Journal of Catalysis最新文献

{"title":"Assembly of functional Co(II)−organic frameworks through a mixed ligand strategy: structure, photocatalytic oxidation of sulfides and CO2 conversion","authors":"Tian-Cai Yue,&nbsp;Xin-Fang Wang,&nbsp;Jian-Bo Huang,&nbsp;Lu-Lu Wang,&nbsp;Duo-Zhi Wang","doi":"10.1016/j.jcat.2026.116700","DOIUrl":"10.1016/j.jcat.2026.116700","url":null,"abstract":"<div><div>Four new Co(II)-based metal–organic frameworks (MOFs) were successfully synthesized by a mixed ligand strategy. The controllable transformation of the bridging groups in the secondary structural units was achieved by modulating the anions in MOFs <strong>1</strong>–<strong>4</strong>. The catalytic performance study indicated that MOF <strong>1</strong> exhibited excellent photocatalytic activity for the oxidation of sulfides to sulfoxides under the air atmosphere and •O₂⁻ and ¹O₂ were the main active species in the photocatalytic reaction process. Furthermore, MOF <strong>1</strong> also could efficiently catalyze the carboxylative cyclization of propargylic amines with CO₂ and the possible catalytic mechanism was explored in detail. Importantly, MOF <strong>1</strong> can exhibit remarkable catalytic activity after five cycles in both reactions. Therefore, MOF <strong>1</strong> can be used as an efficient and stable heterogeneous catalyst for the oxidation of sulfides and the carboxylative cyclization of propargylic amines with CO₂.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116700"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145961877","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":"Inducing polar electric fields via molecular unit symmetry breaking for boosting photocatalysis","authors":"Xiaoyu Nie ,&nbsp;Chengyi Ou ,&nbsp;Jingwen Liang ,&nbsp;Chenglong Ru ,&nbsp;Xiaobo Pan ,&nbsp;Sibo Wang ,&nbsp;Zhi-An Lan","doi":"10.1016/j.jcat.2026.116711","DOIUrl":"10.1016/j.jcat.2026.116711","url":null,"abstract":"<div><div>The separation and transport efficiency of photogenerated charge carriers are critical factors determining the photocatalytic performance of semiconductors. However, the lack of a direct and effective driving force for charge separation leads to rapid recombination of most photogenerated carriers within the bulk or on the surface of photocatalysts, severely limiting their output efficiency. Constructing an internal polarization electric field to drive the directional migration of charges and suppress carrier recombination has been demonstrated as an effective strategy. In this study, we designed and synthesized two conjugated polymers with distinct symmetries via a local π-skeleton modulation strategy of molecular units. We systematically clarified the regulatory mechanism underlying the disruption of molecular structural unit symmetry on the photocatalytic charge transport process. Both experimental results and theoretical calculations demonstrated that the breaking of molecular unit symmetry induces an internal electric field within the photocatalyst, which provides an intrinsic driving force for the directional migration and rapid accumulation of electrons. This process establishes a continuous π-electron delocalization channel, creating a “charge superhighway”, while reducing the exciton binding energy (<em>E</em>_b) to significantly suppress carrier recombination, thereby substantially enhancing the photocatalytic performance. This study demonstrates the polarization effect caused by the disruption of molecular unit symmetry, which can amplify the electric field strength to optimize charge separation and provide a design option for high-efficiency organic photocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116711"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033864","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":"Tris(pentafluorophenyl)borane (BCF)-catalyzed meinwald rearrangement of epoxides","authors":"Hiyab T. Mekonnen ,&nbsp;Guanhua Wang ,&nbsp;Sukaran Arora ,&nbsp;Arjun Raghuraman ,&nbsp;Linda Broadbelt ,&nbsp;Justin M. Notestein","doi":"10.1016/j.jcat.2026.116709","DOIUrl":"10.1016/j.jcat.2026.116709","url":null,"abstract":"<div><div>The isomerization of epoxides is a valuable transformation in synthetic chemistry, offering an atom-economical route to aldehydes and ketones from readily available substrates. In this study, we investigate tris(pentafluorophenyl)borane (B(C₆F₅)₃ or BCF) as a Lewis acid catalyst for the Meinwald rearrangement using propylene oxide and other epoxides as models. The effects of residual water, temperature, and solvent properties such as coordination strength, polarity, and hydrogen-bonding ability are systematically examined to determine their impact on catalytic activity and product selectivity. ¹⁹F and 2D HOESY NMR spectroscopy, along with density functional theory (DFT) calculations, reveal key BCF–solvent interactions that govern catalytic behavior. In particular, [BCF·OH₂]·(solvent) pre-catalyst complexes are proposed to explain the activation period observed in strongly coordinating solvents. BCF is very active for aldehyde formation, and these findings highlight the critical roles of water activity and solvent coordination strength in modulating catalytic activity by determining the amount of free BCF. In addition, hydrogen-bonding ability of the solvent governs the selectivity towards Meinwald rearrangement products in BCF-catalyzed reactions<em>.</em> The insights gained are broadly applicable to understanding catalyst–solvent interactions in other organoborane systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116709"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005831","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":"Kinetic study and modeling of the process for the methyl pelargonate synthesis by 1-octene methoxycarbonylation using CO and the catalytic system Pd(OAc)2–PPh3–p-toluenesulfonic acid","authors":"Nadezhda T. Sevostyanova,&nbsp;Sergey A. Batashev,&nbsp;Dar’ya K. Kozlenko","doi":"10.1016/j.jcat.2026.116674","DOIUrl":"10.1016/j.jcat.2026.116674","url":null,"abstract":"<div><div>A kinetic study of the 1-octene methoxycarbonylation has been carried out. The target product of the reaction is methyl pelargonate (MP), which is of interest as an intermediate for pharmaceutical syntheses. Using the Pd(OAc)₂/PPh₃/TsOH (TsOH is p-toluenesulfonic acid) as a catalytic system, the 1-octene methoxycarbonylation proceeded regioselectively for MP and was complicated by the formation of only branched esters. Under mild conditions, TOF could achieve values of more than 10^-2 s⁻¹, which opens up the possibility this reaction implementing in industry. A model of reaction selectivity for MP and a kinetic model of the reaction have been obtained. These models are the necessary basis to develop the MP synthesis reactor and the technology for producing this product. Optimal conditions for the 1-octene methoxycarbonylation have been found. The interpretation of the established regularities for the reaction has been given within the framework of the hydride mechanism scheme supplemented by reactions of the low-activity Pd-complexes formation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116674"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956888","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 of stable and active (NHC)Pd–phosphine catalysts for the synthesis of high-molecular-weight norbornene-based polymers","authors":"Anna P. Khrychikova ,&nbsp;Evgeniya V. Bermesheva ,&nbsp;Nadezhda V. Nesterova ,&nbsp;Anastasia A. Danshina ,&nbsp;Yulia V. Nelyubina ,&nbsp;Maxim V. Bermeshev","doi":"10.1016/j.jcat.2026.116678","DOIUrl":"10.1016/j.jcat.2026.116678","url":null,"abstract":"<div><div>A series of cationic palladium complexes of the composition [(NHC)Pd(allyl)(PR₃)]⁺BARF⁻ containing N-heterocyclic carbene (NHC) and phosphine ligands of different nature, and a weakly coordinating borate anion were synthesized. Such Pd complexes were for the first time investigated as single-component catalysts for vinyl-addition polymerization of norbornene and its functionalized derivatives. The complexes exhibit high catalytic activity without the need for co-catalysts (to 7·10⁶ g_polymer/mol_Pd h). Polymers synthesized over these Pd complexes in question are characterized by unimodal GPC curves, narrow molecular weight distributions, and linear dependence of the molecular weight on the monomer conversion, which suggests the occurrence of controlled polymerization. It was demonstrated that both the structure of NHC and the nature of phosphine ligand have strong effect on catalytic activity and initiation efficiency. A correlation between Pd—P bond length and the behavior of the complex in the polymerization reaction was revealed, <em>viz</em>.: the shorter Pd—P bond the lower the lability of the phosphine, the initiation efficiency, and the higher the molecular weights of the resulting polymers. As a result, polymerization on the title complexes allows one to obtain polymers with much higher molecular weights compared to polymers synthesized using similar (NHC)Pd systems with other labile ligands. Besides, the synthesized complexes demonstrate high thermal stability and retain their catalytic activity at elevated temperatures. Generally, the presence of the NHC and phosphine ligands in palladium coordination sphere provides a unique balance between the activity, stability, and possibility to obtain high-molecular-weight products. This makes the complexes in hand promising catalysts for targeted synthesis of functional polymeric materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116678"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145956897","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":"Y-induced oxygen vacancy engineering and local electronic reconstruction for enhanced ammonia decomposition over Ni1Ce1-xYxOα","authors":"Zhixian Bao ,&nbsp;Huibin Liu ,&nbsp;Yizhou Zhang ,&nbsp;Zhiheng Wang ,&nbsp;Hao Li ,&nbsp;Haoquan Hu","doi":"10.1016/j.jcat.2026.116718","DOIUrl":"10.1016/j.jcat.2026.116718","url":null,"abstract":"<div><div>Ammonia decomposition is considered an ideal carbon-free pathway to hydrogen production. However, the limited catalytic activity of non-noble metal catalysts for ammonia decomposition remains a major barrier to their industrial deployment. Here, we developed a modulation strategy that simultaneously tunes the structural and electronic properties of Ni-based catalysts to improve their catalytic performance. Yttrium (Y) was introduced as a dopant via a citrate sol–gel auto-combustion method into Ni/CeO₂, enabling compositionally controlled Y incorporation over the electron–defect landscape. This method yields a well-defined Ni₁Ce_1-xY_xO_α structure, in which Y³⁺, with its different ionic radius from Ce⁴⁺, is homogeneously incorporated into the CeO₂ lattice to form a solid solution, generating abundant and stable surface oxygen vacancies and modulating the electronic environment of Ni active sites. Among the Ni₁Ce_1-xY_xO_α catalysts prepared, Ni₁Ce_0.5Y_0.5O_α exhibits the highest activity, achieving 84% NH₃ conversion at 550 °C (GHSV = 30000 mL·g_cat^-1·h⁻¹) and a H₂ production rate of 1687 ± 14 mmol·g_cat^-1·h⁻¹, along with robust thermal stability. The calculated results suggest that Y doping decreases the formation energy of oxygen vacancies and perturbs the local electronic environment, which enhances electron transfer to the Ni active sites, increasing Ni valence electron density. N associative desorption as the rate-determining step (RDS) was determined at Ni₁Ce_0.5Y_0.5O_α, in which the electronic modulation, in synergy with surface oxygen vacancies, reduces the energy barrier for N association by 0.21 eV and renders this step thermodynamically favorable. This work demonstrates that the strategic use of Y as a dual-functional promoter enhances the catalytic activity in ammonia decomposition.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116718"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089810","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":"Enhanced charge transfer and oxygen vacancies by interface engineering for CO2 reforming of toluene","authors":"Yongqi Kuang ,&nbsp;Jiawen Ma ,&nbsp;Sibudjing Kawi ,&nbsp;Shuzhuang Sun ,&nbsp;Yuqianer Zeng ,&nbsp;Lina Liu","doi":"10.1016/j.jcat.2025.116665","DOIUrl":"10.1016/j.jcat.2025.116665","url":null,"abstract":"<div><div>CO₂ reforming of tar reaction (CRT) is a promising method for simultaneous removal and conversion of CO₂ and tar in syngas from the biomass gasification technology, which is essential for utilization and upgrading of syngas. However, the deactivation of supported Ni catalysts by sintering and carbon deposits remains the most challenging issue. In this study, (Mg, Al, Ce)O_x <!-->nanosheet-supported Ni-based catalysts with varying Ce/Ni ratios (0, 0.1, 0.2, 0.3) were constructed from freeze-dried Ni–Ce–Mg–Al LDH precursors with the thermally dried Ni–Ce_0.2–Mg–Al LDH as a reference. The result suggested that freeze drying favored the achievement of loose nanosheets and highly dispersed metals. With the optimized Ce dosage (Ce/Ni = 0.2), the Ni–Ce_0.2–F–R catalyst exhibited the most superior activity and stability over 40h time-on-stream. The possible reason is that Ni–Ce_0.2–F–R catalyst possessed abundant and homogeneously distributed<!--> <!-->Ni–CeO₂ interface, which accelerated the electron transfer from CeO₂ to Ni via Ni–O_v–Ce structure (Ov, oxygen vacancy). An electron-rich state of Ni was thus achieved, which could effectively activate the C–H and C–C bonds. Furthermore, the abundant oxygen defects and stronger alkaline sites of the CeO₂ support promoted the adsorption and activation of CO₂, which was conducive to the elimination of coke adjacent Ni metal sites. <em>In situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) suggested that the abundant surface-active oxygen species facilitated the deep oxidation and ring opening of the benzene ring.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116665"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895321","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 four-component carbonylation reaction of terminal alkynes and arenes toward α, β-unsaturated esters","authors":"Qiangwei Li ,&nbsp;Ting Yang ,&nbsp;Xiao-Feng Wu","doi":"10.1016/j.jcat.2026.116704","DOIUrl":"10.1016/j.jcat.2026.116704","url":null,"abstract":"<div><div>Owing to the high reactivity of the carbon–carbon triple bond, alkynes can react with various reagents to give functionalized alkenes and alkanes, making it a useful compound to build complex molecules. Herein, we reported a one-pot, two-step strategy which use arenes and alkynes as the reactant combined with carbon monoxide to afford α, β-unsaturated esters. The transformation goes through iodonium ions intermediate and proceed under mild conditions, a series of the target products were generated in good to excellent yields.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116704"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014716","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":"Photoredox-catalyzed three-component cyanoalkylation of glycine derivatives: Enabled by dual nitrogen-centered radicals","authors":"Wen-Lin Zou,&nbsp;Zhi Guan,&nbsp;Yan-Hong He","doi":"10.1016/j.jcat.2026.116694","DOIUrl":"10.1016/j.jcat.2026.116694","url":null,"abstract":"<div><div>A photoredox-catalyzed three-component reaction has been developed, in which two distinct nitrogen-centered radicals are generated through sequential reductive and oxidative processes mediated by the photocatalyst. This transformation involves C–C bond cleavage and generation of an α‑aminoalkyl radical as parallel key steps, enabling alkene difunctionalization to achieve <em>N</em>-α-alkylation at the α-C(sp³)-H site of <em>N</em>-aryl glycine derivatives. This method offers a novel approach for the synthesis of unnatural amino acids bearing diverse functional groups. The reaction proceeds under mild conditions and exhibits broad substrate scope, facilitating the preparation of a series of <em>N</em>-aryl glycine derivatives containing cyanoalkyl groups.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116694"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962567","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":"Photocatalytic in-situ reductive fragmentation and coupling of lignin β-O-4 linkages to pinacols","authors":"Jingjing Yang ,&nbsp;Ting Li ,&nbsp;Chengyan Zou ,&nbsp;Jinlan Cheng ,&nbsp;Kaiyi Su ,&nbsp;Bo Jiang ,&nbsp;Hao Li ,&nbsp;Zhengwei Li ,&nbsp;Chaofeng Zhang","doi":"10.1016/j.jcat.2026.116714","DOIUrl":"10.1016/j.jcat.2026.116714","url":null,"abstract":"<div><div>Compared with the aromatic monomer preparation, the lignin catalytic transformation to dimers with higher added value has received extensive attention recently. Different from the stepwise tandem synthesis strategies for dimer preparation, which involve the first lignin depolymerization to monomers and following monomer coupling to dimers, we here achieved the <em>in-situ</em> photocatalytic reductive fragmentation-coupling of the pre-oxidized lignin β-O-4 linkages to pinacols. The optimized TiO₂-R(1 1 0) (rutile) could efficiently achieve the transformation of 2-phenoxy-1-phenylethanone with <em>i</em>-PrOH as the hydrogen donor under UV LED irradiation, providing an 83.0% yield of 2,3-diphenylbutane-2,3-diol and a 78% yield of phenol in 15 h. Mechanism studies indicated that the activated TiO₂-R with critical surface Ti³⁺ species under UV LED irradiation mediated the first photocatalytic cleavage of the C_β–OAr bond of 2-phenoxy-1-phenylethanone to phenol and acetophenone. The generated acetophenone further underwent semi-reduction and carbon radical coupling to provide the pinacol, dominated by the UV LED irradiation and improved by the TiO₂-R(1 1 0) surface. The revelation of the catalytic mechanism can provide ideas for the subsequent direct conversion of lignin to high-value dimer products.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116714"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033866","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}