ACS Catalysis 最新文献

{"title":"Spin-State Engineering of Tetrahedral Fe Sites Directs Selective NO Oxidation to Overcome the Activity-Selectivity Trade-off in NH3-SCR","authors":"Yue Xuan,&nbsp;Luyang Zhao,&nbsp;Xiao Zhu,&nbsp;Bin Wang,&nbsp;Yanjie Liang,&nbsp;Chuan Gao,&nbsp;Yang Yun,&nbsp;Dong Wang","doi":"10.1021/acscatal.6c04913","DOIUrl":"10.1021/acscatal.6c04913","url":null,"abstract":"<p>FeMn-based oxides are widely recognized as one of the most promising catalyst systems for low-temperature selective catalytic reduction (SCR) of NO_<em>x</em> with NH₃; however, their practical application is constrained by the intrinsic trade-off between activity and selectivity. Herein, Cr was introduced into FeMnO_<em>x</em> to regulate the oxidation behavior and reaction pathway through spin-state engineering of Fe sites. Cr doping induces a phase transformation from α-Fe₂O₃ to γ-Fe₂O₃ and generates high-spin tetrahedrally coordinated Fe (Fe_Td) sites. Consequently, FeMnCrO_<em>x</em> maintains NO_<em>x</em> conversions above 90% over a broad temperature window of 120–255 °C, while increasing N₂ selectivity at 175 °C from below 40% to above 90%, with satisfactory resistance toward H₂O and SO₂. Characterizations and density functional theory calculations reveal that the spin-polarized Fe_Td sites selectively channel activated oxygen toward NO oxidation rather than NH₃ over-oxidation. Fe_Td serves as the preferential adsorption and activation site for NO, and the enhanced orbital-selective π-backdonation between Fe_Td and adsorbed reactants (<em>d</em><em>x</em>²-<em>y</em>² → NO π^*, <em>d</em><em>xy</em> → O₂ π^*), enables cooperative NO^δ−/O₂^δ− activation, lowering the NO oxidation barrier from 2.25 to 1.41 eV. The enhanced NO₂ formation enables a Lewis-acid-mediated fast SCR pathway. This work establishes a strategy for directing oxidation capability toward desired reaction pathways through spin-state engineering, providing mechanistic insights into the design for overcoming activity-selectivity trade-offs in NH₃-SCR catalysis.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20220–20234"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092414","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":"In Situ Hydrogen Utilization in Plastic Waste Recycling and Upcycling","authors":"Xinyang Sun,&nbsp;Hongshun Ran,&nbsp;Tao Guo,&nbsp;Yaxuan Jing","doi":"10.1021/acscatal.6c05704","DOIUrl":"10.1021/acscatal.6c05704","url":null,"abstract":"<p>The management of waste plastics poses a significant challenge due to their inherent chemical stability, large-scale production, and short service life. As plastics are primarily composed of carbon and hydrogen, there is growing interest in the high-value conversion of plastic waste for the targeted production of hydrogen. However, the thermodynamic constraints of the processes, along with the associated challenges in hydrogen storage and transportation, limit the practical application of hydrogen production technologies derived from plastic waste. Consequently, in situ utilization of hydrogen generated from plastic waste has emerged as a promising strategy. This perspective elucidates the fundamental principles of in situ hydrogen utilization and establishes a theoretical framework for evaluating existing studies and guiding future research. Based on this framework, we systematically assess the latest advancements, critically addressing the challenges encountered and proposing directions for future research. The objective of this paper is to provide a comprehensive roadmap for the efficient utilization of hydrogen energy derived from plastic waste, thereby facilitating the establishment of a hydrogen circular economy.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19725–19751"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092490","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":"Regiodivergent Oxyfuctionalization of Non-natural Tricyclic Terpenoids Using Sequence Divergent Unspecific Peroxygenases (UPOs)","authors":"Lena Fraedrich,&nbsp;Bonnie Winter,&nbsp;Ahmed Hassanin,&nbsp;Henry Struwe,&nbsp;Gerald Dräger,&nbsp;Jörn Droste,&nbsp;Mehdi D. Davari,&nbsp;Andreas Kirschning,&nbsp;Martin J. Weissenborn","doi":"10.1021/acscatal.6c06279","DOIUrl":"10.1021/acscatal.6c06279","url":null,"abstract":"<p>Unspecific peroxygenases (UPOs) catalyze the H₂O₂-dependent monooxygenation of organic substrates with regioselectivity and chemoselectivity; however, their application to sterically demanding, non-natural terpene skeletons has remained largely unexplored to date. Here, we present a computationally-guided, multiparametric screening pipeline that was used to prioritize 17 structurally distinct UPOs and UPO-like enzymes for the late-stage oxyfunctionalization of chemoenzymatically synthesized tricyclic terpenoids not reported from natural sources. These are accessible via BcBOT2-catalyzed cyclization of non-natural farnesyl diphosphate analogs. The computer-aided pre-screening included an evaluation of expression levels, an analysis of the tunnel architecture for substrate access, and hierarchical docking using geometric criteria close to the attack conformation to rank candidate enzymes. Experimental screening of the prioritized enzymes identified productive UPO-substrate combinations showed correspondence between the docking-based regioselectivity predictions and the product profiles confirmed by GC–MS. <em>Mth</em>UPO FuncLib_18 catalyzed an “orchestrated” linear cascade of three consecutive oxidations of a furan sesquiterpenoid, converting it into an α-hydroxylactone—a transformation that mimics the natural oxidative diversification that biosynthetically follows terpene cyclization. In addition, a single inversion of the stereocenter in the furano sesquiterpenoids diastereomer pair redirected the regioselectivity of <em>M</em>spUPO-mg133 and <em>Chi</em>UPO-II to opposite sides of the furan ring. This finding thus represents a proof-of-concept for regioselectivity reversal through stereochemical changes in the substrate during UPO-catalyzed terpenoid oxidation. Additionally, we were able to access two structures with tertiary alcohols, difficult to achieve by chemical means. In silico comparison of AlphaFold 3 models, supported by multiple-sequence alignment, suggested that the <em>Monosporascus</em> UPOs characterized here form a distinct UPO/UPO-like subgroup characterized by an EHR catalytic motif, a shortened α-helix, an elongated loop, and an active-site lacking aromatic residues and exhibit comparatively the lowest predicted active-site hydrophobicity among all characterized UPOs. Molecular dynamics simulations, combined with an analysis of the near-attack-conformations of selected enzyme-substrate complexes, confirmed that only the experimentally observed oxidation positions achieve sustained proximity to the ferryl oxygen of compound I with catalytically suitable approach angles over timescales in the microsecond timescale. This work thus expands both the known sequence-structure space of catalytically competent UPOs and the accessible chemical space of terpenoids as substrates.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20675–20690"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151426","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":"Diastereoselective Heterogeneous Hydrogenation of Fused Arenes Directed by Amines and Alcohols","authors":"Anish Yadav,Vinay Kadian,William A. Swann,Ratri Biswas,Nicole K. Freundl,Zhenhua Zeng,Christina W. Li","doi":"10.1021/acscatal.6c05744","DOIUrl":"https://doi.org/10.1021/acscatal.6c05744","url":null,"abstract":"Abstract The heterogeneous hydrogenation of aromatic compounds using supported metal catalysts is an efficient strategy to increase the three-dimensionality and molecular complexity of organic molecules. However, most heterogeneous hydrogenation methods lack stereoselectivity or rely upon the steric properties of the substrate for stereocontrol, which limit their predictability and generality for pharmaceutical synthesis applications. In this work, we develop two synthetic methods for the amine- and hydroxyl-directed hydrogenation of benzofused arenes using Rh/C and Pt3Cu/SiO2 as heterogeneous catalysts, respectively. Mechanistic studies on the amine-directed reaction reveal that simultaneous adsorption of the amine and benzene functional groups to the Rh metal surface is extremely strong, outcompeting the adsorption of the benzene or amine individually and enabling good turnover and high diastereoselectivity toward the amine-directed product. A broad scope of benzofused scaffolds are effective substrates, generating up to four stereocenters in a single step. The utility of the method is demonstrated in the synthesis of a pyridine bisoxazoline compound derived from perhydro-cis-aminoindanol.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"54 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209935","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":"Reprogramming Interfacial Hydrogen-Bond Networks via Asymmetric Single-Atom Catalysts","authors":"Jize Li,&nbsp;Limeng Sun,&nbsp;Renyi Li,&nbsp;Zhuoyang Gong,&nbsp;Jiaye Li,&nbsp;Wenchao Hu,&nbsp;Hsingkai Chu,&nbsp;Xudong Peng,&nbsp;Yinning Zhu,&nbsp;Xiaoxia Chang,&nbsp;Ruiqin Zhong,&nbsp;Xiao Hai,&nbsp;Ruqiang Zou","doi":"10.1021/acscatal.6c04933","DOIUrl":"10.1021/acscatal.6c04933","url":null,"abstract":"<p>Interfacial water plays a pivotal role in electrocatalysis by governing proton-coupled electron transfer and reaction kinetics. However, strategies to actively regulate interfacial hydrogen-bond networks remain limited, and the role of atomic-scale catalytic sites in controlling water organization is still poorly understood. Here, we report a rapid Joule-heating strategy that converts symmetric Co-N₄ sites into asymmetric Co-N₃O₁ single-atom sites, enabling precise modulation of the interfacial hydrogen-bond network during catalysis. Combined experimental characterization and theoretical simulations reveal that O coordination breaks the local symmetry of Co centers, reconstructs interfacial water, and weakens over-connected hydrogen-bond networks, providing a more favorable interfacial environment for water-mediated proton transfer and oxygenated-intermediate conversion. As a result, the reconstructed interfacial hydrogen-bond network promotes efficient four-electron oxygen reduction, enabling Co-NC-N₃O₁ to achieve a half-wave potential of 0.866 V, substantially outperforming its symmetric Co-N₄ counterpart and surpassing commercial Pt/C. When integrated into aqueous zinc-air batteries (ZABs), Co-NC-N₃O₁ delivers a peak power density of 217.2 mW cm^–2 and a specific capacity of 805.1 mAh g_Zn^–1. This work reveals that asymmetric single-atom modulation can actively reprogram the interfacial hydrogen-bond network, providing a paradigm for catalyst-water interface engineering.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20259–20272"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090612","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":"PtPd Nanosheets Dominated with (111) Facets Achieving Thermodynamic–Kinetic Synergistic Enhancement of Oxygen Reduction Reaction","authors":"Lili Zhang,&nbsp;Shengwei Yu,&nbsp;Hao Jiang,&nbsp;Meng Zhang,&nbsp;Zikun Li,&nbsp;Xin Luo,&nbsp;Zihao Liu,&nbsp;Zhiwei Hu,&nbsp;Xiaojie Jia,&nbsp;Haibo Jiang,&nbsp;Jianhua Shen,&nbsp;Chunzhong Li","doi":"10.1021/acscatal.6c05462","DOIUrl":"10.1021/acscatal.6c05462","url":null,"abstract":"<p>The oxygen reduction reaction (ORR) in fuel cells suffers from an inherent thermodynamic bottleneck. Current research is mostly confined to independent optimization of either its thermodynamic or kinetic properties, failing to break through the catalytic performance limit imposed by classical models. Herein, PtPd alloy nanosheets dominated by the (111) facets, with a thickness of about 1–2 nm, were synthesized under high-pressure conditions using CO as the direct reduction gas. First-principles calculations demonstrate that PtPd alloy nanosheets thermodynamically optimize ORR by lowering the surface O adsorption energy, thereby positively shifting the onset potential to 1.02 V vs RHE. Furthermore, the distinct d-orbital electronic structure of Pd interacting with Pt enables enhanced electron filling into the antibonding orbitals of the OOH intermediate. This electronic modulation reduces the apparent activation energy by approximately 20 kJ mol^–1, kinetically accelerating the ORR process. This catalyst simultaneously increases the thermodynamic limiting potential and reduces the kinetic activation energy, ultimately leading to a mass activity of up to 1.275 A mg^–1 at 0.95 V_RHE, achieving 53.3 times the activity of commercial Pt/C.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20463–20472"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090860","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":"Metal-Organic Frameworks for Gas-Solid Reactive Carbon Dioxide Capture – Photo/Thermochemical Routes","authors":"Mandiaya Bugri,&nbsp;Thomson C. McCarthy,&nbsp;James M. Crawford","doi":"10.1021/acscatal.6c05917","DOIUrl":"10.1021/acscatal.6c05917","url":null,"abstract":"<p>Metal-organic frameworks (MOFs) are customizable adsorbents with demonstrated value for point-source and direct air capture of carbon dioxide (CO₂). Simultaneously, MOFs are emerging CO₂ reduction catalysts. Combining these independent pillars of success leads to the central focus of our review: the application of MOFs for reactive carbon capture (RCC), a process that eliminates intermediate separation, concentration, and transportation of CO₂ from the point of capture to the reactor. In the context of the present review, we consider a gas-solid RCC process where in one step, CO₂ is loaded on the material and in a second step, a co-reactant is fed to the reactor while energy in the form of heat or light stimulates product formation. Gas-solid RCC on pristine MOFs remains underexplored when compared with post-synthetically modified MOFs, amine-grafted frameworks, and solution-phase systems. This review critically assesses the dual functionality (capture and conversion) of MOFs, emphasizing their structural tunability, porosity, and photo/thermal catalytic activity. We systematically discuss central features, including CO₂ adsorption, thermochemical and photochemical CO₂ reduction pathways, and existing barriers to MOF RCC. We highlight specific features essential to RCC, including CO₂ chemisorption, band-gap modulation, and charge-transfer mechanisms for light-driven CO₂ reduction, and hydrogen/water activation pathways on MOFs. Finally, recent trends, challenges, and prospects in MOF design for RCC are discussed, offering a critical evaluation of their advantages, limitations, and potential for integrated RCC.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19783–19799"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092072","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":"Pendant Phosphonium Outperforms Ammonium by Strengthening Local Electric Fields in a Ruthenium Hydrogenation Catalyst","authors":"Manuel Quiroz,&nbsp;Elise M.-J. Banz Chung,&nbsp;Jack T. Fuller, III,&nbsp;Trinity Riggins,&nbsp;Katherine M. Marczenko,&nbsp;John C. Linehan,&nbsp;Bojana Ginovska,&nbsp;Marcel Schlaf,&nbsp;Eric S. Wiedner","doi":"10.1021/acscatal.6c03159","DOIUrl":"10.1021/acscatal.6c03159","url":null,"abstract":"<p>Pendant ammonium cations are known to enhance catalytic activity through the generation of local electric fields; however, there is little understanding of how the magnitude of these effects can be controlled through the cation identity. In this study, we investigate the impact of pendant pnictonium identity (ammonium versus phosphonium) incorporated into the ligand backbone of [Ru(triphos)(CH₃CN)₃]^<em>n</em>+ complexes for CO₂ hydrogenation to MeOH. Kinetic analysis by operando ¹H NMR spectroscopy demonstrates that the phosphonium-based complex achieves significantly higher turnover frequency and selectivity for production of MeOH compared to its lighter ammonium analogue and the neutral bridgehead control complex. Mechanistic experiments reveal that MeOH is formed through an on-cycle pathway in which the substrate remains bound to the catalyst; however, once partially reduced intermediates dissociate, they accumulate as off-cycle by-products that are not further converted to MeOH. Computational studies demonstrated that phosphonium substitution lowers the free-energy barrier for rate-limiting hydride transfer to the bound formate ligand. Natural bond orbital (NBO) analysis and electrostatic potential calculations indicate that phosphonium exhibits a higher localization of charge than the ammonium analog, resulting in an increased electrostatic stabilization of negative charge in the transition state. These findings demonstrate that changing the identity of a pendant pnictonium group can enhance enhance cationic effects and improve catalytic performance.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19927–19939"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092275","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":"Embrace the Mess: Theory for Disordered Surfaces of Working Catalysts","authors":"Karsten Reuter","doi":"10.1021/acscatal.6c06690","DOIUrl":"10.1021/acscatal.6c06690","url":null,"abstract":"","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19684–19692"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092491","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":"Light-Accelerated Iridium-Catalyzed C–H Borylation","authors":"Máire Griffin,&nbsp;Hrithik Manojkumar,&nbsp;Tabea Heil,&nbsp;Stuart A. Macgregor,&nbsp;Eric Slack,&nbsp;Eli Zysman Colman","doi":"10.1021/acscatal.6c04883","DOIUrl":"10.1021/acscatal.6c04883","url":null,"abstract":"<p>Here, we report a mild, light-assisted iridium-catalyzed C–H borylation protocol for organic substrates. We demonstrate that adapting the Ishiyama–Tagaki–Miyaura–Hartwig (ITMH) protocol for C–H borylation to proceed under photochemical conditions imparts a pronounced rate enhancement compared to the established dark reaction. This photochemistry methodology achieves higher yields across a broad range of substrates and is easily scalable using continuous flow technology.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20247–20258"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092075","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}