The widely studied electrocatalytic CO2 reduction reaction (eCO2RR) has typically been operated at room temperature. However, practical electrolyzers might operate at elevated temperatures, but a major concern is low CO2 solubility. One promising strategy is to construct a hydrophobic interface to enhance CO2 diffusion. Regarding this, atomically precise gold nanoclusters (NCs) can be accurately decorated with hydrophobic ligands to create a local hydrophobic microenvironment to ensure rapid CO2 transfer, yet the temperature effect on the reaction kinetics remains unknown. Here, we report, for the first time, the temperature-dependent eCO2RR performance of hydrophobic Au25(SR)18 NCs by a close interplay between theory and experiment. Simulations revealed that the hydrophobic surface is very conducive to CO2 activation, and the proton transfer process for *COOH and *CO formation can be significantly affected by temperature via modulating interface hydrogen bonding. Particularly, an elevated temperature at 330 K dramatically increases the catalytic activity while simultaneously suppressing the competitive hydrogen evolution reaction. We experimentally demonstrate that Au25 exhibits high eCO2RR performance at 330 K, achieving a high CO Faradaic efficiency of ∼93% and a CO partial current density about 2 times higher than that at room temperature. This work opens exciting opportunities in developing efficient electrocatalysts via synergistic implementation of surface hydrophobicity and temperature-mediated interface engineering.
{"title":"Probing Temperature Effect on Enhanced Electrochemical CO2 Reduction of Hydrophobic Au25(SR)18 Nanoclusters","authors":"Fang Sun, Xia Zhou, Lubing Qin, Zhenghua Tang, Likai Wang, Qing Tang","doi":"10.1021/acscatal.4c05578","DOIUrl":"https://doi.org/10.1021/acscatal.4c05578","url":null,"abstract":"The widely studied electrocatalytic CO<sub>2</sub> reduction reaction (eCO<sub>2</sub>RR) has typically been operated at room temperature. However, practical electrolyzers might operate at elevated temperatures, but a major concern is low CO<sub>2</sub> solubility. One promising strategy is to construct a hydrophobic interface to enhance CO<sub>2</sub> diffusion. Regarding this, atomically precise gold nanoclusters (NCs) can be accurately decorated with hydrophobic ligands to create a local hydrophobic microenvironment to ensure rapid CO<sub>2</sub> transfer, yet the temperature effect on the reaction kinetics remains unknown. Here, we report, for the first time, the temperature-dependent eCO<sub>2</sub>RR performance of hydrophobic Au<sub>25</sub>(SR)<sub>18</sub> NCs by a close interplay between theory and experiment. Simulations revealed that the hydrophobic surface is very conducive to CO<sub>2</sub> activation, and the proton transfer process for *COOH and *CO formation can be significantly affected by temperature via modulating interface hydrogen bonding. Particularly, an elevated temperature at 330 K dramatically increases the catalytic activity while simultaneously suppressing the competitive hydrogen evolution reaction. We experimentally demonstrate that Au<sub>25</sub> exhibits high eCO<sub>2</sub>RR performance at 330 K, achieving a high CO Faradaic efficiency of ∼93% and a CO partial current density about 2 times higher than that at room temperature. This work opens exciting opportunities in developing efficient electrocatalysts via synergistic implementation of surface hydrophobicity and temperature-mediated interface engineering.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546800","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}
The [2σ + 2π] cycloaddition reaction of bicyclo[1.1.0]butanes (BCBs) and alkenes is a powerful method to construct pharmaceutically valuable bicyclo[2.1.1]hexane (BCH) frameworks. Asymmetric strategies developed have enabled [2σ + 2π] cycloaddition reactions of electron-deficient alkenes. However, an effective approach for electron-rich alkenes remains to be realized. Here we report asymmetric [2σ + 2π] cycloaddition reactions of BCBs and electron-rich alkene moieties of vinyl azido and diazo compounds. The chiral Lewis acid-activated BCB ketone complexes are crucial for achieving the reactivity and enantioselectivity. This protocol allows for the synthesis of chiral BCHs featuring two to three quaternary carbon centers and α-chiral tertiary azido or diazo functionalities in up to 98% yield, >19:1 dr, and >99% ee. Broad substrate scope, gram-scale synthesis, and good functional group compatibility demonstrate the practicality for synthesizing complex bicyclic structures. Mechanistic studies reveal that the nucleophilic attack of electron-rich alkenes on the cyclobutyl cation intermediate is the rate-limiting step.
{"title":"Lewis Acid-Catalyzed Asymmetric [2σ + 2π] Cycloaddition Reactions of Bicyclo[1.1.0]butanes and Vinyl Azido/Diazo Compounds","authors":"Haosong Ren, Zhongren Lin, Tianxiang Li, Zhenyue Li, Xinhong Yu, Jun Zheng","doi":"10.1021/acscatal.5c00303","DOIUrl":"https://doi.org/10.1021/acscatal.5c00303","url":null,"abstract":"The [2σ + 2π] cycloaddition reaction of bicyclo[1.1.0]butanes (BCBs) and alkenes is a powerful method to construct pharmaceutically valuable bicyclo[2.1.1]hexane (BCH) frameworks. Asymmetric strategies developed have enabled [2σ + 2π] cycloaddition reactions of electron-deficient alkenes. However, an effective approach for electron-rich alkenes remains to be realized. Here we report asymmetric [2σ + 2π] cycloaddition reactions of BCBs and electron-rich alkene moieties of vinyl azido and diazo compounds. The chiral Lewis acid-activated BCB ketone complexes are crucial for achieving the reactivity and enantioselectivity. This protocol allows for the synthesis of chiral BCHs featuring two to three quaternary carbon centers and α-chiral tertiary azido or diazo functionalities in up to 98% yield, >19:1 dr, and >99% ee. Broad substrate scope, gram-scale synthesis, and good functional group compatibility demonstrate the practicality for synthesizing complex bicyclic structures. Mechanistic studies reveal that the nucleophilic attack of electron-rich alkenes on the cyclobutyl cation intermediate is the rate-limiting step.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547040","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}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.4c07840
Feng Gao, Yisa Xiao, Zimeng Li, Qilong Shen
A copper-catalyzed fluoroalkylation of lithium aryl nbutyl borates with electrophilic fluoroalkylating reagent YlideFluor for the preparation of di-, trifluoromethyl-, and monofluoroalkyl-substituted (hetero)arenes under mild conditions was described. Control experiments indicated that a fluoroalkyl radical, rather than a difluorocarbene intermediate, is involved in the catalytic process. In addition, stoichiometric reactions demonstrated that transmetalation of copper catalyst with lithium aryl nbutyl borate takes place before the single-electron-transfer (SET) oxidation of an ate-type Cu(I) intermediate [CuI(Ar)(SCN)]− by YlideFluor. Based on these mechanistic results, a reasonable catalytic cycle for the copper-catalyzed fluoroalkylation of lithium aryl nbutyl borates was proposed.
{"title":"Sulfonium Ylide Enabled, Copper-Catalyzed Difluoromethylation, Monofluoromethylation, and Monofluoroalkylation of Lithium Aryl nButyl Borates","authors":"Feng Gao, Yisa Xiao, Zimeng Li, Qilong Shen","doi":"10.1021/acscatal.4c07840","DOIUrl":"https://doi.org/10.1021/acscatal.4c07840","url":null,"abstract":"A copper-catalyzed fluoroalkylation of lithium aryl <sup><i>n</i></sup>butyl borates with electrophilic fluoroalkylating reagent YlideFluor for the preparation of di-, trifluoromethyl-, and monofluoroalkyl-substituted (hetero)arenes under mild conditions was described. Control experiments indicated that a fluoroalkyl radical, rather than a difluorocarbene intermediate, is involved in the catalytic process. In addition, stoichiometric reactions demonstrated that transmetalation of copper catalyst with lithium aryl <sup><i>n</i></sup>butyl borate takes place before the single-electron-transfer (SET) oxidation of an ate-type Cu(I) intermediate [Cu<sup>I</sup>(Ar)(SCN)]<sup>−</sup> by YlideFluor. Based on these mechanistic results, a reasonable catalytic cycle for the copper-catalyzed fluoroalkylation of lithium aryl <sup><i>n</i></sup>butyl borates was proposed.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"236 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546805","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}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.4c06815
Zhen Xu, Youbing Zhu, Nianming Jiao, Ketao Shi, Hui Wang
Conversion of crude oil to chemicals is a developing trend in the petroleum industry. Cycloalkanes are main components of crude oil, especially in intermediate- or naphthene-based oil; however, converting cycloalkanes into high-value chemicals, especially light olefins, remains a challenge. In this study, HIM-5 zeolite, with strong Brønsted acidity, small pores, and a large-cavity structure, was proposed as the active material for cyclohexane (a model compound for cycloalkanes) cracking. The external surface of HIM-5 was modified with phosphorus (P) to reduce the acid strength, efficiently improving the catalytic lifetime. To regulate product distribution, an acid–base bifunctional catalyst composed of calcium aluminate (CA) and the most stable zeolite, 1.0P-CIM, was prepared. As the 1.0P-CIM content decreased, the acid amount exhibited an obvious decreasing tendency, while the base amount exhibited the opposite trend. The average light olefins yield over the bifunctional catalysts varied from 11.9–27.8%, while the average BTX (benzene, toluene, xylene) yield was from 31.4–41.6%. Specifically, the light olefins yield in the catalytic system containing 30 wt % zeolite was the highest (27.8%), with an increase of 15.9% compared with that in the 1.0P-CIM system, and the total yield of light olefins and BTX reached the maximum (59.2%). In situ spectroscopic analysis illustrated that CA could activate the reactant, promote ring-opening, and inhibit side reactions such as hydrogen transfer, leading to increased light olefins yield, while the strong acidity of the bifunctional catalyst, when CA content was low, would facilitate BTX formation. Therefore, product distribution could be flexibly adjusted in cyclohexane cracking by changing the acid or base amount in the bifunctional catalyst.
{"title":"Flexible Regulation of Product Distribution in Cyclohexane Cracking Catalyzed by Acid–Base Bifunctional Catalyst","authors":"Zhen Xu, Youbing Zhu, Nianming Jiao, Ketao Shi, Hui Wang","doi":"10.1021/acscatal.4c06815","DOIUrl":"https://doi.org/10.1021/acscatal.4c06815","url":null,"abstract":"Conversion of crude oil to chemicals is a developing trend in the petroleum industry. Cycloalkanes are main components of crude oil, especially in intermediate- or naphthene-based oil; however, converting cycloalkanes into high-value chemicals, especially light olefins, remains a challenge. In this study, HIM-5 zeolite, with strong Brønsted acidity, small pores, and a large-cavity structure, was proposed as the active material for cyclohexane (a model compound for cycloalkanes) cracking. The external surface of HIM-5 was modified with phosphorus (P) to reduce the acid strength, efficiently improving the catalytic lifetime. To regulate product distribution, an acid–base bifunctional catalyst composed of calcium aluminate (CA) and the most stable zeolite, 1.0P-CIM, was prepared. As the 1.0P-CIM content decreased, the acid amount exhibited an obvious decreasing tendency, while the base amount exhibited the opposite trend. The average light olefins yield over the bifunctional catalysts varied from 11.9–27.8%, while the average BTX (benzene, toluene, xylene) yield was from 31.4–41.6%. Specifically, the light olefins yield in the catalytic system containing 30 wt % zeolite was the highest (27.8%), with an increase of 15.9% compared with that in the 1.0P-CIM system, and the total yield of light olefins and BTX reached the maximum (59.2%). <i>In situ</i> spectroscopic analysis illustrated that CA could activate the reactant, promote ring-opening, and inhibit side reactions such as hydrogen transfer, leading to increased light olefins yield, while the strong acidity of the bifunctional catalyst, when CA content was low, would facilitate BTX formation. Therefore, product distribution could be flexibly adjusted in cyclohexane cracking by changing the acid or base amount in the bifunctional catalyst.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546802","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}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.4c07033
Yang Xia, Peng Zhu, Yile Yang, Chang Qiu, Haotian Wang
Electrochemical manufacturing of hydrogen peroxide (H2O2) via oxygen reduction reaction (ORR) has been widely recognized as an alternative to the conventional anthraquinone process, but the output H2O2 concentration that it can reach and the long-term electrolysis stability are still far from industrial requirements. Here, we report the promising potential of the porous solid electrolyte (PSE) reactor for producing high-concentration and high-purity H2O2 in high stability. By identifying the issue of high H2O2 concentration at the cathode/membrane interface that could lead to membrane degradation and low ORR Faradaic efficiencies (FEs), we adopted a water recirculation flow operation instead of continuous flow to effectively carry out the generated H2O2 product from the PSE layer without interfacial accumulation. This recirculation strategy boosted the H2O2 FE from 23% to 50% to produce a 30 wt % H2O2 stream and successfully extended the lifetime of the PSE reactor to ∼1000 h while continuously outputting 20 wt % H2O2 under 100 mA cm–2 operation current.
{"title":"Electrochemical Manufacturing of Hydrogen Peroxide with High Concentration and Durability","authors":"Yang Xia, Peng Zhu, Yile Yang, Chang Qiu, Haotian Wang","doi":"10.1021/acscatal.4c07033","DOIUrl":"https://doi.org/10.1021/acscatal.4c07033","url":null,"abstract":"Electrochemical manufacturing of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) via oxygen reduction reaction (ORR) has been widely recognized as an alternative to the conventional anthraquinone process, but the output H<sub>2</sub>O<sub>2</sub> concentration that it can reach and the long-term electrolysis stability are still far from industrial requirements. Here, we report the promising potential of the porous solid electrolyte (PSE) reactor for producing high-concentration and high-purity H<sub>2</sub>O<sub>2</sub> in high stability. By identifying the issue of high H<sub>2</sub>O<sub>2</sub> concentration at the cathode/membrane interface that could lead to membrane degradation and low ORR Faradaic efficiencies (FEs), we adopted a water recirculation flow operation instead of continuous flow to effectively carry out the generated H<sub>2</sub>O<sub>2</sub> product from the PSE layer without interfacial accumulation. This recirculation strategy boosted the H<sub>2</sub>O<sub>2</sub> FE from 23% to 50% to produce a 30 wt % H<sub>2</sub>O<sub>2</sub> stream and successfully extended the lifetime of the PSE reactor to ∼1000 h while continuously outputting 20 wt % H<sub>2</sub>O<sub>2</sub> under 100 mA cm<sup>–2</sup> operation current.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"130 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539201","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}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.4c07182
Julia Telles de Souza, Alexandre Ferreira Young, Eduardo F. Sousa-Aguiar, Pedro N. Romano, Javier García-Martínez, João M. A. R. De Almeida
This study presents a series of Interzeolite Transformation Intermediates (ITIs) derived from FAU-to-FER interconversion. These hybrid materials, obtained through precise control of the interconversion process, exhibit both large mesoporosity and FER topology-type pore confinement, resulting in high conversion and remarkable shape selectivity despite their disordered structure at the long range. We demonstrated this unique combination of properties in three different catalytic tests. The local order within these ITIs is sufficient to create pore confinement, which not only produces remarkable shape selectivity but also enhances conversion by increasing accessibility. Specifically, the ITIs show a 10-fold increase in activity for Friedel–Crafts alkylation, a 16-fold increase in activity for triisopropylbenzene (TiPBz) cracking, and a two-fold increase in methanol dehydration to dimethyl ether (DME) compared to commercial ferrierite all while maintaining the selectivity of FER. These results highlight the potential of FAU-to-FER ITIs as high-performance catalysts that combine the accessibility of disordered structures with the selectivity typically associated with well-ordered zeolites, opening avenues in zeolite-based catalysis.
{"title":"How Local Order Leads to Shape Selectivity in Disordered Materials: The Case of FAU-FER Interzeolite Transformation Intermediates","authors":"Julia Telles de Souza, Alexandre Ferreira Young, Eduardo F. Sousa-Aguiar, Pedro N. Romano, Javier García-Martínez, João M. A. R. De Almeida","doi":"10.1021/acscatal.4c07182","DOIUrl":"https://doi.org/10.1021/acscatal.4c07182","url":null,"abstract":"This study presents a series of Interzeolite Transformation Intermediates (ITIs) derived from FAU-to-FER interconversion. These hybrid materials, obtained through precise control of the interconversion process, exhibit both large mesoporosity and FER topology-type pore confinement, resulting in high conversion and remarkable shape selectivity despite their disordered structure at the long range. We demonstrated this unique combination of properties in three different catalytic tests. The local order within these ITIs is sufficient to create pore confinement, which not only produces remarkable shape selectivity but also enhances conversion by increasing accessibility. Specifically, the ITIs show a 10-fold increase in activity for Friedel–Crafts alkylation, a 16-fold increase in activity for triisopropylbenzene (TiPBz) cracking, and a two-fold increase in methanol dehydration to dimethyl ether (DME) compared to commercial ferrierite all while maintaining the selectivity of FER. These results highlight the potential of FAU-to-FER ITIs as high-performance catalysts that combine the accessibility of disordered structures with the selectivity typically associated with well-ordered zeolites, opening avenues in zeolite-based catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546804","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}
Polyesters, especially polyethylene terephthalate (PET), are widely used in plastic bottles and clothing fibers because of their stability and cost-effectiveness. Upcycling waste polyesters into value-added materials not only solves the environmental crisis but also realizes significant economic interests. Here, we report a step-economic two-step catalytic process for the upcycling of waste polyester materials, specifically PET, into 1,4-cyclohexanedimethanol (CHDM), an essential monomer for functional polyesters and key feedstock for the liquid crystal industry. The combination of PET methanolysis and hydrogenation of aromatic rings significantly reduces the reaction temperature and energy consumption of the depolymerization of PET, which introduces remarkable engineering benefits. By developing the CO-resistant bifunctional Ru/MnO2 and CuZnZr mixed oxide catalyst system, PET is demonstrated to be converted completely with the final yield of CHDM up to 78%. The implementation of the two-step catalytic process for transforming PET into CHDM holds significant implications for advancing the value chain of polyesters and contributing to waste material utilization for a renewable future.
{"title":"Valorization of Waste Polyester for 1,4-Cyclohexanedimethanol Production","authors":"Yuanchao Huang, Yuxi Si, Xusheng Guo, Chuan Qin, Yongkang Huang, Liang Wang, Xiaofeng Gao, Siyu Yao, Youwei Cheng","doi":"10.1021/acscatal.4c06816","DOIUrl":"https://doi.org/10.1021/acscatal.4c06816","url":null,"abstract":"Polyesters, especially polyethylene terephthalate (PET), are widely used in plastic bottles and clothing fibers because of their stability and cost-effectiveness. Upcycling waste polyesters into value-added materials not only solves the environmental crisis but also realizes significant economic interests. Here, we report a step-economic two-step catalytic process for the upcycling of waste polyester materials, specifically PET, into 1,4-cyclohexanedimethanol (CHDM), an essential monomer for functional polyesters and key feedstock for the liquid crystal industry. The combination of PET methanolysis and hydrogenation of aromatic rings significantly reduces the reaction temperature and energy consumption of the depolymerization of PET, which introduces remarkable engineering benefits. By developing the CO-resistant bifunctional Ru/MnO<sub>2</sub> and CuZnZr mixed oxide catalyst system, PET is demonstrated to be converted completely with the final yield of CHDM up to 78%. The implementation of the two-step catalytic process for transforming PET into CHDM holds significant implications for advancing the value chain of polyesters and contributing to waste material utilization for a renewable future.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546803","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}
Pub Date : 2025-03-03DOI: 10.1021/acscatal.5c00652
Liang Liu, Shiqi Ren, Xianlei Gu, Shouyun Yu
Catalytic kinetic resolution (KR) is an efficient method for synthesizing enantiopure compounds from racemic precursors, offering a valuable tool for asymmetric synthesis. In this study, we report a KR reaction enabled by photoexcited chiral copper complex-catalyzed alkene E → Z isomerization, facilitating the direct synthesis of P-chiral phosphine oxides from racemic tertiary phosphine oxides (TPOs). A series of P-chiral α,β-unsaturated TPOs incorporating pyridinyl groups were obtained with up to 98% enantiomeric excess (ee) and up to 354 selectivity factors (S). Both E- and Z-isomers of α,β-unsaturated TPOs were synthesized with high enantiomeric purity. These P-chiral products can be readily converted into a variety of P-chiral derivatives, including potential chiral biphosphine ligands and Lewis base catalysts, demonstrating the versatility of our approach. This work provides a direct route to synthesizing P-stereogenic phosphine oxides from racemic TPOs via asymmetric photoexcited transition metal catalysis.
{"title":"Kinetic Resolution of α,β-Unsaturated Tertiary Phosphine Oxides via Alkene E → Z Isomerization Catalyzed by a Photoexcited Chiral Copper Complex","authors":"Liang Liu, Shiqi Ren, Xianlei Gu, Shouyun Yu","doi":"10.1021/acscatal.5c00652","DOIUrl":"https://doi.org/10.1021/acscatal.5c00652","url":null,"abstract":"Catalytic kinetic resolution (KR) is an efficient method for synthesizing enantiopure compounds from racemic precursors, offering a valuable tool for asymmetric synthesis. In this study, we report a KR reaction enabled by photoexcited chiral copper complex-catalyzed alkene <i>E</i> → <i>Z</i> isomerization, facilitating the direct synthesis of P-chiral phosphine oxides from racemic tertiary phosphine oxides (TPOs). A series of P-chiral α,β-unsaturated TPOs incorporating pyridinyl groups were obtained with up to 98% enantiomeric excess (ee) and up to 354 selectivity factors (<i>S</i>). Both <i>E</i>- and <i>Z</i>-isomers of α,β-unsaturated TPOs were synthesized with high enantiomeric purity. These P-chiral products can be readily converted into a variety of P-chiral derivatives, including potential chiral biphosphine ligands and Lewis base catalysts, demonstrating the versatility of our approach. This work provides a direct route to synthesizing P-stereogenic phosphine oxides from racemic TPOs via asymmetric photoexcited transition metal catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538346","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}
Pub Date : 2025-03-03DOI: 10.1021/acscatal.4c07453
Peixuan Li, Lei Gao, Lei Tao, Jinbo Pan, Fang Han Lim, Yan-Fang Zhang, Shixuan Du
Two-dimensional (2D) photocatalysts have attracted significant attention in photocatalytic water splitting due to their high surface-area-to-volume ratio and tunable electronic properties. However, enhancing the absorption capacity of 2D photocatalysts remains a fundamental challenge. Through first-principles calculations, we have identified eight scandium/yttrium chalcohalide monolayers (ScSI, ScTeI, ScSeZ, and YTeZ; Z = Cl, Br, I) in the α phase as promising candidates for visible-light-driven overall water splitting, exhibiting appropriate band gaps and band-edge positions. Our analysis of optical absorption spectra demonstrated that the visible-light response increases with the number of layers. Particularly, the absorption intensity of α-ScTeI increases from 15% for the monolayer to 45% for the seven-layer structure. In addition, both monolayer and bulk α-ScTeI show a low exciton binding energy, comparable to that of MoS2, while demonstrating a superior carrier mobility and a longer hot carrier cooling time. These characteristics make them promising candidates for photocatalysis. Our discovery of van der Waals scandium/yttrium chalcohalides as efficient photocatalysts introduces potential candidates for overall water splitting and scalable hydrogen production.
{"title":"Semiconducting Scandium/Yttrium Chalcohalides: Promising Visible-Light-Driven Photocatalysts for Overall Water Splitting","authors":"Peixuan Li, Lei Gao, Lei Tao, Jinbo Pan, Fang Han Lim, Yan-Fang Zhang, Shixuan Du","doi":"10.1021/acscatal.4c07453","DOIUrl":"https://doi.org/10.1021/acscatal.4c07453","url":null,"abstract":"Two-dimensional (2D) photocatalysts have attracted significant attention in photocatalytic water splitting due to their high surface-area-to-volume ratio and tunable electronic properties. However, enhancing the absorption capacity of 2D photocatalysts remains a fundamental challenge. Through first-principles calculations, we have identified eight scandium/yttrium chalcohalide monolayers (ScSI, ScTeI, ScSeZ, and YTeZ; Z = Cl, Br, I) in the α phase as promising candidates for visible-light-driven overall water splitting, exhibiting appropriate band gaps and band-edge positions. Our analysis of optical absorption spectra demonstrated that the visible-light response increases with the number of layers. Particularly, the absorption intensity of α-ScTeI increases from 15% for the monolayer to 45% for the seven-layer structure. In addition, both monolayer and bulk α-ScTeI show a low exciton binding energy, comparable to that of MoS<sub>2</sub>, while demonstrating a superior carrier mobility and a longer hot carrier cooling time. These characteristics make them promising candidates for photocatalysis. Our discovery of van der Waals scandium/yttrium chalcohalides as efficient photocatalysts introduces potential candidates for overall water splitting and scalable hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"52 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539251","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}
Pub Date : 2025-03-03DOI: 10.1021/acscatal.4c06501
Jieying Wan, Ji Yang, Na Yang, Yifei Sun, Chuansheng Hu, Yang Zhao, Xiaoyan Xu, Haifeng Qi, Xiaodong Li, Hao Zhang
Electrochemical nitrate reduction reaction (NO3–RR) presents a sustainable method for ammonia synthesis. Single-atom catalysts possessing the symmetric planar four-ligand structure (M-N4) serve as advantageous catalytic active sites for NO3–RR. However, the inherent extreme symmetry of the standard M-N4 structure limits the reaction kinetics. Herein, we introduce a symmetry-breaking iron single-atom catalyst coordinated with axial chlorine on nitrogen-doped carbon (Cl-Fe-NC) for NO3–RR. Cl-Fe-NC exhibits a 99.4% ammonia Faradaic efficiency (FE) at −0.28 V vs reversible hydrogen electrode (RHE) with a 9396.7 μgNH3 h–1 cm–2 yield rate at −0.68 V vs RHE, remarkably surpassing that of Fe-NC (<80%, 4330.9 μgNH3 h–1 cm–2 at the same potential). Operando synchrotron radiation Fourier transform infrared (SR-FTIR) spectroscopy confirms that key intermediates, such as *NO, *NO-Hx, and σ(N–H), are formed. Density functional theory (DFT) calculations attribute the optimized free energy of NO3–RR intermediates to the axial chlorine design, reducing the potential determination step barrier energy by up to 0.66 eV. The presence of axial Cl atoms modulates the symmetry of the single Fe atom, enhancing the adsorption of nitrate ions and the enrichment of critical intermediates during NO3–RR while inhibiting the hydrogen evolution reaction (HER). This discovery opens avenues for boosting electrochemical ammonia synthesis through the precise modulation of atomic structures by doping heteroatoms for symmetry breaking.
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