ACS Catalysis 最新文献

{"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}

{"title":"Uncovering the Crucial Role of Oxygen Vacancy in Altering Activity and Selectivity of CO2 Hydrogenation on ZnGa2O4 Spinel Surfaces","authors":"Meng-Jia Xi, Xi-Yang Yu, Xue Su, Lei Xiong, Xiaogang Ning, Peng Gao, Zheng-Qing Huang, Chun-Ran Chang","doi":"10.1021/acscatal.5c00660","DOIUrl":"https://doi.org/10.1021/acscatal.5c00660","url":null,"abstract":"While oxygen vacancies (V_Os) on metal oxides are widely reported to play important roles in CO₂ hydrogenation to methanol or other hydrocarbons by cooperating with zeolites, the underlying mechanisms are still far from well understood. Herein, we present a theoretical study to explore the formation mechanism and catalytic roles of V_O in the hydrogenation of CO₂ to methanol on ZnGa₂O₄(100). Our calculations manifest that surface oxygen vacancy generated by producing water can enhance activating both H₂ and CO₂, owing to the emergence of frustrated Lewis pair sites or coordinative unsaturated Zn cation in the sublayer. Moreover, the adsorbed hydride can be stabilized by the coordinative unsaturated Zn cation. Then, oxygen vacancies, together with the hydride, can alter the CO₂ adsorption structures to benefit the formation of *HCOO instead of *COOH, thereby turning the production selectivity from carbon monoxide to methanol. Interestingly, microkinetic modeling reflects that V_O monomer is more active in the methanol production rate (0.37 s^–1) than V_O dimer (6.64 × 10^–3 s^–1) at 643 K, suggesting keeping a high proportion of V_O monomers on the surface is important. Hence, our study provides important insights into the role of oxygen vacancies in altering the catalytic performance of CO₂ hydrogenation on spinel oxide surfaces.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477489","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":"Phase and Composition Engineering of Mn-Doped TiO2 for Hydrogen Peroxide Synthesis through Ion-Mediated Water Oxidation","authors":"Kairui Wang, Xueying Gao, Marshet Getaye Sendeku, Bichen Yuan, Yuan Zhang, Yan Liu, Ying Yang, Lin Ju, Fengmei Wang, Xiaoming Sun","doi":"10.1021/acscatal.4c06275","DOIUrl":"https://doi.org/10.1021/acscatal.4c06275","url":null,"abstract":"An electrochemical two-electron (2e^–) water oxidation process provides a promising approach for on-site H₂O₂ synthesis. The design of an efficient electrocatalyst with high selectivity and productivity is crucial. In this work, manganese atoms are introduced into titanium dioxide (i.e., Mn_<i>x</i>Ti_1–<i>x</i>O_<i>y</i>) with rutile and anatase phases for H₂O₂ synthesis through the two-electron water oxidation reaction. The anatase phase Mn_0.08Ti_0.92O_<i>y</i> exhibits promising activity with a low overpotential of 290 mV at 10 mA cm^–2 and Faradaic efficiency of 58% for H₂O₂ synthesis, which is twice higher than that (∼30%) of the rutile phase counterpart. Moreover, the H₂O₂ production rate on the anatase Mn_0.08Ti_0.92O_<i>y</i> electrode is around 51.2 μmol min^–1 cm^–2, along with 600 ppm of H₂O₂ accumulation within an 8 min reaction. Operando infrared spectroscopic analysis combined with theoretical calculations reveals that carbonate ions in the electrolyte could effectively mediate and promote active oxygen in water oxidation on Mn_0.08Ti_0.92O_<i>y</i> for H₂O₂ synthesis through the peroxocarbonate intermediate pathway. Compared to the rutile phase Mn_0.08Ti_0.92O_<i>y</i>, the much lower energy barrier for the rate-determining step (oxidation of carbonate to peroxocarbonate) of the mediated two-electron water oxidation process on the anatase phase Mn_0.08Ti_0.92O_<i>y</i> is achieved for boosting the catalytic H₂O₂ synthesis. This work highlights an innovative phase modulation strategy and electrolyte ion assisted electrochemical process for improving the efficiency of H₂O₂ synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486421","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":"Boron-Induced Redispersion of Pt Species during Propane Dehydrogenation","authors":"Mengyang Liu, Shaobo Han, Wenna Zhang, Bin Gu, Jingmei Li, Huangzhao Wei, Xin Rong, Chenglin Sun","doi":"10.1021/acscatal.4c07243","DOIUrl":"https://doi.org/10.1021/acscatal.4c07243","url":null,"abstract":"In a propane dehydrogenation (PDH) reaction system, low-Pt catalysts generally suffer from rapid deactivation and poor durability due to easy sintering at high temperatures and in a reductive atmosphere. Herein, we develop a catalyst (PtSnK-B/Al₂O₃, named as PtSnK-B0.32) with both low Pt loading (0.15 wt %) and high durability by facile doping of trace boron into a conventional Pt-based catalyst. Density functional theory (DFT) calculations show that pure Pt clusters have weak binding energy with support, leading to a further undesired Pt sintering process. In contrast, when boron (B) is added to the Pt-based catalyst, the undesired Pt sintering process is significantly inhibited. Moreover, being initiated by propane molecules, the pure Pt clusters are readily to dissociate into Pt atoms due to their longer Pt-Pt bond lengths, then the dissociated Pt atoms are captured by B or BO_<i>x</i> species to form stable Pt–B clusters under PDH conditions. The formation of highly dispersed Pt–B clusters allows the catalyst to achieve high intrinsic activity; compared with the catalyst without B (PtSnK, 0.14 wt % Pt), the <i>E</i>_a value of the B-doped catalyst is obviously reduced. Significantly, the durability of PtSnK-B0.32 is three times that of PtSnK and even twice that of 0.26PtSnK with a Pt loading of 0.26 wt %. The facile synthesis method, lower Pt content, and higher durability provide a promising application perspective.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"129 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486431","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":"Hollow Submicrospherical Ni/Co-Promoted CaO/Ca12Al14O33 for H2 Production from Sorption-Enhanced Water–Gas Shift with In Situ CO2 Conversion via CH4 Reforming of CaCO3","authors":"Chunxiao Zhang, Yingjie Li, Yumeng Deng, Wenqiang Liu, Kuihua Han, Yuzhuo Wang, Zirui He, Jun Jie Wu","doi":"10.1021/acscatal.4c07688","DOIUrl":"https://doi.org/10.1021/acscatal.4c07688","url":null,"abstract":"CaO sorbent/catalyst bifunctional materials are promising for CO₂ capture in sorption-enhanced H₂ production such as sorption-enhanced water–gas shift. For simultaneous H₂ production with CO₂ in situ capture and utilization, the integrated process of sorption-enhanced water–gas shift and in situ CO₂ conversion by CH₄ reforming of CaCO₃ was proposed. This work focused on the tailored design of a CaO sorbent/catalyst bifunctional material for both efficient H₂ production and in situ CO₂ conversion in this integrated process. The template-assisted strategy of hydrothermal carbonization followed by self-reduction and template removal via steam gasification was first proposed to obtain the hollow submicrospherical Ni/Co-promoted CaO/Ca₁₂Al₁₄O₃₃. The as-synthesized material exhibits high and stable H₂ production, CO₂ capture, and in situ CO₂ conversion performance in the integrated process due to the unique hollow submicrospherical structure and enhanced catalytic activity. Ni–Co interaction boosts oxygen vacancy and Ni–Co alloy, which are the active catalytic sites for the water–gas shift and CH₄–CaCO₃ reactions. Moreover, the oxygen vacancy-mediated mechanism on CH₄ reforming of CaCO₃ over the hollow submicrospherical Ni/Co-promoted CaO/Ca₁₂Al₁₄O₃₃ is confirmed. After 20 cycles, CO conversion from sorption-enhanced water–gas shift using the as-synthesized material retains 97.0%, accompanied by high CH₄ conversion of 95.1% and the H₂/CO molar ratio close to unity from CH₄ reforming of CaCO₃.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477352","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":"Bifunctional Copper Metal–Organic Framework Catalyst for Late-Stage Functionalization of Alkenes","authors":"Lu Dong, Hu Chen, Xiaoli Tan, Ning Zhang, Wei Sun, Dechao Li, Guangchao Liang, Yanyuan Jia, Shuo Guo","doi":"10.1021/acscatal.5c00755","DOIUrl":"https://doi.org/10.1021/acscatal.5c00755","url":null,"abstract":"Multifunctional catalysts in organic synthesis are highly attractive, particularly in the construction of complex molecules. In this work, we report a heterogeneous bifunctional Cu-based metal–organic framework (MOF) catalyst, IMU-108, serving as both a photoredox catalyst and a cross-coupling catalyst. IMU-108 was synthesized on a gram scale from Cu(NO₃)₂·3H₂O and 5-mercaptoisophthalic acid precursors through a simple refluxing device. The structure of IMU-108 is formed via an <i>in situ</i> S–S bridge bond connecting zero-dimensional metal–organic polyhedra (MOPs), each composed of 12 Cu–Cu paddle-wheel motifs. These interpolyhedral S–S bonds result in a rigid geometric structure and ensure inner MOPs remain bench-stable while maintaining catalytic activity. We demonstrate the capacity of IMU-108 in heterogeneous photoredox-catalyzed cross-coupling of styrenes and α-bromo esters with boronic acids to yield various substituted 1,1-diaryl alkanes in a single step. The versatility of this method enables late-stage functionalization of complex molecules without the need for <i>de novo</i> synthesis. IMU-108 exhibits good reusability, maintaining its catalytic activity over ten consecutive reaction cycles. Furthermore, computational and mechanistic studies suggest that coordinatively unsaturated copper species on the surface of IMU-108 served as catalytically active sites, possessing competent Single-Electron Transfer (SET) reduction ability and facilitating cross-coupling reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477548","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–Gas Shift Reaction over CuxO/Cu(111) (x < 2) from a DFT-MKM-kMC Study","authors":"Yu-Bi Huang, Gui-Chang Wang","doi":"10.1021/acscatal.4c06825","DOIUrl":"https://doi.org/10.1021/acscatal.4c06825","url":null,"abstract":"Cu-based catalysts benefiting from their low cost and high catalytic activity are widely used in the low-temperature water–gas shift reaction (WGSR) industry. However, there is still a lack of understanding of surface oxides (Cu_<i>x</i>O/Cu(111)) and their influence on the catalytic activity. Herein, we focus on these issues, systematically study the relative stability of copper surface oxides over Cu(111) by ab initio atomistic thermodynamics, and then identify their surface population by Boltzmann statistical mechanics. It was found that p4, p4-OCu_3, and p4-(OCu₃)₂ take up a certain proportion of Cu(111) under ideal conditions. The catalytic activity for WGSR was investigated through a combined approach consisting of density functional theory and multisite mean-field microkinetic modeling (MF-MKM) as well as kinetic Monte Carlo (kMC) simulation on these surfaces. The simulation results illustrate that with the ratio of Cu⁺/(Cu⁰ + Cu⁺) increasing, the catalytic activity exhibits a “volcano-type” relationship, in agreement with the experimental observation. Furthermore, the weakly oxidized phase, p4-OCu₃, in which the ratio of Cu⁺/(Cu⁰ + Cu⁺) on the surface equals 0.273, has the best catalytic activity in this paper. That is because its suitable geometric structure enhances the adsorption of H₂O, thus leading to high activity. It is possible that Cu_<i>x</i>O–Cu⁰ can serve as the active site in Cu(111)-catalyzed-WGSR, in which Cu_<i>x</i>O is used to activate H₂O while Cu⁰ is used to form H₂, and the synergistic effect between them is vital to catalyze WGSR. Besides, doping with Pt or Zn can improve the catalytic performance of p4-OCu₃ by enhancing the CO adsorption or lowering the activation energy of the H₂ combination. It is hoped that our results show that the appropriate Cu⁺/(Cu⁰ + Cu⁺) ratio is the WGSR active site and may extend to other systems like Cu(100)-catalyzed WGSR and even Cu/CeO₂.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"5 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486430","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}