ACS Catalysis 最新文献

{"title":"Accelerated Optimization of Compositions and Chemical Ordering for Bimetallic Alloy Catalysts Using Bayesian Learning","authors":"Xiangfu Niu, Shuwei Li, Zheyu Zhang, Haohong Duan, Rui Zhang, Jianqiu Li, Liang Zhang","doi":"10.1021/acscatal.5c00467","DOIUrl":"https://doi.org/10.1021/acscatal.5c00467","url":null,"abstract":"Alloy materials are crucial to various applications, including catalysis and energy storage, due to their superior performance, cost-efficiency, and tunable properties. However, the vast compositional space and complex chemical ordering of alloys pose significant challenges in identifying the optimal material designs. We present an active learning framework utilizing Bayesian optimization to streamline the discovery of high-performance alloy materials. Applying this framework to PtNi oxygen reduction reaction (ORR) catalysts, we successfully identified the global optimal structures featuring a Pt shell and a PtNi core. Our approach was further extended to explore different morphologies and compositions, revealing the most favorable chemical orderings for ORR. This work provides a comprehensive strategy for the accelerated design of multicomponent alloy materials and highlights the critical role of chemical ordering in optimizing the structure–performance relationship, facilitating the development of high-performance catalysts for energy applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495762","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":"Identification of Sabatier Descriptors for Hydrodeoxygenation Activity and Selectivity on Supported Molybdenum Oxide Catalysts","authors":"Andrew J. Kohler, Mahmudul H. Khan, Brent H. Shanks","doi":"10.1021/acscatal.4c07504","DOIUrl":"https://doi.org/10.1021/acscatal.4c07504","url":null,"abstract":"While molybdenum oxide shows promise in deoxygenating lignin monomers to petrochemically relevant aromatics and alkenes, its current applicability is hindered by its tendency to oversaturate the aliphatic byproducts to alkanes, limiting the ability of the product stream to be directly integrated into the existing infrastructure. Previously, detailed kinetic experiments indicated that this parasitic alkane pathway can result from competitive C–O hydrogenolysis during deoxygenation rather than direct hydrogenation of alkenes. Here, we evaluate how modulating the properties of the molybdenum active site could ameliorate this pathway for short-chain (&lt;C₅) carbonyl hydrodeoxygenation (HDO) by synthesizing a library of catalysts across an array of metal oxide supports (Al₂O₃, Nb₂O₅, SiO₂, TiO₂, and ZrO₂) at incremental MoO_<i>x</i> surface densities to alter the degree of two-dimensional MoO_<i>x</i> oligomerization. The study reveals that MoO_<i>x</i> structure sensitivity for oxygen removal highly depends on the supporting metal oxide. Notably, the electronegativity of the support and the MoO_<i>x</i> structure alter the electronic density of the average Mo active site (as quantified by the terminal Mo=O bond Raman shift) in parallel, leading to a Sabatier relationship between oxygen adsorption strength and the overall rate of oxygen removal. Conversely, this combinatorial MoO_<i>x</i> structure/support effect does not apply to the selectivity between the alkane and alkene products. Instead, the support appears to be the primary driver of the competitive hydrogenolysis pathway, with the support’s point of zero charge (PZC) being an apparent Sabatier descriptor for the relative alkane selectivity, implying the bridging Mo–O-support bond as the hydrogenolysis site. Interestingly, the Sabatier optimum for the hydrogenolysis pathway is reactant dependent as a shift to stronger binding on higher PZC supports occurs for molecules with less stable intermediates like the more lignin-relevant aldehyde molecules.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495759","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":"Activity Regulation of a Glutamine Amidotransferase Bienzyme Complex by Substrate-Induced Subunit Interface Expansion","authors":"Franziska Jasmin Funke, Sandra Schlee, Isabel Bento, Gleb Bourenkov, Reinhard Sterner, Matthias Wilmanns","doi":"10.1021/acscatal.4c07438","DOIUrl":"https://doi.org/10.1021/acscatal.4c07438","url":null,"abstract":"Glutamine amidotransferases are multienzyme machineries in which reactive ammonia is generated by a glutaminase and then transferred through a sequestered protein tunnel to a synthase active site for incorporation into diverse metabolites. To avoid wasteful metabolite consumption, there is a requirement for synchronized catalysis, but any generally applicable mechanistic insight is still lacking. As synthase activity depends on glutamine turnover, we investigated possible mechanisms controlling glutaminase catalysis using aminodeoxychorismate synthase involved in folate biosynthesis as a model. By analyzing this system in distinct states of catalysis, we found that incubation with glutamine leads to a subunit interface expansion by one-third of its original area. These changes completely enclose the glutaminase active site for sequestered catalysis and the subsequent transport of volatile ammonia to the synthase active site. In view of similar rearrangements in other glutamine amidotransferases, our observations may provide a general mechanism for the catalysis synchronization of this multienzyme family.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495758","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":"Tuning Vacancy in Metal Oxide Support to Enhance Activity and Durability of Pt Catalysts for the Methanol Oxidation Reaction","authors":"Ahmed M. Jasim, Gan Xu, Matthias J. Young, Yangchuan Xing","doi":"10.1021/acscatal.5c00259","DOIUrl":"https://doi.org/10.1021/acscatal.5c00259","url":null,"abstract":"Coupling Pt with metal oxides has been shown to be an effective approach for catalyst durability enhancement in the methanol oxidation reaction (MOR). Here, we report tuning valence in niobium oxide (NbO_x) as a support by tin oxide (SnO₂) as a promoter to mediate the Pt electrocatalysis in MOR. The catalyst was designed to consist of Pt supported on SnO₂-modified NbO_x coated on carbon black (Pt-TNb/C), which shows significantly enhanced electrochemical durability and activity in MOR that are better than the catalyst without SnO₂ modification (Pt-Nb/C) and those reported in the literature. Electron diffraction pair distribution function analysis showed an increase in the Nb–Nb bond length after SnO₂ incorporation, from 3.80 to 3.84 Å, indicative of a tuning effect. X-ray photoelectron spectroscopy further confirmed valence mediation in the Pt-TNb/C catalyst, as evidenced by the positive binding energy peak shifts of 0.49 and 0.66 eV in Nb 3d_5/2 and Nb 3d_3/2, respectively, as compared to those of the Pt-Nb/C catalyst. The Pt-Nb/C catalyst has MOR peak currents of 2.71 A/mg-Pt at the beginning and 1.94 A/mg-Pt at the end of 1000 cycles in 1.0 M methanol in 0.5 M H₂SO₄ electrolyte, corresponding to a 28.41% activity loss. However, the Pt-TNb/C catalyst with SnO₂ tuning has a much smaller loss at only 3.77%, with MOR peak currents of 3.45 A/mg of Pt at the beginning and 3.32 A/mg of Pt at the end under the same test conditions. The high durability and activity of the new catalyst are attributed to the effect of valence tuning of the niobium oxide, in addition to a bifunctional effect from tin oxide.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495760","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":"Recent Advances in Desulfurization of VOSCs: Multiple Catalysts and Coupling Enzymes","authors":"Rui Tian, Shiying Fan, Xinyong Li, Shaomin Liu","doi":"10.1021/acscatal.4c08111","DOIUrl":"https://doi.org/10.1021/acscatal.4c08111","url":null,"abstract":"The presence of volatile organic sulfur compounds (VOSCs) poses serious hazards to both the environment and human health, highlighting the importance and urgency of developing efficient abatement technologies. Effective desulfurization catalysts should demonstrate sufficient catalytic activity at low temperatures, high selectivity, and robust resistance to carbon and sulfur. Achieving these attributes needs careful optimization of three key factors of the catalysts: acidity, redox properties, and active oxygen species. In this review, we explore the design and optimization of multiple catalysts by focusing on the three key factors mentioned. We also discuss the synergistic degradation of multicomponent VOSCs, along with the mechanism of catalytic reaction, catalyst deactivation, and regeneration. It is noteworthy that an innovative catalysis at room temperature is highlighted, which combines chemical and biological methods to enhance the desulfurization performance through the integration of enzymes and inorganic components. The catalytic reaction mechanism and the catalyst design by coupling the biological enzymes and inorganic substances to achieve room catalysis is systemically elaborated. It is hopeful that this review will inspire researchers in academia and industry and promote their collaborations to address future environmental desulfurization challenges by combining chemical and biological approaches.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"33 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495816","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":"HPW Monomer-Confined FAU Zeolite with Modulated Acidity for Efficient Benzene Alkylation","authors":"Wenhua Feng, Hongxin Ding, Qingying Yao, Jinwen Zhang, Li Zhang, Yuanhang Ren, Xueying Chen, Lin Ye, Bin Yue, Heyong He","doi":"10.1021/acscatal.4c07714","DOIUrl":"https://doi.org/10.1021/acscatal.4c07714","url":null,"abstract":"Acid catalysts play a crucial role in the petroleum refining and petrochemical industry. However, immobilizing homogeneous catalysts on solid support with controllable acidity and stability is still challenging. In this work, a strategy to modulate the acid strength and density of catalysts by encapsulating specific amounts of monodispersed phosphotungstic acid in FAU zeolite (HPW@USY-x, x represents P wt %) is described. The confinement of HPW monomers in the FAU structure was illustrated by high SNR ADF-STEM. Also, the variation of the acid strength, acid density, and the spatial interaction between acidic protons of HPW and of USY over HPW@USY-x was studied in detail by ³¹P MAS NMR and the longitudinal relaxation time T1. In addition, HPW@USY-x with modulated acidity exhibited superior catalytic activity in the alkylation of benzene with cyclohexene (CHE) to cyclohexylbenzene (CHB). Specifically, the HPW@USY-0.50 catalyst with a moderate strength of Brønsted acid and optimal desorption energy for both reactants and products achieved 100% CHE conversion and 99.2% CHB selectivity. This work may provide an alternative way to immobilize homogeneous catalysts and modulate acidity simultaneously.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495763","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":"Pd(II)-Catalyzed Asymmetric C–H Functionalization/Dearomatization of Naphthols through Axial-to-Central Chirality Transfer","authors":"Ke-Xin Kong, Tao Zhou, Wen-Kui Yuan, Xin-Shang Hui, Ya Li, Bing-Feng Shi","doi":"10.1021/acscatal.5c00136","DOIUrl":"https://doi.org/10.1021/acscatal.5c00136","url":null,"abstract":"All-carbon chiral spirocycles are highly sought-after structural motifs found in various biological drugs, natural products, chiral ligands, and catalysts. However, their catalytic asymmetric synthesis remains a significant challenge due to steric hindrance and ring strain. Herein, we present the efficient synthesis of all-carbon chiral spirocycles through a Pd(II)-catalyzed asymmetric C–H functionalization/dearomatization reaction of naphthols, utilizing an axial-to-central chirality transfer strategy. This mild and versatile protocol accommodates a broad range of functionalized naphthols and alkynes, achieving good yields and enantioselectivities (up to 93% yield and 96% ee). Additionally, the practical application of this method is illustrated through the investigation of the photophysical properties of the resulting spirocycles, highlighting their potential as host materials for organic light-emitting diodes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486499","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":"Zinc Hollow-Fiber Penetration Electrode Promotes Ampere-Level CO2 Electroreduction for Viable Applications","authors":"Xiaohu Liu, Shoujie Li, Aohui Chen, Xiao Dong, Jianing Mao, Chang Zhu, Gangfeng Wu, Yiheng Wei, Jiayu Xia, Huanyi Zhu, Xiaotong Wang, Ziran Xu, Guihua Li, Yanfang Song, Wei Wei, Wei Chen","doi":"10.1021/acscatal.4c07490","DOIUrl":"https://doi.org/10.1021/acscatal.4c07490","url":null,"abstract":"CO₂ conversion into value-added chemicals via the electrochemical CO₂ reduction reaction (eCO₂RR) offers substantial environmental and economic benefits. Among all eCO₂RR products, CO shows vital significance due to its extensive application in chemical industrial synthesis, yet its production via eCO₂RR is hindered by the requirements of noble metal catalysts. Zinc-based catalysts are potential cost-effective alternatives while still confronting the inadequacy of eCO₂RR activity and CO selectivity. This study introduces an architecturally optimized zinc hollow-fiber penetration electrode (Zn HPE) that achieves a CO Faradaic efficiency exceeding 90% while sustaining stable operation for 110 h at 800 mA cm^–2. In situ X-ray absorption analysis along with operando Raman spectroscopy confirms the maintenance of metallic Zn⁰ during eCO₂RR. Transmission Fourier transform infrared spectroscopy confirmed that the superior performance of Zn HPE is attributed to its unique penetration effect, ensuring the local enrichment and rapid replenishment of CO₂ at the surface active sites. Besides, the effect of local CO₂ enrichment with high coverage on lowering the energy barrier for forming the *COOH intermediate and subsequent CO₂-to-CO conversion enhancement was also elucidated via density functional theory calculations. The techno-economic analysis further suggests the prominent cost advantage of Zn HPE. This work presents a promising approach for designing efficient CO₂ electroreduction electrodes for viable applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486419","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":"Rhodium-Catalyzed Asymmetric Allylic Dearomatization of β-Naphthols with gem-Difluorinated Cyclopropanes","authors":"Zi-Qi Yang, Yiliang Gong, Qing Gu, Shu-Li You","doi":"10.1021/acscatal.5c00315","DOIUrl":"https://doi.org/10.1021/acscatal.5c00315","url":null,"abstract":"Transition-metal-catalyzed allylation reactions using gem-difluorinated cyclopropanes have drawn considerable interest in recent years. However, linear-selective and enantioselective 2-fluoroallylic substitution reaction is underexplored. Herein, we report a rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols with gem-difluorinated cyclopropanes. In the presence of a rhodium catalyst consisting of commercially available rhodium precursor and chiral bisphosphine ligand, linear-selective 2-fluoroallylic β-naphthalenones bearing quaternary carbon centers were obtained in good yields and enantioselectivity (up to 86% yield and 95% ee). Mechanistic studies disclosed that the NaBAr^F additive in this reaction is critical, and a kinetic resolution is operated for the C–C cleavage of the gem-difluorinated cyclopropane.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"88 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486435","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":"Zwitterionic Dual Halogen Bond-Catalyzed Electrophilic Bromination of Electron-Deficient Arenes under Mild Conditions","authors":"Muyin Zhang, Zhihai Ke","doi":"10.1021/acscatal.5c00619","DOIUrl":"https://doi.org/10.1021/acscatal.5c00619","url":null,"abstract":"Halogen bonding has become a prominent tool in organocatalysis, offering versatile and efficient applications. This paper presents a metal-free method to catalyze electrophilic bromination reactions of electron-deficient arenes through zwitterionic dual halogen bond catalysis. We study the potential of an underexplored class of zwitterionic iodonium compounds as both halogen bond donors and acceptors. This method is particularly significant as it operates under mild conditions, which is beneficial for maintaining the integrity of sensitive substrates. Furthermore, density functional theory calculations were used to gain insights into the dual halogen bond activation mode underlying the catalytic process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486420","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}