ACS Catalysis 最新文献

{"title":"Nickel-Catalyzed C(sp3)–H Arylation for the trans-Selective Synthesis of Sterically Congested Cyclopropanes and Other Cycloalkanes","authors":"Fengjie Huang,&nbsp;Erwan Brunard,&nbsp;Àlex Díaz-Jiménez,&nbsp;Joanna Wencel-Delord","doi":"10.1021/acscatal.6c06078","DOIUrl":"10.1021/acscatal.6c06078","url":null,"abstract":"<p>Cyclopropanes with a <em>gem</em>-substitution pattern are of significant structural importance, with key applications in the fields of drug design and agrochemistry. However, despite substantial progress in 4d- and 5d-metal-catalyzed C–H activation of cyclic alkanes, direct functionalization of <em>gem</em>-dimethyl substituted cyclopropanes remained an unmet challenge. In this paper, we set out a preliminary general strategy to address this challenge. Not only abundant and inexpensive Ni-catalyst can be used, but also the uncommon <em>trans</em>-selectivity can be attained under the optimized reaction conditions. This direct arylation reaction demonstrates a broad substrate scope in terms of aryl-iodide coupling partner. In addition to this, it can be directly applied to the functionalization of other cyclic alkanes, including adamantyl cores, which are notoriously challenging to process. The experimental mechanistic studies, in combination with DFT calculations, provide a rational explanation for the mechanism of this transformation and the uncommon <em>trans</em>-selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20655–20663"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092087","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":"Heterogenization of Ru(bda) Molecular Catalyst with Redox-Active and Proton-Buffering Porphyrin Linkers for Acidic Water Oxidation","authors":"Feiyang Zhang,&nbsp;Jun Li,&nbsp;Xin Cui,&nbsp;Kaixuan Wang,&nbsp;Zhuoming Wei,&nbsp;Weili Shi,&nbsp;Yu Guo,&nbsp;Yuxiang Song,&nbsp;Yonglong Li,&nbsp;Huatian Xiong,&nbsp;Shaoqi Zhan,&nbsp;Licheng Sun,&nbsp;Biaobiao Zhang","doi":"10.1021/acscatal.6c05703","DOIUrl":"10.1021/acscatal.6c05703","url":null,"abstract":"<p>We report a porphyrin-bridged Ru(bda) coordination polymer integrated with carbon nanotubes, constructed from the well-defined homogeneous water oxidation catalyst in acid. The porphyrin linker simultaneously provides redox activity and proton-buffering functionality, enabling acidic water oxidation at an ultralow Ru loading (0.021 mg_Ru·cm^–2). The resulting composite reaches current densities up to 200 mA·cm^–2 in acid, exceeding previously reported molecular water oxidation catalyst-based anodes by one to two orders of magnitude. At identical metal loadings, it also outperforms both RuO₂ and IrO₂ benchmarks in both activity and stability. Electrochemical, spectroscopic, and theoretical results support porphyrin protonation and reversible oxidation, suggesting that ligand redox activity, together with proton management, contributes to the enhanced catalytic performance. These findings underscore the transformative potential of ligand engineering in molecular integration strategies for advancing artificial photosynthetic energy conversion systems.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20573–20585"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092493","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 Dispersion of In2O3 into H-CHA and Reversible Formation of Isolated In(I)/In(III) Species under H2/O2 Redox Cycling","authors":"Tsz Lok Wan,Yuriko Ando,Mengwen Huang,Shinta Miyazaki,Yuxuan Xie,Fei Wang,Kai Li,Akihiko Anzai,Takashi Toyao,Ken-ichi Shimizu","doi":"10.1021/acscatal.6c05230","DOIUrl":"https://doi.org/10.1021/acscatal.6c05230","url":null,"abstract":"Abstract The reductive dispersion of metal oxides into isolated cationic species in zeolites is an important strategy for generating well-defined catalytic sites, yet its kinetics and molecular mechanism remain insufficiently understood. Here, we investigate the H2-induced redispersion of In2O3 physically mixed with H-CHA using in situ/operando UV–vis spectroscopy, In K-edge X-ray absorption near-edge structure (XANES), SEM-EDS mapping, modulation-excitation spectroscopy, H2-TPR, XRF, and density functional theory (DFT) calculations. Time-resolved UV–vis spectroscopy quantitatively tracks the consumption of bulk-like In2O3 under H2 and reveals that the redispersion rate depends on temperature, H2 concentration, In2O3 precursor properties, and zeolite framework. Higher temperatures and H2 concentrations accelerate the process, with the highest reliable initial rate observed at 600 °C under 10% H2. In K-edge XANES indicates selective formation of reduced In species assigned to framework-stabilized In+ rather than metallic In0, demonstrating a partial-reduction pathway in CHA. H2-TPR provides quantitative redox evidence consistent with reductive solid-state ion exchange and reversible reduction of isolated oxygen-containing In species. SEM–EDS mapping shows the disappearance of surface In-rich domains after H2 treatment, consistent with indium redistribution, while XANES provides bulk-sensitive evidence for formation of reduced In species. Operando redox-cycling experiments reveal reversible interconversion between In(I) and oxygen-containing In(III) species under H2/O2 switching. DFT calculations using representative 1Al and 2Al CHA models suggest that local Al environments can influence the relative stability of framework-bound reduced In(I) and oxygen/hydroxyl-containing In(III)-type species. Together, these results support a two-step mechanism in which bulk In2O3 is first reduced to mobile In+ species and then anchored at acid sites within the zeolite framework. This work provides mechanistic insight into reductive redispersion and offers design principles for regenerable indium-based zeolite catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"19 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209938","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":"Synergy of Ni Nanoparticles and MoO\u0000 x\u0000 Species for Selective Hydrodeoxygenation of Lignin into Cycloalkanes","authors":"Zifan Wu,Yuting Qiu,Longyu Zhang,Lu Chen,Qian Yang,Yichuan Li,Yuan Pan,Bin Liu,Bin Dong,Chenguang Liu,Yongming Chai","doi":"10.1021/acscatal.6c02892","DOIUrl":"https://doi.org/10.1021/acscatal.6c02892","url":null,"abstract":"Abstract The selective hydrodeoxygenation of lignin as a substitute for fossil resources into aviation fuel-range cycloalkanes faces significant challenges due to its complex structure and diverse reaction pathways. Herein, we introduced MoOx species onto Ni nanoparticles-loaded Beta zeolite (Ni-0.2MoOx/Beta), which catalyzed the complete hydrodeoxygenation of lignin dimers and lignin-derived phenols into the corresponding cycloalkanes under mild conditions (200 °C, 2 MPa H2). Ni-0.2MoOx/Beta also enabled the hydrodeoxygenation of real lignin, achieving a cycloalkanes selectivity of over 83%. Mechanistic studies indicated that the synergistic effect between Ni nanoparticles and MoOx species was key to enhancing the hydrodeoxygenation performance. Ni nanoparticles enabled the adsorption and dissociation of H2, and horizontally adsorbed benzene ring in the oxygen-containing substrate, while adjacent MoOx species with abundant oxygen vacancies facilitated the vertical adsorption of oxygen-containing groups in the ring-saturated intermediates and the activation of C–O bonds. Simultaneously, the strong hydrogen spillover on Ni-0.2MoOx/Beta ensured the benzene ring hydrogenation and the cleavage of C–O bonds. This work provides an approach for designing non-noble metal catalysts for lignin hydrodeoxygenation, holding significant value for advancing the application of lignin-based aviation fuels.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"39 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210187","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":"Localized Surface Plasmon Resonance-Induced Interfacial Dynamic Charge Circulation in Plasmonic Ohmic Heterojunctions for Optimizing Hydrogen Evolution Kinetics","authors":"Xiaolong Ma,&nbsp;Zhiqiang Wu,&nbsp;Teng Li,&nbsp;Youji Li,&nbsp;Zhiliang Jin,&nbsp;Noritatsu Tsubaki,&nbsp;Doron Aurbach,&nbsp;Janusz Lipkowski,&nbsp;Paolo Fornasiero","doi":"10.1021/acscatal.6c04688","DOIUrl":"10.1021/acscatal.6c04688","url":null,"abstract":"<p>It remains a formidable challenge to precisely regulate interfacial charge transfer kinetics via architecting high-efficiency heterointerfaces, thereby achieving optimized hydrogen evolution reaction (HER) activity. Here, we report a strategy based on work function-mediated heterojunction engineering, through which the V₂C MXene/ZnS plasmon ohmic heterojunction (ZC-10) was precisely designed and synthesized, achieving the synergistic optimization of hydrogen evolution kinetics from the dual dimensions of carrier transport and electronic structure. Combined results from in situ XPS, KPFM, EPR, and femtosecond transient absorption (fs-TA) spectroscopy, alongside density functional theory (DFT) calculations, demonstrate that the introduction of V₂C MXenes not only significantly enhances the light-harvesting capability of the ZnS but also simultaneously activates both the enriched excited-state electrons and intrinsic free electrons within V₂C MXenes via the localized surface plasmon resonance (LSPR) effect. These electrons are co-converted into high-energy excited electrons. These energetic electrons undergo reverse injection into the conduction band of ZnS for stabilization, which establishes a dynamic charge circulation mechanism at the heterojunction interface, thereby prolonging the carrier lifetime of the ZC-10 plasmon ohmic heterojunction. Meanwhile, the d–p orbital hybridization effect in the ZC-10 heterojunction activates its d¹⁰ electronic configuration, thereby simultaneously optimizing the d–p double orbital center. Such synergistic modulation of the electronic structure effectively balances the kinetics of the hydrogen adsorption/desorption (<em>H</em>_ADS/<em>H</em>_DES) processes, substantially lowering the Gibbs free energy of <em>H</em>^* adsorption (Δ<em>G</em>_H). This work provides an example for designing high-performance MXene-based plasmon photocatalysts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20144–20159"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050262","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":"Carbon-Supported Pt-Rich Cr-Mn-Fe-Co-Ni-Pt Nanoparticles for Enhanced Oxygen Reduction Reaction","authors":"Wiljar Lobjakas,&nbsp;Rutha Jäger,&nbsp;Peeter Valk,&nbsp;Priit Möller,&nbsp;Mairis Bērziņš,&nbsp;Jaan Aruväli,&nbsp;Peeter Paaver,&nbsp;Marian Külaviir,&nbsp;Jekaterina Kozlova,&nbsp;Valdek Mikli,&nbsp;Enn Lust,&nbsp;Jaak Nerut","doi":"10.1021/acscatal.6c04746","DOIUrl":"10.1021/acscatal.6c04746","url":null,"abstract":"<p>In this work, a fast moving bed pyrolysis method was used for the synthesis of multimetal catalyst nanoparticles, which have higher ORR activity and durability than those of the Pt–C catalyst synthesized by the same method and a commercial Pt–C catalyst. Carbon-supported multimetal catalyst nanoparticles (Cr₁₀Mn₁₀Fe₁₀Co₁₀Ni₁₀Pt₅₀) were synthesized, and the Pt fraction increased from 55 to 66 at% by acid washing. Structural characterization revealed that multimetal catalysts consist of well-dispersed nanoparticles, whose diffraction patterns were assigned to an L1₀-type ordered intermetallic structure rather than to the disordered fcc structure characteristic of the conventional CrMnFeCoNi Cantor alloy. The mass and specific activities (MA, SA) of both catalysts in 0.1 M HClO₄ at 0.9 V vs RHE are approximately three times higher than those for commercial Pt–C, reaching 780 A g_Pt^–1 and 17 A m_Pt^–2, respectively. The activity enhancement reflects a genuine increase in intrinsic site activity rather than a surface area effect. After 10,000 potential cycles, the multimetal catalysts retained 84–87% of their initial electrochemically active surface area (ECSA), compared with 66% for commercial Pt–C. Although the multimetal catalysts showed lower relative retention of MA and SA than commercial Pt–C, their higher initial activities resulted in substantially higher absolute ORR activities after cycling. Degradation analysis indicated selective dissolution of 3d metals during potential cycling and possible Pt redeposition, reinforcing the formation of a Pt-rich near-surface region, which contributes to higher retention of the ECSA of these catalysts. This performance arises from the combination of an ordered L1₀ intermetallic structure, a Pt-rich near-surface region, and a chemically complex subsurface, enabling high intrinsic ORR activity while mitigating the loss of electrochemically accessible Pt surface area.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20160–20174"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092071","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":"Redefining the Value Proposition of Photoelectrochemical Systems: Unique Reaction Knobs for Selective Chemical Synthesis","authors":"Kaijian Zhu,&nbsp;Lan Wen,&nbsp;Fatwa F. Abdi","doi":"10.1021/acscatal.6c06578","DOIUrl":"10.1021/acscatal.6c06578","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19676–19683"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092073","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":"Near-Atomic Indium Catalysts Enable Cost-Efficient High-Pressure Reverse Water–Gas Shift","authors":"Xinhuilan Wang,&nbsp;Saleh Ibrahim S. Altuwayjiri,&nbsp;Polina Tolstova,&nbsp;Alejandra Rendón-Patiño,&nbsp;Rafia Ahmad,&nbsp;Motaz Khawaji,&nbsp;Mohnnad H. Alabsi,&nbsp;Luigi Cavallo,&nbsp;Jean Marcel R. Gallo,&nbsp;Jorge Gascon","doi":"10.1021/acscatal.6c04882","DOIUrl":"10.1021/acscatal.6c04882","url":null,"abstract":"<p>The reverse water–gas shift (RWGS) reaction is a pivotal step for converting CO₂ into value-added chemical intermediates, yet its implementation under industrially relevant high-pressure conditions remains limited by catalyst deactivation, insufficient productivity, and prohibitive material costs. Here, we report a near-atomic indium catalyst supported on monoclinic ZrO₂ that addresses these challenges. Strong In–O–Zr interfacial interactions formed at low indium loadings promote oxygen-vacancy formation while suppressing the over-reduction and sintering of indium oxide, enabling stable operation at temperatures up to 500 °C and pressures of 20 bar. Under these demanding conditions, a catalyst containing only 2.5 wt % In₂O₃ achieves a CO yield of 42.2 ± 1.9% with a CO productivity of 1305 ± 58 mmol g_cat^–1 h^–1, exceeding previously reported high-pressure RWGS catalysts. Importantly, the low indium content translates into an estimated metal cost of the catalyst of around 12 USD kg^–1, comparable to conventional RWGS catalysts while delivering substantially higher performance. These results demonstrate that interface-engineered, low-loading oxide catalysts provide a cost-effective and scalable pathway for high-pressure RWGS, enabling further advancement toward industrial deployment.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20273–20286"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148760344","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":"Palladium-Catalyzed Divergent Cycloaddition of Arylalkynes with Norbornene Derivatives","authors":"Sakura Takahashi,&nbsp;Mamoru Tobisu,&nbsp;Yusuke Ano","doi":"10.1021/acscatal.6c04049","DOIUrl":"10.1021/acscatal.6c04049","url":null,"abstract":"<p>A palladium-catalyzed (3 + 2) cycloaddition between arylalkynes and norbornene derivatives via C–H bond cleavage is reported. This reaction enables the selective synthesis of benzo-fused five-membered cyclic products from a variety of arylalkynes, including electronically biased and alkyl(aryl)alkynes. Notably, the use of a bulky bidentate ligand leads to the (2 + 2) cycloaddition, giving cyclobutene derivatives from the same starting materials. Mechanistic studies indicate that both cycloadditions proceed through hydropalladation of the arylalkynes by Pd(0) and AcOH to generate a vinyl–Pd intermediate. Density functional theory calculations suggest a ligand-to-ligand hydrogen transfer mechanism for this step. The subsequent turnover-determining step is proposed to vary with the ligand environment, involving either C–H bond cleavage or reductive elimination, thereby governing pathway selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20025–20037"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149050272","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":"Residue-Position-Dependent Modulation of Urethanase Activity for Polyurethane Depolymerization","authors":"Mingna Zheng,&nbsp;Jiawei Liu,&nbsp;Xiaomin Zhu,&nbsp;Caihua Liang,&nbsp;Ziqin Li,&nbsp;Qingzhu Zhang,&nbsp;Weixin Zhang,&nbsp;Wenxing Wang,&nbsp;Ren Wei,&nbsp;Weiliang Dong,&nbsp;Yanwei Li","doi":"10.1021/acscatal.6c04525","DOIUrl":"10.1021/acscatal.6c04525","url":null,"abstract":"<p>Enzymatic depolymerization of hydrolyzable plastics, such as polyurethane (PU), opens a promising route for the eco-friendly recycling of plastic waste. A comprehensive understanding of the molecular mechanisms governing enzyme-catalyzed PU hydrolysis is crucial for engineering high-performance enzymes. Here, we combined extensive molecular dynamics simulations, hybrid quantum mechanics/molecular mechanics calculations, and experimental mutagenesis to elucidate how residues in distinct spatial regions regulate substrate binding and catalysis in UMG-SP2. Our results reveal that residues in the first shell (e.g., L140) stabilize the substrate in a catalytically productive conformation within the active-site pocket. Three flexible loop regions, H215–L227, L320–D346, and S377–L400, are identified as potential regulators of substrate capture. Furthermore, we quantify the contributions of individual surface-exposed charged residues to the reaction-relevant electric fields in the active site. The reaction mechanism comprises acylation and deacylation stages, with the rate-determining step corresponding to water-assisted nucleophilic attack. Experimental mutagenesis demonstrates that substitutions at residues in different spatial regions selectively modulate substrate binding and catalytic activity, leading to distinct and substrate-dependent effects on low-molecular-weight dicarbamate hydrolysis and PU depolymerization. Collectively, these findings reveal a residue-position-dependent modulation framework for urethanase activity and establish a general mechanism-guided strategy for advancing enzymatic PU depolymerization and recycling.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20089–20101"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090605","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}