ACS Catalysis 最新文献

{"title":"Defect-Rich Carbon-Blocked Delocalized Sulfur Quantum Dots for Efficient Catalytic Acetylene Hydrochlorination","authors":"Renqin Chang, Guangyu Cheng, Tao Feng, Saisai Wang, Jiale Huang, Yuchen Zhang, Chunxiao Jin, Yuxue Yue, Jia Zhao, Xiaonian Li","doi":"10.1021/acscatal.4c04906","DOIUrl":"https://doi.org/10.1021/acscatal.4c04906","url":null,"abstract":"Porous carbon-supported quantum dot (QD) catalysts have attracted widespread attention due to their tunable energy level structure, electron transport capability, and quantum confinement effects. However, significant challenges remain in their controlled synthesis and large-scale production. To achieve this, a novel nanodigging technique (NDT) was developed for the facile synthesis of carbon-based catalysts loaded with sulfur quantum dots (S-QDs), and <i>in situ</i> Raman, <i>in situ</i> DRIFTS, and <i>quasi-in situ</i> X-ray photoelectron spectroscopy (XPS) techniques were performed to systematically investigated the formation mechanism of S-QDs on the carbon matrix during microwave heating. The optimal SC-600 catalysts exhibited appreciable catalytic performance in hydrochlorination of acetylene to vinyl chloride (VCM), demonstrating a high space-time yield (STY) of 23.74 kg_VCM kg_S^–1 h^–1, and durability (over 300 h). Experiment and theoretical calculations revealed that the S-QDs, in conjunction with surrounding carbon atoms, form a Frustrated-Lewis-Pair-like structure that displays significant surface charge polarization, thereby improving the selective adsorption and activation of reactants. Specifically, the p−π interactions and nonclassical hydrogen bonding effectively activate acetylene and HCl, respectively, and following a Langmuir–Hinshelwood mechanism to efficiently produce VCM. This discovery provides valuable insights into the design of carbon material surface charge distribution and spatial transfer, facilitating the targeted and controllable design and synthesis of high-efficiency QD catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536428","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":"Photocatalytic CH4 Upgrading to Multicarbon Products","authors":"Shuya Hao, Qing Han, Gengfeng Zheng","doi":"10.1021/acscatal.4c05009","DOIUrl":"https://doi.org/10.1021/acscatal.4c05009","url":null,"abstract":"Methane is both a greenhouse gas and an abundant C₁ fuel resource that exists in nature. The selective photocatalytic upgrading of methane into multicarbon (C₂₊) chemicals can both mitigate the greenhouse effect and promote the utilization and value of methane, in which the C–C coupling step is key to the production of multicarbon products. Achieving this targeted upgrading under ambient temperature and pressure conditions requires efficient activation of the C–H bonds in methane as well as the balancing of the adsorption and desorption of various free radicals and C₁ intermediates to facilitate efficient C–C coupling. In this Review, we delve into the recent advances in the photocatalytic upgrading of methane to C₂₊ products. The importance of catalyst design, including the active site assembly, crystal surface, and valence reconstruction, is first emphasized. Then, we discuss how coreactants such as carbon dioxide and carbon monoxide can be introduced to enhance the carbon chain growth pathways. Furthermore, we also summarize the developments of looping systems and photoelectrocatalysis. Finally, we conclude with an outlook for the future advancement in this photocatalytic methane upgrading field. This Review aims to provide a general framework for investigating photocatalytic methane C–C coupling reactions toward multicarbon products, thereby suggesting future research directions toward environmentally friendly and efficient methane upgrading strategies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541967","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":"Closing the Loop of Cyclopolymerization of Nonconjugated α,ω-Diolefin Diasteroselectivity and α-Olefin Polymerization Enantioselectivity","authors":"Olga D’Anania, Fabio De Stefano, Claudio De Rosa, Giovanni Talarico, Rocco Di Girolamo","doi":"10.1021/acscatal.4c05020","DOIUrl":"https://doi.org/10.1021/acscatal.4c05020","url":null,"abstract":"The cyclopolymerization of α,ω-dienes catalyzed by transition metals (TMs) is one of the most attractive synthetic routes for the production of cyclic polyolefins (COPs). These COPs exhibit unique properties that confer enhanced performance and durability, making them highly desirable for advanced applications. By variation of the catalytic system, controlled microstructures of COPs can be achieved, particularly regarding the configuration of cyclic units and the cyclization ratio. The relationship between the catalyst structure, diastereoselectivity, and cyclization efficiency in the cyclopolymerization of 1,5-hexadiene (1,5-HD) and 1,7-octadiene (1,7-OD) has been explored by a combined study based on the density functional theory (DFT) calculation and experimental study involving the synthesis and characterization of the resulting polymers. DFT calculations explained the <i>trans</i>-selectivity of the majority of metallocene and nonmetallocene systems as well as the peculiar <i>cis</i>-selectivity of the nonmetallocene pyridylamido complex for 1,5-HD polymerization. The predicted diastereoselectivity was successfully corroborated by ¹H and ¹³C NMR spectroscopic data collected from the synthesized polymers. Analyses by WAXS and DSC and the study of mechanical properties were performed to investigate their structural/property relationships. DFT calculations have been used also for explaining the experimental switching to <i>cis</i>-selectivity for the cyclopolymerization of 1,7-OD achieved by the TM systems promoting the <i>trans</i>-selectivity of 1,5-HD. The comparison with the enantioselectivity of α-olefin polymerization has been used as a key guideline for this work closing the loop between the diastereoselectivity of nonconjugated α,ω-diolefin cyclopolymerization and the enantioselectivity of the α-olefin polymerization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519374","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":"Correction to “Impact of Sn Lewis Acid Sites on the Dehydration of Cyclohexanol”","authors":"Karen A. Resende, Ruixue Zhao, Yue Liu, Eszter Baráth, Johannes A. Lercher","doi":"10.1021/acscatal.4c05977","DOIUrl":"https://doi.org/10.1021/acscatal.4c05977","url":null,"abstract":"Page 11747: The acknowledgment should read as given here. K. A. R. would like to thank the Alexander von Humboldt Foundation and the Coordination for the Improvement of Higher Education Personnel (CAPES) for the financial support. J. A. L. is grateful for the support for this work by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (Impact of catalytically active centers and their environment on rates and thermodynamic states along reaction paths, FWP 47319). The authors acknowledge Dr. David S. Potts (Department of Chemical and Biomolecular Engineering, University of Illinois Urbana–Champaign, Urbana, Illinois, USA) for carrying out the adsorption measurements and Prof. David W. Flaherty (Department of Chemical and Biomolecular Engineering, University of Illinois Urbana–Champaign, Urbana, IL 61801 USA; School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, USA) for fruitful discussions. This article has not yet been cited by other publications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519373","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":"Stereodivergent Synthesis of Atropisomeric Indole-Fused δ-Lactams Bearing All-Carbon Quaternary Stereocenters via Cu-Catalyzed Desymmetric Arene Amidation","authors":"Bo-Han Zhu, Yu-Jie Ye, Guan-Zhi Liu, Si-Chao Wu, Xiuyuan Zou, Long Li, Chengzhe Huang, Qing Sun, Long-Wu Ye, Peng-Cheng Qian","doi":"10.1021/acscatal.4c04504","DOIUrl":"https://doi.org/10.1021/acscatal.4c04504","url":null,"abstract":"Great achievements have been made in constructing valuable chiral lactams via noble metal-catalyzed intramolecular γ-amidations using dioxazolones as nitrene precursors. However, most of them are limited to synthesizing central chirality, and the preparation of all-carbon quaternary stereocenters and C−N axial chirality is extremely challenging and still under-explored. Herein, a Cu-catalyzed desymmetric arene δ-lactamizations of dioxazolones is disclosed, leading to the diastereodivergent synthesis of chiral indole-fused δ-lactams bearing all-carbon quaternary stereocenters and C−N axial chirality in generally good yield, stereoselectivity, and regioselectivity with wide substrate scope. Interestingly, all four stereoisomers of δ-lactams containing all-carbon quaternary stereocenters and C−N axial chirality can be readily achieved simply by varying the configurations of the single chiral copper catalyst and base treatments. Additionally, this reaction probably undergoes a Cu-catalyzed singlet nitrene transfer/rearrangement and remote enantiocontrol process strongly supported by control experiments and theoretical calculations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142519442","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":"Understanding the Different Roles of Adsorbed Oxygen and Lattice Oxygen Species in the Distinct Catalytic Performance of Metal Oxides for o-Xylene Oxidation","authors":"Ying Ma, Lian Wang, Jinzhu Ma, Guangzhi He, Daiqiang Li, Hong He","doi":"10.1021/acscatal.4c04284","DOIUrl":"https://doi.org/10.1021/acscatal.4c04284","url":null,"abstract":"Metal oxides have always been considered as promising non-noble metal catalysts for VOC elimination and generally show distinct performance based on their reactive oxygen species (ROS). This work originally investigated the roles of adsorbed oxygen (O_ads) and lattice oxygen (O_lat) species in the catalytic oxidation of <i>o</i>-xylene. A series of metal oxide catalysts were synthesized through the pyrolysis of MOF precursors. The CeO₂ catalyst showed performance superior to that of other metal oxides at lower temperature, while the Co₃O₄ catalyst had advantages over other metal oxides in the complete oxidation of <i>o</i>-xylene and CO₂ generation but also exhibited a larger decrease of <i>o</i>-xylene conversion with the drop of O₂ concentration. The <i>o</i>-xylene-TPD and <i>o</i>-xylene-TPSR (¹⁸O₂/He) profiles of CeO₂, Co₃O₄, and CuO indicated that the O_ads served as the primary ROS of CeO₂ and that the O_lat played decisive roles in the cases of Co₃O₄ and CuO. Notably, the surface O_lat of Co₃O₄ could be rapidly and completely replenished by gaseous oxygen, relying more on gaseous oxygen compared to CuO. Furthermore, <i>in situ</i> DRIFTS studies and DFT calculations disclosed the interactions of different ROS with <i>o</i>-xylene. The O_ads on the CeO₂ surface favored the adsorption and cleavage oxidation of the aromatic ring at lower temperature, while the O_lat on the Co₃O₄ and CuO surface preferentially oxidized methyl groups and favored the oxidation of intermediates. Therefore, the different interactions with <i>o</i>-xylene and replenishment of ROS are responsible for the performance differences of CeO₂, Co₃O₄, and CuO in the catalytic oxidation of <i>o</i>-xylene. This work might provide insights into the catalytic mechanism of metal oxides and benefit the design and application of efficient metal oxide catalysts for VOC elimination.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490338","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":"Metal Carbene-Directed Intramolecular Vinylogous Reactions of Vinyldiazoacetates","authors":"Marlyn S. Rada, Dmitry M. Bystrov, Diana Navarrete Carriola, Daniel Wherritt, Michael P. Doyle","doi":"10.1021/acscatal.4c05839","DOIUrl":"https://doi.org/10.1021/acscatal.4c05839","url":null,"abstract":"Intramolecular addition reactions of electrophilic metallovinylcarbenes with nucleophiles that do not have access to the carbene center undergo addition to the vinylogous position, forming products that rely on subsequent transformations of vinylmetal intermediates. Catalytic addition to a carbon-carbon double bond elicits the formation of an intermediate carbocation whose proton loss causes protodemetalation of the vinylmetal intermediate. Addition to the azido group results in the formation of aliphatic 1,2,3-triazines by [3 + 3]-cycloaddition. Catalytic intramolecular reactions with a carbamate nucleophile yield a carbonyl ylide whose loss of isobutylene produces oximidovinyl-oxazolidinone esters with high enantioselectivity. Comparisons are made between rhodium, copper, gold, and silver catalysts","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490101","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":"Role of LiOH in Aqueous Electrocatalytic Defluorination of Perfluorooctanoic Sulfonate: Efficient Li–F Ion Pairing Prevents Anode Fouling by Produced Fluoride","authors":"Ziyi Meng, Madeleine K. Wilsey, Astrid M. Müller","doi":"10.1021/acscatal.4c04523","DOIUrl":"https://doi.org/10.1021/acscatal.4c04523","url":null,"abstract":"Per- and polyfluoroalkyl substances (PFAS) pose a significant environmental and health threat due to their high toxicity, widespread use, and persistence in the environment. Electrochemical methods have emerged as promising approaches for PFAS destruction, offering cost-effective and energy-efficient solutions. We established recently that electrocatalysis with nonprecious materials enabled the complete defluorination of perfluorooctanesulfonate (PFOS) in aqueous 8.0 M LiOH. Here, we reveal the mechanistic role of LiOH in the efficient aqueous electrocatalytic PFOS defluorination. Our results demonstrate that synergistic effects of high lithium and high hydroxide ion concentrations are essential for complete PFOS defluorination. Two-dimensional NMR data of electrolytes post pulsed electrolysis provide experimental evidence for Li–F ion pairing, which plays a crucial role in preventing anode fouling by produced fluoride, thus enabling sustained C–F bond cleavage. This Li–F ion pairing was increased at high pH, and elevated temperatures enhanced diffusion of Li–F ion pairs into the bulk electrolyte. High hydroxide ion concentrations additionally removed fluoride from the anode surface by competitive adsorption, corroborated by XPS data. Our findings provide quantitative mechanistic insights into the electrocatalytic defluorination process and offer a general route of enhancing the efficiency of anodic PFAS defluorination.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489883","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":"Efficient IrIII Photosensitizer Incorporated in the Metal–Organic Framework with the Bis-lophine-bipyridine Motif for C(sp3)-C/N–H Cross-Coupling Reactions","authors":"Yuan Chen, Ao-Gang Liu, Zi-Tong Chen, Xiao-Huan Liang, Jun-Tao Yan, Bao Li","doi":"10.1021/acscatal.4c04666","DOIUrl":"https://doi.org/10.1021/acscatal.4c04666","url":null,"abstract":"Photocatalytic technology offers a potential solution to energy and environmental issues. The performance of photocatalysts directly affects the efficiency of photocatalysis. Iridium(III)-based catalysts have garnered attention due to their unique electronic structure and high catalytic activity. However, most Ir^III catalysts are homogeneous and face issues such as low stability and difficulty in recycling. The research on heterogeneous Ir^III catalysts has become a hot topic, aiming to improve their stability and recyclability. In this study, we designed a tetracarboxylate ligand containing bipyridine modified with a bilophthalene unit, constructed a Zr-based metal–organic framework (MOF) with a 2-fold interpenetrating structure, and introduced [Ir^III(ppy)₂]⁺ units through postmodification to form Ir@Zr-MOF. The heterostructure enhanced the utilization of light energy and photocatalytic efficiency. Apart from the electron transfer pathway between the original zirconium clusters and the bis-lophine-bipyridine unit, comparative studies of theoretical models showed that the introduction of the [Ir^III(ppy)₂]⁺ unit reduced the energy level and enhanced the absorption of visible light in the 500–550 nm range, corresponding to the charge transfer between the modified bis-lophine-bipyridine and [Ir^III(ppy)₂]⁺ unit. Ir@Zr-MOF, as a photocatalyst, can facilitate the trifluoromethylation of coumarins and the oxidative dehydrogenative coupling reaction of ethers with aryl hydrazones. The conversion yields of the related reactions can reach up to 95%. The mechanism presumes that the generation of superoxide radicals and the corresponding holes produced by Ir@Zr-MOF are crucial for the photocatalytic reaction. The generation of superoxide radicals can be verified by ESR. The host–guest interactions and hole effects of Ir@Zr-MOF with reaction substrates were also explored through theoretical simulations. This work provides a strategy for the heterogenization of Ir^III catalysts, offering insights for the preparation of photosensitizers and the enhancement of light energy utilization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489905","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":"Nickel-Catalyzed Regio- and Stereoselective Hydroalkylation of Allenes: Exploiting the Unique Reactivity of Diazo Compounds as an Alkylating Source","authors":"Ujjwal Karmakar, Jaehan Bae, Jin A Kim, Seoyeon Kim, Won-Geun Yang, Eun Jin Cho","doi":"10.1021/acscatal.4c05410","DOIUrl":"https://doi.org/10.1021/acscatal.4c05410","url":null,"abstract":"The reactivity of allenes has historically been limited with no previous examples of their hydroalkylation using diazo compounds in any transition-metal catalytic framework. In this study, we present a Ni-catalyzed regio- and stereoselective hydroalkylation reaction of allenes utilizing diazo compounds as alkylating agents. The success of this method can be attributed to the use of a pyridine-based P,N ligand, which combines the advantages of both phosphine and nitrogen ligands. Additionally, the carbonyl group in the diazo compound facilitates the formation of stable intermediates. Our detailed mechanistic studies reveal that the reaction proceeds through an initial interaction with the diazo compound, followed by engagement with the allene.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490098","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}