Journal of Catalysis最新文献

英文中文

Enabling bimetallic cooperativity in tetrameric Ru(II) complexes for efficient and selective aerobic oxidative amidation of primary amines 使四聚体Ru（II）配合物中的双金属协同作用有效和选择性地进行伯胺的有氧氧化酰胺化

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-10-01 DOI: 10.1016/j.jcat.2026.117230

Nimesh R. Chauhan,Priyanka V. Patat,Sakshi,Angshuman Roy Choudhury,Komal M. Vyas

引用次数: 0

From single atoms to nanoparticles: growing rhodium nanoparticles on MgO toward stable COx-free hydrogen production from ammonia 从单原子到纳米粒子：在氧化镁上生长铑纳米粒子，以稳定地从氨中产生无氧化酶的氢

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-10-01 DOI: 10.1016/j.jcat.2026.117211

Ahmet Safa Aydogdu,Yasin Kalay,Büşra Sekizkardeş,Ugur Unal,Özge D. Bozkurt,Adam S. Hoffman,Jiyun Hong,Jorge E. Perez-Aguilar,Simon R. Bare,Samira F. Kurtoğlu-Öztulum,Alper Uzun

引用次数: 0

Structure–reactivity relationships in [Cp*Ru(MeCN)3][PF6]-catalyzed anti- and syn-selective hydrosilylation of internal alkynes and 1,3-diynes [Cp*Ru(MeCN)3][PF6]催化内炔和1,3-二炔反选择性和同选择性硅氢化反应的结构-反应关系

IF 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-10-01 DOI: 10.1016/j.jcat.2026.117229

Konrad Stęsik,Kinga Stefanowska,Jędrzej Walkowiak,Adrian Franczyk

引用次数: 0

Simple donor functionalization in D-A type conjugated polymers for improved photocatalytic H2O2 production activity under visible light D-A型共轭聚合物的简单给体功能化提高可见光下光催化生产H2O2的活性

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-09 DOI: 10.1016/j.jcat.2026.116756

Changzhi Han , Tianci Chen , Shibo Lv , Jingwen Pan , Sihui Xiang , Jia-Xing Jiang

Anthraquinone (AQ) based organic conjugated polymers are promising photocatalysts for H₂O₂ photosynthesis from O₂ and H₂O, since the AQ unit with strong electron withdrawing ability can not only promote the charge separation but also act as redox active center to generate H₂O₂ via oxygen reduction reaction (ORR). Herein, three novel donor–acceptor type organic polymers are reported to elucidate the influence of simple donor functionalization on charge dynamics and ORR activity. Compared to biphenyl donor without functionalized group, acetylene functionalized diphenylacetylene donor and diacetylene functionalized 1,4-diphenylbutadiyne donor show reduced twisted angles between adjacent benzene rings and increased coplanarity of polymer chains, which promotes the charge transfer and separation along the polymer chains. Besides, the presence of diacetylene group in donor extends the π conjugation and broadens the light absorption range of DPB-AQ. Benefiting from the donor–acceptor structure, broad absorption range of visible light, upgraded charge transfer and separation ability, DPB-AQ exhibits a higher photocatalytic H₂O₂ yield of 7.8 mmol h⁻¹ g⁻¹ than BPH-AQ (1.0 mmol h⁻¹ g⁻¹) and DPA-AQ (3.8 mmol h⁻¹ g⁻¹) in pure water without additives. This work highlights the critical role of simple donor functionalization in polymers for H₂O₂ photosynthesis from H₂O and O₂.

蒽醌（AQ）基有机共轭聚合物具有很强的吸电子能力，不仅能促进电荷分离，还能作为氧化还原活性中心通过氧还原反应（ORR）生成H2O2，是O2和H2O光合作用的光催化剂。本文报道了三种新的给体-受体型有机聚合物，以阐明简单给体功能化对电荷动力学和ORR活性的影响。与不含官能团的联苯给体相比，乙炔官能团化的二苯基乙炔和二乙炔官能团化的1,4-二苯基丁二炔给体相邻苯环之间的扭角减小，聚合物链的共平面度增大，促进了电荷沿聚合物链的转移和分离。此外，二乙炔基团的存在扩大了DPB-AQ的π共轭，扩大了其光吸收范围。在无添加剂的纯水条件下，DPB-AQ光催化H2O2产率为7.8 mmol h−1 g−1，高于BPH-AQ （1.0mmol h−1 g−1）和DPA-AQ （3.8mmol h−1 g−1）。这项工作强调了简单的供体功能化在聚合物中从H2O和O2进行H2O2光合作用的关键作用。

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引用次数: 0

Manganese-catalyzed transfer hydrogenation of indoles to indolines: reaction scope and mechanistic investigation 锰催化吲哚转移加氢制吲哚：反应范围及机理研究

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-04 DOI: 10.1016/j.jcat.2026.116732

Ying Xu , Zihan Zhang , Yizhou Wang , Longfei Li , Ning Ma , Zheng Wang , Huiliang Li , Yanping Ma , Wen-Hua Sun

A family of new ligands (L1–L8) and non-pincer-type PN-Mn(I) complex Mn1 containing the imidazoline motif have been successfully employed for the transfer hydrogenation of N-unprotected indoles with H₃NBH₃ (AB) as the hydrogen source, giving high efficiencies (TON up to 7200) and good compatibility with functional groups, which surpasses the activity of most effective noble metal catalysts for this reaction. The reaction kinetics investigations, control experiments, and DFT computations highlighted that the central amido/amino-based bifunctional activation step employed a concerted N–H and B-H activation reaction pathway, and the hydride/proton-transfer process is the rate-determining step. More importantly, a proposed catalytic cycle involves an outer-sphere pathway for the reduction of the isomerized CN bond rather than the CC bond in the indole. Furthermore, this catalytic protocol provides a convenient and efficient method for the synthesis of a wide variety of indolines (26 examples) and saturated N-heterocycles such as tetrahydroberberine (2 examples).

一类新的配体（L1-L8）和含有咪唑啉基的非钳型PN-Mn(I)配合物Mn1以H3NBH3 （AB）为氢源，成功地用于n-无保护的吲哚的转移加氢反应，具有很高的效率（TON高达7200）和与官能团的良好相容性，其活性超过了大多数有效的贵金属催化剂。反应动力学研究、对照实验和DFT计算表明，中心氨基/氨基双功能活化步骤采用协同的N-H和B-H活化反应途径，氢化物/质子转移过程是速率决定步骤。更重要的是，所提出的催化循环涉及一个外球途径，用于还原吲哚中的异构化CN键而不是CC键。此外，该催化方案为多种吲哚类化合物（26例）和饱和n -杂环化合物如四氢小檗碱（2例）的合成提供了一种方便高效的方法。

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引用次数: 0

Carbonylation catalysis of aryl halides through active-site engineering 活性位点工程催化芳基卤化物羰基化

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-05 DOI: 10.1016/j.jcat.2026.116733

Arjun Neyyathala , Felix Jung , Claus Feldmann , Simon Barth , Jan-Dierk Grunwaldt , Ivana Jevtovikj , Stephan A. Schunk , Paolo Dolcet , Silvia Gross , Schirin Hanf

Crystalline palladium phosphide nanoparticles supported on silica (Pd₃P/SiO₂, 5 wt% Pd) are explored as catalysts for the alkoxycarbonylation of lignin-derived aromatic synthons, using model aryl halides as representative substrates. The detailed characterization by PXRD, HAADF-STEM, HRTEM, EDX, ICP-AES, XPS, CO-DRIFTS, and CO chemisorption confirmed the formation of the Pd₃P phase with uniform nanoparticle size distribution. The catalytic performance was evaluated in a three-phase reaction system comprising a CO gas atmosphere, a liquid phase containing the solvent and substrate and a solid catalyst. The incorporation of phosphorus into the palladium lattice resulted in a more than two-fold enhancement in catalytic activity compared to conventional Pd-based heterogeneous catalysts. The Pd₃P/SiO₂ catalyst also outperformed several reported heterogeneous and commonly used homogeneous catalysts. This enhanced reactivity is attributed to the electronic and geometric effects introduced by phosphorus, which generate highly active, spatially-isolated Pd sites. These findings demonstrate the potential of Pd–P phase engineering for the design of the next-generation of carbonylation catalysts.

研究了二氧化硅负载的结晶磷化钯纳米颗粒（Pd3P/SiO2, 5 wt% Pd）作为木质素衍生芳香族合成物烷氧羰基化的催化剂，以模拟芳基卤化物为代表底物。通过PXRD、HAADF-STEM、HRTEM、EDX、ICP-AES、XPS、CO- drifts和CO化学吸附等详细表征，证实了Pd3P相的形成，具有均匀的纳米粒度分布。在一个由一氧化碳气体气氛、含有溶剂和底物的液相和固体催化剂组成的三相反应体系中评估了催化性能。与传统的钯基非均相体系相比，磷掺入钯晶格导致催化活性提高了两倍以上。Pd3P/SiO2催化剂的性能也优于几种已报道的多相和常用的均相催化剂。这种增强的反应性归因于磷引入的电子和几何效应，它们产生了高活性的、空间隔离的Pd位点。这些发现证明了Pd-P相工程在设计下一代羰基化催化剂方面的潜力。

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引用次数: 0

Copper-catalyzed boron radical-enabled 1,4-selective diboryldimerization of styrenes 铜催化硼自由基活化苯乙烯的1,4选择性二硼基二聚反应

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-09 DOI: 10.1016/j.jcat.2026.116754

Zhihui Jia , Fengxiang Zhu , Xiao-Feng Wu

A copper-catalyzed, boron radical-mediated strategy for the 1,4-diboryldimerization of styrenes is described. This method enables the direct coupling of two olefin units with concomitant installation of two boryl groups, providing efficient access to 1,4-diboryl-1,4-diphenylbutane derivatives from simple starting materials. The reaction proceeds under mild conditions and exhibits broad functional group tolerance, accommodating various substituted styrenes with good efficiency and, in many cases, high diastereoselectivity. Mechanistic investigations, including radical-trapping and control experiments, support a pathway involving boryl and carbon-centered radical intermediates, distinguishing this process from classical two-electron migratory insertion mechanisms. This work offers a practical and step-economical route to extended diborylated frameworks and highlights the potential of merging copper catalysis with radical chemistry for olefin dimerofunctionalization.

描述了一种铜催化，硼自由基介导的苯乙烯1,4-二硼基二聚化策略。该方法使两个烯烃单元的直接偶联与两个硼基的同时安装，提供了从简单的起始原料高效地获得1,4-二硼基-1,4-二苯基丁烷衍生物。该反应在温和的条件下进行，并表现出广泛的官能团耐受性，以良好的效率容纳各种取代苯乙烯，并且在许多情况下具有高的非对映选择性。机制研究，包括自由基捕获和控制实验，支持涉及硼基和碳中心自由基中间体的途径，将这一过程与经典的双电子迁移插入机制区分开来。这项工作为扩展二硼化框架提供了一条实用和经济的途径，并强调了将铜催化与自由基化学合并用于烯烃二聚功能化的潜力。

引用次数: 0

Cu-catalyzed regioselective borylative cyclization of silicon-bridged allenyl bromides: toward 4-silacyclohexenyl boronates 铜催化硅桥接烯基溴的区域选择性硼化环化：生成4-硅环己烯基硼酸盐

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jcat.2026.116727

Fei Ye , Xiao-Fang Wang , An-Jiu Wen , Chen-Li Jin, Wen-Hao Shi, Jian Cao, Zheng Xu, Li-Wen Xu

The development of mild and straightforward synthetic approaches that simultaneously construct the silacyclic scaffold and introduce of functional group in a single step remain largely elusive. Herein, we report a copper(I)-catalyzed borylative cyclization of silicon-tethered allenyl bromides with diboron reagents, enabling efficient access to novel boryl-functionalized silacyclohexenes. This robust method affords a diverse range of 4-silacyclohexenyl boronates in moderate to good yields with high regio- and chemoselectivity across a broad substrate scope. Further transformation of the alkenyl boronate moiety provides access to a series of novel functionalized six-membered silacycles. Mechanistic insights, supported by DFT calculations, reveal key factors governing the regioselectivity of the cyclization step.

同时构建硅环支架和在一步中引入官能团的温和而直接的合成方法的发展在很大程度上仍然是难以实现的。在此，我们报道了铜(I)催化的二硼试剂对硅系烯基溴的硼化环化反应，从而有效地获得了新型的硼基功能化硅环己烯。这种稳健的方法提供了不同范围的4-硅环己烯基硼酸盐在中等到良好的产量具有高区域和化学选择性在广泛的底物范围。硼酸烯基部分的进一步转化提供了一系列新的功能化六元硅环。由DFT计算支持的机理见解揭示了控制环化步骤区域选择性的关键因素。

引用次数: 0

Unraveling the distinct catalytic features of methane activation in an iron-containing hemicryptophane cage FeO-TPA@Hm: insights from molecular cage architecture and electronic interactions 揭示含铁半氪烷笼中甲烷活化的独特催化特征FeO-TPA@Hm：来自分子笼结构和电子相互作用的见解

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-02-02 DOI: 10.1016/j.jcat.2026.116731

Xin-Rui Mao, Chao-Yu Zhao, Yi-Zhou Gong, Ke-Xin Xing, Guang-Shan Zhu, Cai-Yun Geng

In this study, we present a comprehensive investigation of the methane C–H activation catalyzed by an iron-containing hemicryptophane molecular cage FeO-TPA@Hm, combined with an in-depth exploration of the reaction mechanisms via electronic structure analysis, revealing distinctive features in both the reactivity and mechanism of this catalytic system. It was found that the modulation of the electronic states at the active center is achieved by the Hm molecular cage structure, breaking the conventional “inert framework + active center” paradigm and endowing the system with unprecedented activity and mechanisms. Furthermore, the hydrophobic microenvironment of the Hm cage further enhances the catalytic performance, providing a theoretical explanation for the exceptional catalytic behaviors observed experimentally. This study proposes a balanced catalyst design strategy that synergistically integrates moderate electronic effects with efficient hydrophobic enhancement, aiming to maximize both catalytic efficiency and selectivity in methane conversion processes. Overall, the findings offer significant theoretical insights and practical guidance for the development of methane activation catalysts, opening new avenues for research in catalytic chemistry and related fields.

在本研究中，我们对含铁半氪烷分子笼FeO-TPA@Hm催化的甲烷C-H活化进行了全面的研究，并通过电子结构分析对反应机理进行了深入的探讨，揭示了该催化体系在反应性和机理上的鲜明特点。研究发现，Hm分子笼结构实现了活性中心电子态的调制，打破了传统的“惰性框架 + 活性中心”范式，使体系具有前所未有的活性和机制。此外，Hm笼的疏水微环境进一步提高了催化性能，为实验观察到的异常催化行为提供了理论解释。本研究提出了一种平衡的催化剂设计策略，将适度的电子效应与高效的疏水增强协同结合，旨在最大限度地提高甲烷转化过程的催化效率和选择性。研究结果为甲烷活化催化剂的开发提供了重要的理论见解和实践指导，为催化化学及相关领域的研究开辟了新的途径。

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引用次数: 0

Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction 用MOF涂层调制Cu电极微环境：来自分子动力学和CO还原电化学实验的见解

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.jcat.2026.116723

Manish Maurya , Hannah Fejzić , Xavier C. Krull , Huy Nguyen , Matthew Neurock , Joseph T. Hupp , Chibueze V. Amanchukwu , Rachel B. Getman

Metal-organic frameworks (MOFs) present a compelling strategy for tuning electrochemical interfaces by reshaping interfacial solvent structure. In this study, we examine how MOF coatings influence the microenvironment at copper electrodes during the CO electroreduction reaction (CORR) using a combined approach of molecular dynamics (MD) simulations and electrochemical experiments. Two MOFs, NU-901 and ZIF-8, are selected to explore the impact of pore size and channel hydrophobicity on electrochemical activity and interfacial concentration in acetonitrile (ACN) and dimethyl sulfoxide (DMSO) electrolytes. Electrochemical measurements reveal that MOF@Cu electrodes exhibit lower Faradaic efficiencies for CO hydrogenation products (ethylene and methane) compared to bare copper but have dramatic impacts on the interfacial microenvironment. NU-901, with its larger pores and strong interactions with DMSO, traps DMSO molecules and enhances CO coordination in DMSO but suppresses CORR selectivity in favor of the hydrogen evolution reaction (HER). ZIF-8, with smaller pores and hydrophobic channels, limits the interfacial water concentration, and, in ACN, promotes CO coordination. The simulations provide insights into how MOFs can act as physical modulators of reactant delivery and interfacial structure to control electrochemical microenvironments. This work highlights the value of molecular dynamics in uncovering how structural features of MOFs influence interfacial phenomena, even when catalytic performance is not directly improved.

金属有机框架（MOFs）通过重塑界面溶剂结构来调整电化学界面是一种引人注目的策略。在这项研究中，我们使用分子动力学（MD）模拟和电化学实验相结合的方法研究了在CO电还原反应（CORR）过程中，MOF涂层如何影响铜电极上的微环境。选择NU-901和ZIF-8两种mof，探讨了孔径和通道疏水性对乙腈（ACN）和二甲基亚砜（DMSO）电解质中电化学活性和界面浓度的影响。电化学测量表明，MOF@Cu电极对CO加氢产物（乙烯和甲烷）的法拉第效率比裸铜低，但对界面微环境有显著影响。NU-901具有较大的孔隙和与DMSO的强相互作用，能捕获DMSO分子并增强CO在DMSO中的配位，但抑制了CORR选择性，有利于析氢反应（HER）。ZIF-8具有较小的孔隙和疏水通道，限制了界面水浓度，并在ACN中促进CO配位。模拟提供了mof如何作为化学物质传递和界面结构的物理调节剂来控制电化学微环境的见解。这项工作强调了分子动力学在揭示mof的结构特征如何影响界面现象方面的价值，即使在催化性能没有直接改善的情况下。

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