ACS Catalysis 最新文献

{"title":"Largely Promoted C–H Activation in Methane with O2 via d-Orbital Hybridization Induced by CuOx Supported on ZnO","authors":"Yufei Cui, Wenhao Zhou, Hui Yang, Yongqing Ma, Ganhong Zheng, Chuhong Zhu, Meiling Wang, Bin Chen","doi":"10.1021/acscatal.4c06051","DOIUrl":"https://doi.org/10.1021/acscatal.4c06051","url":null,"abstract":"Efficiently converting methane (CH₄) to C1 products such as CH₃OH, HCHO, and CH₃OOH is considered a promising route for the chemical industry, while the huge challenge of low CH₄ activation rate still remains. Here, the promising Cu/ZnO composite catalyst with CuO_<i>x</i> supported on ZnO is synthesized to modify the electronic structure and utilized for CH₄ conversion. The fast e^– transfer channel of ZnO → Cu → O₂ facilitates O₂ dissociation to ^•OOH, which promotes charge separation and, in parallel, enables CH₄ oxidation to ^•CH₃ by h⁺ left in ZnO with the acceleration effect of in situ generated ^•OOH. Mechanistic studies revealed that additional d-π*/d-σ-orbital hybridization between the catalyst and adsorbed O₂/CH₄ molecules plays decisive roles in O₂ and CH₄ activation, which resulted in the highest ^•CH₃ signal, so far as we know, and ultimately a remarkably high C1 products yield of 21.25 mmol g^–1 h^–1 with 100% selectivity over the optimized 1 wt % Cu/ZnO photocatalyst. This work offers valuable guidance for catalyst designation in CH₄ conversion in the presence of O₂.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"52 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981491","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":"Machine Learning Potentials for Heterogeneous Catalysis","authors":"Amir Omranpour, Jan Elsner, K. Nikolas Lausch, Jörg Behler","doi":"10.1021/acscatal.4c06717","DOIUrl":"https://doi.org/10.1021/acscatal.4c06717","url":null,"abstract":"The production of many bulk chemicals relies on heterogeneous catalysis. The rational design or improvement of the required catalysts critically depends on insights into the underlying mechanisms on the atomic scale. In recent years, substantial progress has been made in applying advanced experimental techniques to complex catalytic reactions <i>in operando</i>, but in order to achieve a comprehensive understanding, additional information from computer simulations is indispensable in many cases. In particular, <i>ab initio</i> molecular dynamics (AIMD) has become an important tool to explicitly address the atomistic level <i>structure</i>, <i>dynamics</i>, and <i>reactivity</i> of interfacial systems, but the high computational costs limit applications to systems consisting of at most a few hundred atoms for simulation times of up to tens of picoseconds. Rapid advances in the development of modern machine learning potentials (MLP) now offer a promising approach to bridge this gap, enabling simulations of complex catalytic reactions with <i>ab initio</i> accuracy at a small fraction of the computational costs. In this Perspective, we provide an overview of the current state of the art of applying MLPs to systems relevant for heterogeneous catalysis along with a discussion of the prospects for the use of MLPs in catalysis science in the years to come.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981492","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":"Helix Zipper Regulating Formolase Activity","authors":"Zijian Tan, Zijing Tang, Hongli Wei, Ruke Zhang, Ling Sun, Weidong Liu, Haifeng Liu, Leilei Zhu, Yanhe Ma","doi":"10.1021/acscatal.4c07452","DOIUrl":"https://doi.org/10.1021/acscatal.4c07452","url":null,"abstract":"Formolase catalyzes the carboligation of C1 compound formaldehyde, providing a unique opportunity for producing multicarbon compounds with formaldehyde as the sole substrate. Elucidating the molecular rationale determining the activity of formolase, especially at low concentrations of formaldehyde, is essential for improving its catalytic performance in the C1 compound conversion. In this study, a channel-modulating helix formed a zipper structure with its neighboring helix that was identified to regulate the catalytic activity of formolase_BFD, especially at low concentrations of formaldehyde. Up to 24.1-fold increased catalytic efficiency was obtained after engineering the channel-modulating helix to fine-tune the shape of substrate/product channel. The activity of the best variant was enhanced by 27.3-fold at 20 mM formaldehyde and 86.5-fold at 40 mM formaldehyde compared to the starting point. Crystallization and molecular dynamic simulations revealed that the engineered zipper structure enhanced the activity of formolase_BFD by enlarging the substrate/product channel entrance and tightening the bottom of the channel, which increased the availability of substrate formaldehyde to promote the formation of C3 product 1,3-dihydroxyacetone.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"49 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981493","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":"Cobalt-Catalyzed Chemoselective π–σ–π-Type Tandem Reductive Coupling to Access Isoquinolines via Carbocobaltation of Nitriles","authors":"Ling Tang, Xueyu Liu, Xintong Wang, Xianmao Liu, Xinmiao Huang, Qian Ni, Chen He, Gen Luo, Yuanhong Ma","doi":"10.1021/acscatal.4c07667","DOIUrl":"https://doi.org/10.1021/acscatal.4c07667","url":null,"abstract":"Transition metal-catalyzed reductive coupling chemistry has been recognized as a powerful tool for the synthesis of diverse organic molecules. However, despite enormous progress in this field, there is no precedent for the tandem reductive coupling of widely accessible nitriles with electrophiles that contain σ- and π-type (σ/π-type) electrophilic functional groups simultaneously. Herein, we have established a unique cobalt catalysis system, enabling the chemoselective reductive coupling/tandem cyclization reaction of aryl halides (Br, Cl, I) bearing carbonyl moiety with a variety of aryl, alkenyl, and alkyl nitriles via the carbocobaltation of nitriles that is unknown yet. The protocol allows for the modular synthesis of structurally diverse isoquinolines with wide substrate scope (&gt;60 examples), good functionalities tolerance, and good chemoselectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"149 7 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981494","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":"Optimizing Ethylene Production through Enhanced Monomolecular β-Scission in Confined Catalytic Cracking of Olefin","authors":"Yanfen Zuo, Lei Ye, Wenjie Yang, Bo Peng, Jing Zhang, Xingtian Shu, Youhao Xu, Jichang Liu","doi":"10.1021/acscatal.4c05323","DOIUrl":"https://doi.org/10.1021/acscatal.4c05323","url":null,"abstract":"Confined catalytic cracking of olefins on shape-selective zeolites involves a complex reaction network with multiple β-scission types. Herein, grand canonical Monte Carlo and molecular dynamics simulations were adopted to confirm the inferior adsorption and superior diffusion of 1-pentene in the H-ZSM-5 zeolites at a reaction temperature between conventional catalytic cracking and steam cracking operating temperatures, which was the favorable condition for the monomolecular cracking pathway to improve the ethylene selectivity. Subsequently, the feasibility of improving ethylene production via enhancing the monomolecular reaction pathway was confirmed through repetitive experiments in which the catalytic cracking of 1-pentene was carried out over H-ZSM-5 zeolites. More notably, the ethylene selectivity reached a maximum of 36.2% and the ethylene/propylene ratio exceeded 1, which meant that optimizing ethylene production could be achieved by increasing the temperature of the catalytic cracking, at a milder condition than that of steam cracking. On the basis of density functional theory calculations at high temperature and kinetics analysis, it was rationalized that the dominant β-scission type evolved as the reaction temperature increased. Under the confined effect of zeolites, bimolecular pathways were suppressed while monomolecular pathways were enhanced, and even the primary (ethyl) carbenium ion-involving monomolecular pathway by rare assembly of 1-pentene was activated. Such an observation provides a feasible approach to the ethylene production via olefin-confined cracking and enriches the connotation of carbocation chemistry in zeolites.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"68 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974766","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":"Evolutionary Specialization of a Promiscuous Designer Enzyme","authors":"Reuben B. Leveson-Gower, Laura Tiessler-Sala, Henriette J. Rozeboom, Andy-Mark W. H. Thunnissen, Jean-Didier Maréchal, Gerard Roelfes","doi":"10.1021/acscatal.4c06409","DOIUrl":"https://doi.org/10.1021/acscatal.4c06409","url":null,"abstract":"The evolution of a promiscuous enzyme for its various activities often results in catalytically specialized variants. This is an important natural mechanism to ensure the proper functioning of natural metabolic networks. It also acts as both a curse and blessing for enzyme engineers, where enzymes that have undergone directed evolution may exhibit exquisite selectivity at the expense of a diminished overall catalytic repertoire. We previously performed two independent directed evolution campaigns on a promiscuous designer enzyme that leverages the unique properties of a noncanonical amino acid (ncAA) <i>para</i>-aminophenylalanine (pAF) as catalytic residue, resulting in two evolved variants which are both catalytically specialized. Here, we combine mutagenesis, crystallography, and computation to reveal the molecular basis of the specialization phenomenon. In one evolved variant, an unexpected change in quaternary structure biases substrate dynamics to promote enantioselective catalysis, while the other demonstrates synergistic cooperation between natural side chains and the pAF residue to form semisynthetic catalytic machinery.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"83 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968429","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":"Water-Controlled Coking Dynamics during High-Pressure Methanol-to-Olefins Reaction over SAPO-34","authors":"Chengwei Zhang, Xinqiang Wu, Yanan Zhang, Li Wang, Yan Jin, Mingbin Gao, Mao Ye, Yingxu Wei, Zhongmin Liu","doi":"10.1021/acscatal.4c06239","DOIUrl":"https://doi.org/10.1021/acscatal.4c06239","url":null,"abstract":"Water, as a co-feed and decoking agent for catalyst regeneration, is increasingly recognized as a crucial component in methanol to olefins (MTO) catalysis over zeolites. In this study, water-controlled coking dynamics and improved diffusion efficiency have been revealed in a high-pressure MTO reaction over the SAPO-34 zeolite catalyst. Through gas chromatograph–mass spectrometry (GC-MS), matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry (MALDI FT-ICR MS), and ultraviolet–visible spectroscopy (UV–vis), the kinetic behavior of water-delayed coking has been confirmed mainly in two aspects: suppressing the aging of active hydrocarbon pool species (HCPs, e.g., phenyl, naphthyl species) to form polyaromatic hydrocarbons (PAHs) within the CHA cages and hindering the cross-linking of PAHs between CHA cages. For the deactivated SAPO-34 catalyst, the restoration of methanol conversion from 5% to 40% upon switching from methanol to water–methanol co-feed and from 5% to 100% after high-pressure steam treatment further confirms the in situ coke decomposition capability of high-pressure water under the real MTO reaction conditions. Moreover, structured illumination microscopy (SIM) offers a direct visualization of the retained organic species and their spatiotemporal distribution within individual SAPO-34 crystals under the influence of water, thereby providing visual evidence for water-delayed coking dynamics and the improved diffusion process. Thus, the mechanistic insights into water-controlled coking and diffusion dynamics unveiled in this study provide a crucial theoretical foundation for the application of water-related techniques in the MTO industry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"90 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974555","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":"Substrate Promiscuity Engineering of ScALDO Enables a Versatile Minimized Enzyme Cascade for Efficient Utilization of Various Sugars","authors":"Shiming Tang, Zhiteng Zhang, Daocheng Liao, Ying Lin, Yuanyuan Huang, Suiping Zheng","doi":"10.1021/acscatal.4c07497","DOIUrl":"https://doi.org/10.1021/acscatal.4c07497","url":null,"abstract":"The depletion of fossil fuels has turned researchers’ attention toward utilizing waste biomass resources and their monomeric sugars to produce chemicals. In this study, we reshaped the active site pocket of alditol oxidase from <i>Streptomyces coelicolor</i> (ScALDO) through substrate promiscuity engineering, and a mutant ScALDO/Q288G was identified with high promiscuity toward C3 to C6 aldoses and alditols. Active site pocket volume analysis, spatial steric hindrance analysis, molecular dynamics simulations, and kinetic parameter studies revealed that ScALDO/Q288G achieves oxidation of cyclic <span>d</span>-glucose through an expanded active site pocket, reduces spatial hindrance for substrates, and facilitates hydride transfer. To further clarify the catalytic mechanism of ScALDO/Q288G in oxidizing cyclic aldoses, we proposed a possible mechanism that involves initial hydride transfer followed by spontaneous hydration and ring opening. Further combinatorial mutations produced an optimal variant, ScALDO/Q288G/E53D/V256E/E348P (M4), showing over a 68.8-fold increase in activity for D-xylose and 268-fold for D-ribose, while also demonstrating significant <span>d</span>-glucose oxidation activity. M4 also maintains significant activity toward smaller substrates, such as <span>d</span>-glyceraldehyde, and exhibits superior thermal stability (<i>T</i>_m = 68.7 °C). Using M4, we established a minimized glycolytic cascade (MGC). MGC efficiently utilizes diverse substrates, including <span>d</span>-glucose, D-xylose, <span>l</span>-arabinose, D-galactose, and xylitol, to produce pyruvate, with a conversion of 5 mM <span>d</span>-glucose to 9.08 mM pyruvate within 24 h, achieving a yield of 90.8%. In conclusion, we created M4, which exhibits high catalytic promiscuity toward C3 to C6 aldoses and alditols, thus enabling the establishment of an MGC for the utilization of various sugars. Beyond its application in MGC, M4 holds the potential to be used in all cascades involving aldoses and alditols of various sizes to reduce the number of enzymes required.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968430","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-Catalyzed Dehydrogenation Enhanced by Charge Transfer from MoOx Promoter","authors":"Byung Gwan Park, Jihyeon Lee, Yoojin Lee, Hyeongeon Lee, Jueun Kim, Eonu Nam, Jong-Seong Bae, Jeong Woo Han, Kwangjin An","doi":"10.1021/acscatal.4c04684","DOIUrl":"https://doi.org/10.1021/acscatal.4c04684","url":null,"abstract":"Incorporating metal oxides is a sensible strategy for enhancing the efficiency of precious metals. Upon the introduction of molybdenum oxide, diverse coordination structures were formed on the support surface depending on the concentration used. This modified surface architecture orchestrates consequential alterations in the electronic and geometric configurations of the active metal, concurrently influencing the catalytic performance. In this study, MoO_<i>x</i> species were introduced into Pd in a controlled manner to substantially enhance the dehydrogenation activity of the <i>N</i>-heterocyclic liquid organic hydrogen carrier system. Pd−MoO_<i>x</i>/Al₂O₃ catalyst─featuring an optimal 0.18 wt % Mo loading─demonstrated noteworthy improvement in activity, surpassing Pd/Al₂O₃ by factors of 1.57 and 1.24, accompanied by enhanced recyclability in two distinct LOHC systems. Integrated characterization and theoretical calculations elucidated the modification of the electronic properties of both Pd and Al₂O₃ upon MoO_<i>x</i> introduction and the corresponding adsorption behavior of the reactants, highlighting the charge transfer phenomenon from Pd to MoO_<i>x</i>.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142974769","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":"Access to Axially Chiral Biaryl Benzylamines via Ancestral Enzyme-Enabled Reductive Amination Desymmetrization","authors":"Wen-Qing Zheng, Xin-Xin Zhu, Zheng Zhu, Tairan Yang, Lifen Zheng, Rui Pan, Shenlin Wang, Lixin Zhang, Qi Chen, Jian-He Xu, Yongtao Xie, Gao-Wei Zheng","doi":"10.1021/acscatal.4c06881","DOIUrl":"https://doi.org/10.1021/acscatal.4c06881","url":null,"abstract":"Axially chiral biaryl benzylamines are present in numerous natural products, pharmaceuticals, chiral ligands, and catalysts. However, the direct catalytic synthesis of these functional molecules using a robust strategy remains a formidable challenge. Reductive amination desymmetrization of biaryl dialdehydes offers a powerful approach for the construction of axially chiral biaryl benzylamines but suffers from extensive undesirable side reactions. Herein, we engineered ancestral imine reductases to enable reductive amination desymmetrization of biaryl dialdehydes, allowing the construction of a wide range of axially chiral biaryl benzylamines with up to 99% conversion and 99% enantiomeric excess (ee). The ratio of the product to byproducts was up to 97:3 and over 90:10 in most cases. This work presents an alternative strategy for accessing axially chiral biaryl benzylamines and will stimulate the development of associated bioactive molecules and catalysts/ligands.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"21 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961379","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}