ACS Catalysis 最新文献

{"title":"Cobalt(III)-Catalyzed Synthesis of Chiral 1,2-Amino Alcohols by C–H Carboamidation","authors":"Wilfrido E. Almaraz-Ortiz, Nicolai Cramer","doi":"10.1021/acscatal.5c05544","DOIUrl":"https://doi.org/10.1021/acscatal.5c05544","url":null,"abstract":"An efficient enantioselective synthesis of vicinal amino alcohols by C–H functionalization of pyrazolo-substituted arenes and <i>O</i>-allyl hydroxylamines as amino alcohol C3-synthon with built-in amidation capability is reported. The transformation is enabled by a chiral cyclopentadienyl cobalt(III) complex, providing enantioselectivities of up to 98:2 er with a broad range of substrates. The generated chiral β-amino alcohols are versatile building blocks of high synthetic value. Notably, turnover numbers of up to 52 were achieved ranging in the very top-end for asymmetric high-valent cobalt C–H functionalization catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"6 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229077","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":"Preparation and Comparative Evaluation of Membrane Separators for Aqueous Electrochemical Nitrogen Reduction Reaction Measurements","authors":"Maximilian Christis, Xiang Li, Johannes Dittloff, Julius Kühne, Verena Streibel, Ian D. Sharp, Saswati Santra","doi":"10.1021/acscatal.5c02775","DOIUrl":"https://doi.org/10.1021/acscatal.5c02775","url":null,"abstract":"Catalyst screening for electrochemical nitrogen (N₂) reduction to ammonia (NH₃) suffers from spurious results caused by various sources of contamination associated with the experimental setup and the environment. As a crucial component of the electrochemical cell, a separator membrane is necessary to prevent the oxidation of as-synthesized NH₃, specifically for low-yield aqueous electrochemical nitrogen reduction reactions (EC-N₂RR). However, there remains a key need for a robust and contamination-free membrane, including systematic assessments of its electrochemical suitability for this reaction. Here, we report a simple yet effective cleaning process for the recently introduced microporous Celgard membrane. We show that the cleaned Celgard membrane outperforms other commonly used EC-N₂RR membranes in alkaline electrolytes, exhibiting superior ion transport compared to a Nafion proton exchange membrane and enhanced chemical inertness and structural stability compared to a Fumasep anion exchange membrane. Beyond guiding membrane selection, this study provides a comprehensive strategy for managing contamination and a framework for designing and operating nearly contamination-free EC-N₂RR workstations, enabling reliable catalyst screening for aqueous EC-N₂RR.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"42 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209836","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":"Regioselective Multiboration and Hydroboration of Alkenes and Alkynes Enabled by a Platinum Single-Atom Catalyst","authors":"Paweł Huninik, Priti Sharma, Vitthal B. Saptal, Martin Slaby, Rostislav Langer, Pawan Kumar, Ali Shayesteh Zeraati, Xiyang Wang, Martin Petr, Michal Otyepka, Manoj B. Gawande, Radek Zbořil, Stepan Kment, Jędrzej Walkowiak","doi":"10.1021/acscatal.5c03767","DOIUrl":"https://doi.org/10.1021/acscatal.5c03767","url":null,"abstract":"Selective multiboration including di- and triboration and hydroboration of alkynes and alkenes face significant challenges in organic synthesis, including achieving high regioselectivity, functional group tolerance, and catalyst stability while requiring mild conditions to maintain reactivity. These transformations have been predominantly explored by using homogeneous catalysts. In this study, we report the scalable synthesis of heterogeneous platinum single-atom catalyst (Pt-SAC) supported on ultrathin nanosheets of graphitic carbon nitride via a rapid microwave-assisted method. The Pt-SAC enables 1,2-diboration of sterically hindered alkenes and 1,2,2-triboration of alkynes with B₂pin₂ under mild conditions. For the diboration of styrene, the catalyst achieves 99% yield with 95% selectivity, a turnover number (TON) of 3711, and a turnover frequency (TOF) of 247 h^–1. The catalyst also promotes the regioselective hydroboration of alkenes and alkynes, yielding <i>anti</i>-Markovnikov alkylboranes and vinylboranes, respectively. Computational calculations reveal that the enhanced reactivity on the Pt-SAC catalyst arises from adsorption-induced weakening of key bonds (C=C and B–H), thereby significantly lowering the activation energy barriers. The Pt-SAC exhibits stability and recyclability, maintaining performance over at least eight consecutive runs without detectable Pt leaching. This study highlights the potential of Pt-SAC as a robust and versatile platform for organoboron transformations under mild conditions, with relevance to applications in pharmaceutical, agrochemical, and polymer synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"40 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209841","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":"Operando Elucidation of Filamentous Carbon Gasification Kinetics and Mechanisms on a Spent Ni/CeO2 Catalyst","authors":"Monia R. Nielsen, Tianyu Li, Rajat Sainju, Seth March, Chunxiang Zhu, Pu-Xian Gao, Steven L. Suib, Yuanyuan Zhu","doi":"10.1021/acscatal.5c02824","DOIUrl":"https://doi.org/10.1021/acscatal.5c02824","url":null,"abstract":"Coking is the leading cause of catalyst deactivation in many important hydrocarbon conversion technologies. Understanding regeneration mechanisms is critical for developing effective carbon removal strategies that improve catalyst longevity and reduce operational costs. Here, we present a spatially resolved <i>operando</i> investigation of the regeneration of a spent Ni/CeO₂ catalyst under industrially relevant air-like conditions, using in-situ environmental transmission electron microscopy (ETEM) combined with semantic segmentation. By deconvoluting competing gasification events for filamentous carbon removal, we found three distinct gasification modes─while fast catalytic gasification was expected, less steady noncatalytic combustion and cooperative gasification were also present and even more prevalent. Microstructure-informed kinetics directly linked the maximum gasification rates to axial filament consumption through either Ni/carbon contact or filament breakage, emphasizing the pivotal role of edge-plane carbon sites across all gasification pathways. Moreover, our <i>operando</i> characterization uncovered a Ni(−C_<i>x</i>)-limited carbon diffusion mechanism, which challenges the conventional carbon bulk diffusion model typically assumed for catalytic gasification. Furthermore, adverse processes such as Ni/carbon contact disruption and gasification-induced catalyst sintering were also identified. Collectively, these findings provide mechanistic insights into carbon gasification processes, highlighting critical pathways and potential pitfalls that can guide the optimization of catalyst regeneration strategies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"28 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209837","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":"Cu-Catalyzed Three-Component Carbofunctionalization of 1,3-Dienes","authors":"Vincent R. Viviani, Travis L. Buchanan, An Thien Ho, John A. Little, Andrei G. Popov, Matthew Barnett, Kira Q. McMahon, Samuel N. Gockel, Kami L. Hull","doi":"10.1021/acscatal.5c04439","DOIUrl":"https://doi.org/10.1021/acscatal.5c04439","url":null,"abstract":"The carboamination of 1,3-dienes provides direct and efficient access to allylic amines in a step-economical fashion. Herein, we disclose a three-component 1,3-diene carboamination reaction that provides modular access to a multitude of allylic amines. A representative scope of 1,3-dienes, activated alkyl halides, and amines is demonstrated to serve as components for this reaction, with yields ranging from up to 96%. High regioisomeric ratios are observed with both substituted and unsubstituted diene derivatives for either 1,2- or 1,4-carboamination (≥12:1). Mechanistic investigations demonstrate that the reaction proceeds via atom transfer radical addition to the diene, affording an isolable allylic halide intermediate. The scope was expanded to a general carbofunctionalization, by adding an exogenous O, S, P, or C nucleophile and base to the reaction upon formation of the allylic halide, in a two-step, one-pot process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"121 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215887","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":"Boosting Toluene Selectivity over Mo-Modified Ni@Silicalite-1 Catalysts in Hydrogenolysis of Vapor-Phase m-Cresol","authors":"Jimei Zhang, Yanchun Shi, Junwen Chen, Sihan Sun, Bi Wu, Lei Wang, Qiang Chen","doi":"10.1021/acscatal.5c03303","DOIUrl":"https://doi.org/10.1021/acscatal.5c03303","url":null,"abstract":"The hydrogenolysis of biobased phenolics into high-value arenes is considered as the potential alternative strategy to petroleum-based arenes, but the widely used Ni-based catalysts generally suffer from a poor arenes yield. Herein, we demonstrated a strategy by introducing Mo species into Ni@Silicalite-1 (Ni@S-1) to drive the diffusion of Ni particles embedded at the external surface layer of S-1 into its deeper internal crystals to form uniformly confined NiMo bimetallic nanoparticles (2–5 nm) with rich oxygen vacancies. As for hydroxyl hydrogenolysis of vapor-phase <i>m</i>-cresol as an example, NiMo@S-1 presented a remarkable toluene production rate of 480.3 μmol_[toluene]·g_[Ni]^–1·s^–1 with a hydroxyl hydrogenolysis rate of 501.9 μmol_{[<i>m</i>-cresol]}·g_[Ni]^–1·s^–1 at 350 °C under reported minimal metal Ni loading, suggesting the achievement of the highest hydroxyl hydrogenolysis rate over disclosed Ni-based catalysts by far. As analyzed, such induced confined structures enforce the <i>m</i>-cresol adsorbed onto the metal surface via the vertical geometry for the shape-selective effect of zeolites, and the oxygenophilic oxygen vacancies of NiMo@Silicalite-1 further strengthen the vertically oriented <i>m</i>-cresol to interact with active sites through the hydroxyl group rather than the phenyl group, thus greatly enhancing the desired hydroxyl hydrogenolysis process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"214 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209839","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":"Million-Fold Activation of C–H Bonds by Fluorinated Nonheme FeIV═O Complexes via Second Sphere Equatorial Substitution and Catalytic Epoxidation to Boot","authors":"Bittu Chandra, Chupeng Li, Mursaleem Ansari, Jin Xiong, Alex Lovstedt, Yisong Guo, Marcel Swart, Lawrence Que, Jr","doi":"10.1021/acscatal.5c04331","DOIUrl":"https://doi.org/10.1021/acscatal.5c04331","url":null,"abstract":"Fe^IV═O units found in the active sites of nonheme iron oxygenases and related synthetic analogs are intriguing intermediates capable of performing challenging oxygenation reactions. The first crystal structure of such a crucial species in a synthetic complex, [Fe^IV(O_<i>anti</i>)(TMC)(MeCN)]²⁺ (<b>TMC-<i>anti</i></b>), reported in 2003, utilizes a 14-TMC (tetramethylcyclam) N₄-macrocyclic ligand. With a half-life of 10 h at 25 °C, <b>TMC-<i>anti</i></b> is quite a sluggish oxidant, but axial ligand replacements enhance <b>TMC-<i>anti</i></b> reactivity by as much as 50-fold. Herein we switch to an N₄-equatorial modification approach by replacing the <i>N</i>-methyl groups in <b>TMC-<i>anti</i></b> with N–CH₂–aryl groups and fluorinated analogs in the secondary coordination sphere to generate even more reactive Fe^IV(O)L complexes, namely [Fe^IV(O_<i>anti</i>)(TB^F8C)(MeCN)]²⁺ (<b>2-<i>anti</i></b>, <i>t</i>_1/2 = 6 min at 25 °C), [Fe^IV(O_<i>syn</i>)(TB^F8C)(MeCN)]²⁺ (<b>2-<i>syn</i></b>, <i>t</i>_1/2 = 2 min at 25 °C) and [Fe^IV(O_<i>syn</i>)(TB^F8C)(Cl)]⁺ (<b>3-<i>syn</i></b>, <i>t</i>_1/2 = 1.5 min at −20 °C). Surprisingly, despite the increased steric bulk introduced around the Fe^IV═O moiety, <b>2-<i>syn</i></b> and <b>3-<i>syn</i></b> exhibit reaction rates as much as a million-fold higher than <b>TMC-<i>anti</i></b> in C–H bond cleavage as well as oxo-transfer reactions, including unprecedented catalytic epoxidation of olefins by <b>2-<i>syn</i></b>. Computations confirm the dramatic reactivity enhancement upon introduction of polyfluorinated arenes into the second coordination sphere of the nonheme Fe^IV═O complexes, which distort the Me₄cyclam that decreases the energy gap between the ground <i>S</i> = 1 and the excited <i>S</i> = 2 spin states.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209840","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":"Branched Regioselectivity in the Heterogeneous Hydroformylation of Terminal Olefins: A “Two-Step Process” Method and Kinetic Optimization","authors":"Muhan Li, Yifan Sun, Weixiang Wang, Zhangxinyu Fan, Xiao Chen, Shule Zhang, Huanjun Wang, Hongwei Niu, Tiefeng Wang, Boyang Liu, Qin Zhong","doi":"10.1021/acscatal.5c04539","DOIUrl":"https://doi.org/10.1021/acscatal.5c04539","url":null,"abstract":"Hydroformylation of olefins to aldehydes is an important reaction in the chemical industry. The development of heterogeneous catalysts has attracted much attention due to their ease of separation and environmental friendliness. Although researchers have focused more on linear products, branched aldehydes also have wide applications, serving as important chemical products or intermediates in fragrance, pharmaceutical, and other fields. In this work, we propose a tandem “two-step process” method to obtain high regioselectivity of branched aldehydes with the same catalyst, even when using terminal olefins as the reactants. The method includes the isomerization process of the terminal olefins to internal olefins and the subsequent heterogeneous hydroformylation process, converting internal olefins to branched aldehydes. The kinetic model of heterogeneous hydroformylation of internal olefins is also established, and the predicted <i>b</i>/<i>l</i> ratio under different reaction conditions is consistent with the experimental results. After the optimization of reaction conditions, the highest <i>b</i>/<i>l</i> ratio of the ″two-step process” for 1-octene reaches 33.34, which is 39 times higher than that obtained by direct hydroformylation and surpasses all branched regioselectivities reported in other literature, to the best of our knowledge. This work not only deepens the mechanistic understanding of heterogeneous hydroformylation of both terminal and internal olefins but also provides inspiration and practical guidance for the industrial production of branched aldehydes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209864","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":"Quantifying Site Heterogeneity in Microporous Aluminosilicates and Implications for Catalysis","authors":"Edgard A. Lebrón-Rodríguez, Fillipp E. Salvador, Zahra Alikhani, Jerome M. Evans, Levi Callahan, Nicole K. Mitchell, Chenyao Huang, Sudipta Ganguly, Faysal Ibrahim, Ive Hermans","doi":"10.1021/acscatal.5c01948","DOIUrl":"https://doi.org/10.1021/acscatal.5c01948","url":null,"abstract":"Zeolites and related microporous materials are key acid catalysts for many crucial transformations in both the gas and liquid phases for processes such as hydrocarbon refining, isomerization, and biomass upgrading. However, their catalytic behavior becomes complex under harsh hydrothermal conditions due to the formation of nonframework sites, which can significantly impact reaction rates and selectivity, complicating reproducibility and research evaluations. Therefore, in this work, we set out to establish characterization and titration protocols to identify and quantify site heterogeneity (i.e., differentiate between framework, partially hydrolyzed, and extraframework sites) of steamed microporous aluminosilicates, in contrast to solely using Brønsted and Lewis designations. For this purpose, we employ commercial MFI aluminosilicates (ZSM-5) of differing site heterogeneity and Si/Al ratios to quantify their site distribution through a combination of temperature-programmed desorption and FTIR protocols while contextualizing their effect on propane cracking rate constants. From the conclusions obtained, the present work provides a nuanced titration strategy on how to quantitatively determine the site heterogeneity of aluminosilicates and Al content without catalyst modification and with considerations for physisorbed species, base type, and size. We also reinforce literature observations of how water can induce changes in Al coordination even at ambient conditions, especially with increasing Al content, before catalysis, which adds variability in rate measurements. These observations and approaches should be extendable to other acidic zeolites and present ways to determine the site heterogeneity of materials in their dried state, in an accessible manner, that can serve as a starting point to evaluate structure–performance relationships.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209835","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":"Stereoselective Synthesis of 2-Deoxy-α-O-glycosides Enabled by Cobalt-Catalyzed Hydrogen Atom Transfer and Radical-Polar Crossover","authors":"Xiong Xiao, Hui Jie Yang, Xin-Yu Fang, Jin-Tao Li","doi":"10.1021/acscatal.5c06507","DOIUrl":"https://doi.org/10.1021/acscatal.5c06507","url":null,"abstract":"We report a stereocontrolled glycosylation strategy for synthesizing 2-deoxy-α-<i>O</i>-glycosides via cobalt-catalyzed metal-hydride hydrogen atom transfer (MHAT) and radical-polar crossover (RPC) processes. This method achieves reagent-controlled stereoselectivity by modulating ligand environments, silane additives, and solvent effects, eliminating dependence on neighboring-group participation. Mechanistic studies reveal a sequence involving Co(III)–H-mediated hydrogen atom transfer, radical generation, and nucleophilic trapping of a Co(IV)–R intermediate to establish α-selectivity. Compared to conventional glycosylation protocols, this multitunable platform and chemoselectively compatible reaction conditions enable flexible 2-deoxy sugar assembly with extensive functional group tolerance, especially for substrates containing basic nitrogenous functional groups. The methodology provides a versatile and mild foundation for constructing structurally diverse glycoconjugates, including steroidal glycosides and nitrogen-containing acceptors such as ribonucleosides, deoxyribonucleosides, aniline, pyrrole, indole, and carbazole, demonstrating considerable potential for bioactive molecule development.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215930","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}