light-induced directed C–H activation was proposed. This provides a novel, green, sustainable and efficient solution for the <em>ortho</em>-trifluoromethylation reaction of aromatic amides.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116367"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826036","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":"Insights into the roles of Niδ+ species on the selective hydrogenation of oleic acid to jet fuel","authors":"Jinlin Mei ,&nbsp;Zhentao Liu ,&nbsp;Xiaoyang Kong ,&nbsp;Aocheng Wang ,&nbsp;Dongze Li ,&nbsp;Dong Li ,&nbsp;Yanjun Gong ,&nbsp;Xiaochun Zhu ,&nbsp;Chunming Xu ,&nbsp;Xilong Wang","doi":"10.1016/j.jcat.2025.116375","DOIUrl":"10.1016/j.jcat.2025.116375","url":null,"abstract":"<div><div>Revealing the exact catalytic sites and reaction mechanism is crucial for the production of bio-jet fuel from biomass-derived oleic acid. The activation of C–O bonds and C–C bonds of oleic acid were the keys in waste oil upgrading, yet the active sites and mechanism still remain inconclusive on Ni-based catalysts. Herein, we studied the activation characteristics of C-O bonds and C–C bonds of Ni species to clearly distinguish the role of Ni^δ+ of Ni-based catalysts in selective hydrogenation reaction. The ultrafine Ni species of Ni/ZS-NP (Ni/ZSM-22-SBA-15) promoted the generation of more Ni^δ+ species, which could greatly facilitate the adsorption of reactants. Then the adsorbed carboxyl groups on Ni^δ+ was further hydrogenated by H, which was activated by the adjacent metal sites. Meanwhile, the activation of C-O and C–C bonds adsorbed on Ni^δ+ species occurred in the subsequently selective hydrogenation process, and the higher jet fuel yield implied that the activation of C–C bonds by Ni^δ+ species in the isomerization and hydrocracking reactions was particularly significant. Ni/ZS-NP exhibited the higher jet fuel yield of 62.3 % and the higher iso/n alkane ratio of 3.33 at 320 °C, which were superior to the catalysts reported in the previous literature. These findings distinguish different roles of Ni species in Ni-based catalysts, providing different insights into the fundamental understanding of the selective hydrogenation process of oleic acid hydrogenation to jet fuel.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116375"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826033","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":"PPh2H-involving mixed ligands-controlled Rh-catalyzed iso-selective hydroformylation of 1,3-butadiene","authors":"Jun-Hui Zhu ,&nbsp;An-Jiu Wen ,&nbsp;Fei Ye ,&nbsp;Lin Shi ,&nbsp;Wen-Jing Shang ,&nbsp;Shu-Yuan Tian ,&nbsp;Zheng Xu ,&nbsp;Li Li ,&nbsp;Chun-Gu Xia ,&nbsp;Li-Wen Xu","doi":"10.1016/j.jcat.2025.116377","DOIUrl":"10.1016/j.jcat.2025.116377","url":null,"abstract":"<div><div>The hydroformylation of olefins is a cornerstone of homogeneous catalysis and industrial chemistry, yet achieving precise regioselectivity, particularly for 1,3-butadiene, remains a formidable challenge. Here we introduce a transformative rhodium-based catalytic system that achieves unprecedented efficiency in the hydroformylation of 1,3-butadiene, yielding dialdehydes with exceptional efficiency (up to 88 %). Our strategy employs a mixed dual-ligand system combining a tetradentate phosphine ligand and a diphenylphosphane, which synergistically facilitate the two-stage hydroformylation process during the catalytic cycle of CO insertion. This cooperative function of mixed ligands enables the selective production of 2-ethylbutanedial with a record-breaking <em>iso</em>-selectivity of up to 67.8 %. Mechanistic investigations, supported by computational and experimental studies, reveal the critical and competitive role of binary mixed-ligand catalysis (BMLC) and ligand-relay catalysis (LRC) in this reaction. Specifically, three coordination modes derived from multidentate phosphine and monodentate diphenylphosphane ligands alternately govern key steps of the catalytic cycle, including olefin activation and regioselective insertion<em>.</em></div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116377"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819474","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":"Unveiling the surface hydroxyl-modulated effects for Cu1/γ-Al2O3 (110) in the direct oxidation of methane to methanol","authors":"Yanjun Chen ,&nbsp;Mengyao Sun ,&nbsp;Weiye Li ,&nbsp;Zhi Li ,&nbsp;Dong Li ,&nbsp;Lian Kong ,&nbsp;Xiaoqiang Fan ,&nbsp;Zean Xie ,&nbsp;Xiaoying Sun ,&nbsp;Bo Li ,&nbsp;Zhen Zhao","doi":"10.1016/j.jcat.2025.116376","DOIUrl":"10.1016/j.jcat.2025.116376","url":null,"abstract":"<div><div>Surface microchemical environments of catalysts can bring potential modulations on catalytic processes, particularly for isolated active centers with high structural sensitivity. In this work, we focus on the direct methane (CH₄)-to-methanol (CH₃OH) (DMTM) oxidation with oxygen (O₂), and theoretically decipher the critical effects of surface hydroxyl (–OH) species on single-atom copper supported on alumina (Cu₁/γ-Al₂O₃). On the one hand, OH-(Cu, Al) (bonding with Cu and Al) can alleviate the orbital splitting of Cu₁ 3d and thus inhibit its migration. Simultaneously, the changes in orbital interactions also largely intensify O₂ activation, thereby facilitating the formation of highly reactive Cu−O^- species that can trigger CH₄ homolysis with a lower energy barrier. On the other hand, OH-(Al, Al) (bonding with Al and Al) plays the role of a proton bridge and alters the generation channel of the second CH₃OH molecule. Specifically, OH-(Al, Al) first releases H to combine with the foreign OH*, and the newly formed H₂O* can weaken CH₃* adsorption, subsequently mediating methanol formation and reconstructing OH-(Al, Al). In addition, the presence of –OH promotes the surface desorption of CH₃OH and thus greatly prevents product overoxidation. This work provides insights into exploiting efficient DMTM catalysts from the perspective of surface functional group modifications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116376"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144826032","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":"Adsorption-competition driven volcano catalysis in TS-1: the critical role of Ti3+-VO defect concentration tailored by hydrogen reduction","authors":"Yujie Liao,&nbsp;Sijia Wang,&nbsp;Daiyi Yu,&nbsp;Yang Zheng,&nbsp;Jundi Wang,&nbsp;Yuxia Zhong,&nbsp;Zhihua Zhang,&nbsp;Xuezhi Duan,&nbsp;Xinggui Zhou","doi":"10.1016/j.jcat.2025.116379","DOIUrl":"10.1016/j.jcat.2025.116379","url":null,"abstract":"<div><div>A novel hydrogen-mediated thermal reduction strategy is employed to introduce Ti³⁺-V_O defects into TS-1 without foreign element contamination. Defect concentrations are precisely tuned by adjusting reduction conditions, and their impact on propylene epoxidation with hydrogen and oxygen (HOPO) was investigated. The formation of Ti³⁺ species and oxygen vacancies is confirmed by XPS and EPR. Meanwhile, XRD, FT-IR, and N₂-BET indicated no significant alterations to the MFI framework and porosity of TS-1. In-situ DRIFTS and kinetics experiments revealed that Ti³⁺-V_O defects simultaneously promoted the adsorption of both propylene and PO, with propylene adsorption dominating at low defect concentrations and PO adsorption dominating at high concentrations, causing a volcano-shaped relationship between catalytic activity and Ti³⁺-V_O defect concentration. Consequently, TS-1 with optimal defect concentration can significantly enhance propylene conversion, PO selectivity, and PO formation rate in HOPO reaction. The findings highlight the importance of precise defect engineering for optimizing the catalytic activity of TS-1.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116379"},"PeriodicalIF":6.5,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819472","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":"Mechanistic insights into nitrogen activation on atomic Ru clusters in self-pillared pentasil using operando atomistic models and experimental kinetics","authors":"Geet Gupta ,&nbsp;Weiye Qu ,&nbsp;Zihao Rei Gao ,&nbsp;Wei-Ling Huang ,&nbsp;Ryan Zhou ,&nbsp;Lu Ma ,&nbsp;Nayeon Kang ,&nbsp;Paul Haghi Ashtiani ,&nbsp;Fan Bu ,&nbsp;Jeffrey T. Miller ,&nbsp;Michael Tsapatsis ,&nbsp;Chao Wang ,&nbsp;Brandon C. Bukowski","doi":"10.1016/j.jcat.2025.116374","DOIUrl":"10.1016/j.jcat.2025.116374","url":null,"abstract":"<div><div>Alternative catalysts to the industrial Haber Bosch process have been of significant interest in the field of heterogeneous catalysis, yet realizing ammonia synthesis under mild conditions (e.g., 300 °C and 10 bar) is challenging due to the low per-pass conversion. One strategy is to promote the associative ammonia synthesis mechanism which eschews direct N-N bond cleavage. Here we use self-pillared pentasil, a self-pillared hierarchical zeolite built by thin MFI zeolite nanosheets, as a support for subnanometric Ru clusters to synthesize ammonia. We show that Ru remains well-dispersed during reaction and further demonstrate that ammonia synthesis rates are higher than Cs-Ru/MgO. Reaction kinetics show a positive order in H₂ providing evidence for the associative mechanism, which then becomes negative in H₂ if Ru is allowed to aggregate into nanoparticles. <em>Operando</em> Density Functional Theory models for Ru speciation in SPP, free energy diagrams, and microkinetic modeling were then applied to develop a reaction mechanism that involves sequential hydrogenation of N₂ from metallic Ru clusters. For this hydrogenation to occur, there are site requirements for N₂ to adopt a bridge-bound configuration that facilitates sequential hydrogenation on single sites and metal clusters. These site requirements in turn inform the design of improved zeolite-supported ammonia synthesis catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116374"},"PeriodicalIF":6.5,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819473","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":"Extended π-conjugation of D–A ligand enabling a CuI-based hybrid compound as sensitive fluorescent sensor and efficient photodegradation catalyst for tetracycline","authors":"Ya-Li Yang ,&nbsp;Bing Shao ,&nbsp;Yi Huang ,&nbsp;Bi-Liu Lan ,&nbsp;Min Pan ,&nbsp;Zi-Ling Li ,&nbsp;Zhong Zhang","doi":"10.1016/j.jcat.2025.116372","DOIUrl":"10.1016/j.jcat.2025.116372","url":null,"abstract":"<div><div>The judicious selection and rational design of the chromogenic ligands are deemed as a critical aspect to enhance the photoluminescent and/or photocatalytic performance of organic–inorganic hybrid materials. Here, a D–A type Schiff-base ligand, N-(anthracen-9-ylmethylene)pyrazine-2-amine (<strong>AIPZ</strong>) was deliberated-designed and prepared which drives the generation of a one-dimensional CuI hybrid compound, <strong>1D-CuI(AIPZ)</strong>. Though both <strong>2D-CuI(APZ)</strong>, a two-dimensional CuI-based hybrid from 2-aminopyrazine (<strong>APZ</strong>), and <strong>1D-CuI(AIPZ)</strong> are equipped with one-dimensional CuI modules, the photoluminescence studies and optoelectronic property measurements disclosed that the latter features the optimized energy band structure, intensified photoluminescent behavior, and higher carrier separation and transfer ability. Remarkably, <strong>1D-CuI(AIPZ)</strong> is competent as a bifunctional material for selective fluorescent detection of tetracycline (TC) with 0.261 µM detection limit in the dark, and photocatalytically eliminating 94.14 % of this pollutant within 60 min under visible light irradiation. The insight into the contribution of the extended D–A structure of <strong>AIPZ</strong> on the superior photoluminescence efficiency and photocatalytic activity of <strong>1D-CuI(AIPZ)</strong> than <strong>2D-CuI(APZ)</strong> was established by the combined experimental and theoretical approaches. Moreover, the promising applicability of <strong>1D-CuI(AIPZ)</strong> for the detection and photocatalytic treatment of TC-containing wastewater was validated by two experimental facts: the satisfactory recovery rate for monitoring TC in real water matrices, the preservation of more than 70 % of degradation rate for TC irradiated by the natural light. This work offers a feasible ligand-engineering approach to integrate and optimize the fluorescent detection and photocatalytic removal abilities of the organic–inorganic hybrid materials for common environmental pollutants.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116372"},"PeriodicalIF":6.5,"publicationDate":"2025-08-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144802933","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-catalyzed ring-opening hydrocyanation of methylenecyclopropanes toward cyano-substituted quaternary carbon centers","authors":"Jianxi Chen,&nbsp;Zhaohang Jiang,&nbsp;Ting Wang,&nbsp;Mingdong Jiao,&nbsp;Xianjie Fang","doi":"10.1016/j.jcat.2025.116361","DOIUrl":"10.1016/j.jcat.2025.116361","url":null,"abstract":"<div><div>Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes represents a useful transformation, typically yielding 1,2-hydrofunctionalization products as the major outcome. In this work, we report an unprecedented, highly selective nickel-catalyzed hydrocyanation of methylenecyclopropanes that affords 1,4-hydrofunctionalization products, forming acyclic cyano-substituted quaternary carbon centers. Mechanistic studies suggest that this reaction proceeds via a <em>β</em>-carbon elimination process involving a diene intermediate. DFT calculations further revealed that the regioselectivity for quaternary carbon center formation was controlled by a delicate interplay of steric and noncovalent interactions during the C–CN reductive elimination step.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116361"},"PeriodicalIF":6.5,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144802937","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":"Structure-oriented optimization of hierarchical porous conjugated polymers for enhanced PET-RAFT polymerization","authors":"Qing Jiang, Yunye Huang, Zhen Lu, Yuanhao Lin, Xiafeng Liao, Danni Tang, Linxi Hou, Longqiang Xiao","doi":"10.1016/j.jcat.2025.116366","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116366","url":null,"abstract":"Hierarchically porous materials are highly valued for their large surface areas and tunable pore architectures, making them promising heterogeneous catalysts for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. However, the specific influence of pore structure on catalytic performance remains poorly understood. In this study, hierarchically porous conjugated organic polymers (COPs) were synthesized using a silica hard-template method and employed as photocatalysts for PET-RAFT polymerization. Under white LED light irradiation, the effects of template size and concentration on pore structure and photocatalytic performance were systematically investigated. Notably, a silica template with a concentration of 60 mg/mL and a particle size of 300 nm produced a COP with an average pore size of 6.91 nm, which exhibited the best photocatalytic performance. The polymerization rate under these conditions was 2.5 times higher than that of the control. The synergy among micropores, mesopores, and macropores enhanced photocatalytic efficiency by increasing surface area, promoting mass transfer, and improving charge carrier mobility. Spectroscopic and electrochemical analyses further revealed that the optimized pore structure significantly enhances charge carrier dynamics by facilitating charge separation and migration. This structural modulation effectively reduces charge recombination, thereby improving the photocatalytic efficiency in PET-RAFT polymerization. These findings provide valuable insights into the rational design of porous photocatalysts for advanced PET-RAFT systems.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"70 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144797550","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}