ACS Catalysis 最新文献

{"title":"Ni-Catalyzed Deoxygenative Cross-Coupling of Alcohols with Aryl Chlorides via an Organic Photoredox Process","authors":"Weikang Xiong,&nbsp;Tengfei Kang*,&nbsp;Fei Li,&nbsp;Huijuan Liao,&nbsp;Yonggang Yan,&nbsp;Jianyang Dong,&nbsp;Gang Li and Dong Xue*,&nbsp;","doi":"10.1021/acscatal.4c0390910.1021/acscatal.4c03909","DOIUrl":"https://doi.org/10.1021/acscatal.4c03909https://doi.org/10.1021/acscatal.4c03909","url":null,"abstract":"<p >Cross-electrophile coupling from naturally abundant materials is of significant value in organic synthesis. Herein, we established a highly efficient deoxygenative cross-coupling reaction using alcohols and industrial preferred aryl chlorides as coupling partners by the merging of photoredox and nickel catalysis with diaryl ketone as a photocatalyst. This methodology features a broad substrate scope and high functional group tolerance, with straightforward application of scale-up synthesis and late-stage modification of structurally complex natural products and pharmaceuticals, including C-4 alkylated pyridines. This protocol most likely proceeds via a HAT and β-scission process to form alkyl radicals from benzoxazolium salt-alcohol adducts.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273722","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":"Hydrogen Peroxide Generation and Hydrogen Oxidation Reaction on Pt/Co/Pt(111) and Pt/Co/Pt(100) Single-Crystal Model Catalyst Surface","authors":"Kenta Hayashi*,&nbsp;Takeru Tomimori,&nbsp;Yoshihiro Chida,&nbsp;Naoto Todoroki and Toshimasa Wadayama,&nbsp;","doi":"10.1021/acscatal.4c0310610.1021/acscatal.4c03106","DOIUrl":"https://doi.org/10.1021/acscatal.4c03106https://doi.org/10.1021/acscatal.4c03106","url":null,"abstract":"<p >To mitigate proton-exchange membrane (PEM) degradation, suppressing hydrogen peroxide (H₂O₂) generation is desired for the anode catalyst of PEM fuel cells (PEMFCs), while keeping the hydrogen oxidation reaction (HOR) activity. In this study, Pt/Co/Pt(111) and Pt/Co/Pt(100), approximately 2 nm-thick epitaxially stacked layers of Pt and Pt–Co alloy deposited on Pt(111) and Pt(100) single-crystal surfaces, respectively, were used as microstructural surface models of the Pt–Co anode catalyst, and the H₂O₂ generation and HOR mechanisms were discussed using the substrate generation/tip collection and tip generation/substrate collection modes of a scanning electrochemical microscope. We found that H₂O₂ generation on Pt/Co/Pt(111) was much lower than that on clean Pt(111), whereas the H₂O₂ generation property of Pt/Co/Pt(100) was similar to that of clean Pt(100). The influence of the underlying Co (Pt–Co) layers on H₂O₂ generation is discussed from the viewpoints of two previously proposed mechanisms: the adsorbed hydrogen (H_ads)-related and water-adlayer-related mechanisms. Considering the applied potential dependence of H₂O₂ generation, the former H_ads-related mechanism could not explain the H₂O₂ generation behavior of Pt/Co/Pt(100), whereas the latter water-adlayer-related mechanism could apply to both Pt/Co/Pt(111) and Pt/Co/Pt(100). Regarding the HOR, Pt/Co/Pt(100) showed a higher activity than that of clean Pt(100), whereas the activity of Pt/Co/Pt(111) was lower than that of the corresponding clean Pt(111). Such surface-atomic-arrangement-dependent HOR activities of Pt induced by the underlaid Co (Pt–Co) layers can be explained by weakened hydrogen adsorption energy, which can be rationalized by cyclic voltammogram features. The results clarify the alloying effect of Pt with Co for suppressing H₂O₂ generation while maintaining substantial HOR activity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270097","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":"Metallaphotoredox Synthesis of Axially Chiral Tetrasubstituted Allenes through Regio- and Enantioselective 1,4-Carbocyanation of 1,3-Enynes","authors":"Keyi Peng, Ya-Sheng Cao, Quanyuan Wang, Ziwei Xia, Ya Chen, Yixin Lu, Guo-Jun Deng","doi":"10.1021/acscatal.4c04330","DOIUrl":"https://doi.org/10.1021/acscatal.4c04330","url":null,"abstract":"Radical 1,4-difunctionalization of 1,3-enynes represents a promising approach for the rapid creation of allenes from readily available feedstocks. However, the enantioselective synthesis of tetra-substituted chiral allenes from 1,3-enynes via a radical pathway remains difficult. Herein, we disclose an enantioselective decarboxylative 1,4-carbocyanation of 1,3-enynes through photoredox and copper dual catalysis, affording a wide array of axially chiral tetra-substituted allenes in a highly chemoselective, regioselective, and enantioselective manner. This mild and redox-neutral protocol exhibits broad substrate scope and good functional group tolerance and enables late-stage allenyation of natural and drug-like molecules.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142160965","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":"On the Structure Sensitivity of CO2 Hydrogenation over Cu/ZrO2: Insights into the Role of the Support and the Active Sites","authors":"Tomás Vergara*,&nbsp;Daviel Gómez,&nbsp;Lucas Warmuth,&nbsp;Annika E. Enss,&nbsp;Martin Peterlechner,&nbsp;Rodrigo Pallacán,&nbsp;Vlad Martin Diaconescu,&nbsp;Laura Simonelli,&nbsp;Felix Studt,&nbsp;Patricia Concepción,&nbsp;Romel Jiménez and Alejandro Karelovic*,&nbsp;","doi":"10.1021/acscatal.4c0380310.1021/acscatal.4c03803","DOIUrl":"https://doi.org/10.1021/acscatal.4c03803https://doi.org/10.1021/acscatal.4c03803","url":null,"abstract":"<p >The well-known structure sensitivity of CO₂ hydrogenation to methanol has shown to be an impactful topic for the performance of the catalyst and yet remains unaddressed for Cu nanoparticles supported on ZrO₂, a material that has shown to be involved in the active site and the reaction mechanism of methanol formation. Herein, Cu/ZrO₂ catalysts were studied to unravel the underlying structure–activity relationships by combining surface and bulk characterization techniques, kinetic measurements, operando<i>-</i>DRIFTS and DFT calculations. Contrary to Cu over inert supports, the results showed different trends and two distinct kinetic regimes. For Cu nanoparticles larger than 2 nm, they are in accordance with previously reported results, this is, a change in the number of active sites, without affecting the nature of them. Conversely, it is demonstrated that the active sites are markedly different over the regime of nanoparticles smaller than 2 nm, accessed for ultralow Cu contents of 0.1 wt %, as evidenced from the systematic change of kinetic parameters and from operando<i>-</i>DRIFTS. The distinct active sites were identified as isolated Cu species (i.e., single atoms and Cu incorporated into the lattice of ZrO₂) and highly stable Cu clusters, both of which would allocate the formation of products for low metal contents. The results are certainly related to the interaction between Cu and ZrO₂ and unequivocally disclose the relationship between activity regimes and the nature of active sites as a function of the Cu particle size. Furthermore, they demonstrate that distinct active sites can be accessed just by varying the metal content on active reducible supports. As such, the findings are of particular relevance for the fundamental understanding of the interaction between Cu and ZrO₂ and its interdependence with the size of the Cu nanoparticles, as well as for the rational design of catalysts for CO₂ hydrogenation to methanol.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142273721","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":"Effects of Acid Sites and Formaldehyde Decomposition on the Catalyst Lifetime for Methanol-to-Olefins over Ca-Modified HZSM-5","authors":"Jinsong Luo,&nbsp;Tianci Xiao,&nbsp;Wu Wen,&nbsp;Jun Bao,&nbsp;Chengyuan Liu* and Yang Pan*,&nbsp;","doi":"10.1021/acscatal.4c0284210.1021/acscatal.4c02842","DOIUrl":"https://doi.org/10.1021/acscatal.4c02842https://doi.org/10.1021/acscatal.4c02842","url":null,"abstract":"<p >The pursuit for higher light olefin selectivity and extended catalyst lifetime has been a hot topic in the methanol-to-olefins (MTO) process. The incorporation of Ca in HZSM-5 (Ca-modified HZSM-5) could exhibit outstanding catalytic stability and high C3+ olefins yield. In this work, synchrotron radiation photoionization mass spectrometry was applied to study the lifetime enhancement mechanism of Ca-modified HZSM-5. It is interesting to note that the mechanism differs in the cases of different Ca-loading. Under low Ca-loading, the main reason for lifetime enhancement is the modification of acid sites, which limited hydrogen transfer reactions and subsequent coking process. While higher Ca-loading would introduce CaO species over HZSM-5, which showed prominent activity for HCHO elimination. The decomposition of HCHO would suppress the HCHO-mediated aromatic formation pathway during the MTO process, therefore alleviating the coking process. Moreover, the elimination mechanism of HCHO over CaO was investigated using in situ IR measurements. This study provides some additional insights into the role of acid sites and CaO during the Ca-modified HZSM-5 catalyzed MTO process.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270065","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":"Iridium-Catalyzed Asymmetric Cascade Allylation/[1,4]-Phospha-Brook Rearrangement Reaction","authors":"Zhi-Yuan Yi,&nbsp;Hui Xu,&nbsp;Xin Chang,&nbsp;Yanfeng Dang*,&nbsp;Xiu-Qin Dong* and Chun-Jiang Wang*,&nbsp;","doi":"10.1021/acscatal.4c0407810.1021/acscatal.4c04078","DOIUrl":"https://doi.org/10.1021/acscatal.4c04078https://doi.org/10.1021/acscatal.4c04078","url":null,"abstract":"<p >Chiral δ-carbonyl phosphates and their derivatives represent important structural units frequently found in natural products and biologically active molecules and have been extensively employed as key intermediates in organic synthesis. Herein, an unprecedented iridium-catalyzed asymmetric cascade allylation/[1,4]-phospha-Brook rearrangement of β-keto phosphonates with vinyl ethylene carbonate was established, offering an efficient synthetic strategy to access highly functionalized chiral δ-carbonyl phosphates that are difficult to access via known methods. This protocol features easily available starting materials, mild reaction conditions, high chemo-/regio-/enantioselectivity, and a wide substrate scope. Notably, this methodology can be extended to various β-functionalized phosphonates. The gram-scale reaction, diverse functional transformations, and stereodivergent synthesis of chiral δ-hydroxyl phosphates containing two nonadjacent stereocenters demonstrated the synthetic potential of this method. The synthetic utility of this cascade reaction was further confirmed in the concise formal synthesis of natural products hormosirene, dictyopterene A, and biologically active (<i>R</i>)-MCPA-CoA. Control experiments and density field theory computational mechanistic studies revealed that this transformation undergoes asymmetric allylation via kinetic resolution followed by a unique [1,4]-phospha-Brook rearrangement. Ligand–substrate interactions were identified to rationalize the kinetic resolution and chiral induction. The stronger σ-bond of P–O than that of O–C makes the [1,4]-phospha-Brook rearrangement kinetically and thermodynamically favorable.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270098","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":"Ni-Catalyzed Deoxygenative Cross-Coupling of Alcohols with Aryl Chlorides via an Organic Photoredox Process","authors":"Weikang Xiong, Tengfei Kang, Fei Li, Huijuan Liao, Yonggang Yan, Jianyang Dong, Gang Li, Dong Xue","doi":"10.1021/acscatal.4c03909","DOIUrl":"https://doi.org/10.1021/acscatal.4c03909","url":null,"abstract":"Cross-electrophile coupling from naturally abundant materials is of significant value in organic synthesis. Herein, we established a highly efficient deoxygenative cross-coupling reaction using alcohols and industrial preferred aryl chlorides as coupling partners by the merging of photoredox and nickel catalysis with diaryl ketone as a photocatalyst. This methodology features a broad substrate scope and high functional group tolerance, with straightforward application of scale-up synthesis and late-stage modification of structurally complex natural products and pharmaceuticals, including C-4 alkylated pyridines. This protocol most likely proceeds via a HAT and β-scission process to form alkyl radicals from benzoxazolium salt-alcohol adducts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142160920","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 Reaction Kinetics and Thermodynamics for Photocatalytic CO2 Reduction through Spin Polarization Manipulation","authors":"Mingyang Li, Shiqun Wu, Dongni Liu, Zhicheng Ye, Chengxuan He, Jinlong Wang, Xiaoyi Gu, Zehan Zhang, Huizi Li, Jinlong Zhang","doi":"10.1021/acscatal.4c03802","DOIUrl":"https://doi.org/10.1021/acscatal.4c03802","url":null,"abstract":"The intrinsic properties of electrons, “spin”, significantly influence chemical reactions, particularly in catalysis, in terms of reaction rates and pathways. Notably, the effect of electron spin polarization (SP) has been demonstrated to significantly impact photocatalytic processes, yet the exact mechanism remains unclear. In this study, we achieved a controlled manipulation of the material’s SP degree by strategically modulating the Co vacancies (V_Co) within Co_3–<i>x</i>O₄ as corroborated by magnetic circular dichroism (MCD), positron annihilation spectroscopy, X-ray absorption fine structure (XAFS), and density functional theory (DFT) calculations. Carrier kinetic investigation reveals that the inherent SP of the material and external magnetic field augmented SP significantly enhances charge carrier mobility while attenuating the recombination of photoinduced carriers. Significantly, SP confers a thermodynamic benefit in CO₂ reduction, favoring reactant adsorption and concurrently diminishing the free energy requisite for the rate-determining step. Remarkably, a CO production rate of 0.354 μmol h^–1 (5 mg of catalyst) with 100% selectivity is achieved through manipulation of SP within Co_3–<i>x</i>O₄ and applying an external magnetic field. This work reveals the mechanisms of SP effects on photocatalytic reactions, offering insights into the design of CO₂ reduction photocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142160921","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":"Saccharide-Assisted Resolution of Bioactive Chiral Carboxylic Acids via NHC-Catalyzed Regioselective Transesterification","authors":"Shuolu Dai, Juan Zou, Haiqi Wang, Min Xu, Erjuan Xu, Jia Song, Yu Hong, Shaojun Li, Wen-Xin Lv, Yonggui Robin Chi","doi":"10.1021/acscatal.4c04076","DOIUrl":"https://doi.org/10.1021/acscatal.4c04076","url":null,"abstract":"The utility of unprotected saccharides as chiral auxiliaries in asymmetric synthesis remains largely undeveloped despite their ready availability, configurational diversity, and chiral purity. Here, we disclose an efficient achiral NHC catalytic strategy to regioselectively install racemic α,α-disubstituted carboxylic esters on specific OH groups of saccharides and simultaneously achieve their dynamic kinetic resolution, which makes unprotected saccharides effective chiral auxiliaries. Multiple controlling parameters, including stereoelectronic and steric effects, are employed to ensure regioselectivity amplification and stereodifferentiation. By varying the structures of NHC catalysts, this strategy is suitable for dynamic kinetic resolution of diverse racemic targets by installing them on different OH sites of structurally diverse unprotected saccharides, greatly expanding the application of saccharides in asymmetric synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142160922","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":"Effects of Acid Sites and Formaldehyde Decomposition on the Catalyst Lifetime for Methanol-to-Olefins over Ca-Modified HZSM-5","authors":"Jinsong Luo, Tianci Xiao, Wu Wen, Jun Bao, Chengyuan Liu, Yang Pan","doi":"10.1021/acscatal.4c02842","DOIUrl":"https://doi.org/10.1021/acscatal.4c02842","url":null,"abstract":"The pursuit for higher light olefin selectivity and extended catalyst lifetime has been a hot topic in the methanol-to-olefins (MTO) process. The incorporation of Ca in HZSM-5 (Ca-modified HZSM-5) could exhibit outstanding catalytic stability and high C3+ olefins yield. In this work, synchrotron radiation photoionization mass spectrometry was applied to study the lifetime enhancement mechanism of Ca-modified HZSM-5. It is interesting to note that the mechanism differs in the cases of different Ca-loading. Under low Ca-loading, the main reason for lifetime enhancement is the modification of acid sites, which limited hydrogen transfer reactions and subsequent coking process. While higher Ca-loading would introduce CaO species over HZSM-5, which showed prominent activity for HCHO elimination. The decomposition of HCHO would suppress the HCHO-mediated aromatic formation pathway during the MTO process, therefore alleviating the coking process. Moreover, the elimination mechanism of HCHO over CaO was investigated using in situ IR measurements. This study provides some additional insights into the role of acid sites and CaO during the Ca-modified HZSM-5 catalyzed MTO process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142166547","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}