{"title":"揭示原子分散金在促进光催化二氧化碳还原和芳基醇氧化中的作用","authors":"","doi":"10.1016/S1872-2067(24)60109-9","DOIUrl":null,"url":null,"abstract":"<div><div>Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity, abundant surface active sites, and efficient charge separation. Nevertheless, the roles of different forms of atomically-dispersed metals (<em>i</em>.<em>e</em>., single-atoms and atomic clusters) in photocatalytic reactions remain ambiguous. Herein, we developed an ethylenediamine (EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms (Au<sub>SA</sub>), Au clusters (Au<sub>C</sub>), and a mixed-phase of Au<sub>SA</sub> and Au<sub>C</sub> (Au<sub>SA+C</sub>) on CdS. In addition, we elucidate the synergistic effect of Au<sub>SA</sub> and Au<sub>C</sub> in enhancing the photocatalytic performance of CdS substrates for simultaneous CO<sub>2</sub> reduction and aryl alcohol oxidation. Specifically, Au<sub>SA</sub> can effectively lower the energy barrier for the CO<sub>2</sub>→*COOH conversion, while Au<sub>C</sub> can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation. As a result, the Au<sub>SA</sub> and Au<sub>C</sub> co-loaded CdS show impressive overall photocatalytic CO<sub>2</sub> conversion performance, achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g<sup>−1</sup> h<sup>−1</sup>, with the selectivities of 93% and 99%, respectively. More importantly, the solar-to-chemical conversion efficiency of Au<sub>SA+C</sub>/CdS reaches 0.57%, which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature (<em>ca</em>. 0.1%). This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions, which is anticipated to pave a new avenue in energy and environmental applications.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":15.7000,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO2 reduction and aryl alcohol oxidation\",\"authors\":\"\",\"doi\":\"10.1016/S1872-2067(24)60109-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity, abundant surface active sites, and efficient charge separation. Nevertheless, the roles of different forms of atomically-dispersed metals (<em>i</em>.<em>e</em>., single-atoms and atomic clusters) in photocatalytic reactions remain ambiguous. Herein, we developed an ethylenediamine (EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms (Au<sub>SA</sub>), Au clusters (Au<sub>C</sub>), and a mixed-phase of Au<sub>SA</sub> and Au<sub>C</sub> (Au<sub>SA+C</sub>) on CdS. In addition, we elucidate the synergistic effect of Au<sub>SA</sub> and Au<sub>C</sub> in enhancing the photocatalytic performance of CdS substrates for simultaneous CO<sub>2</sub> reduction and aryl alcohol oxidation. Specifically, Au<sub>SA</sub> can effectively lower the energy barrier for the CO<sub>2</sub>→*COOH conversion, while Au<sub>C</sub> can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation. As a result, the Au<sub>SA</sub> and Au<sub>C</sub> co-loaded CdS show impressive overall photocatalytic CO<sub>2</sub> conversion performance, achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g<sup>−1</sup> h<sup>−1</sup>, with the selectivities of 93% and 99%, respectively. More importantly, the solar-to-chemical conversion efficiency of Au<sub>SA+C</sub>/CdS reaches 0.57%, which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature (<em>ca</em>. 0.1%). This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions, which is anticipated to pave a new avenue in energy and environmental applications.</div></div>\",\"PeriodicalId\":9832,\"journal\":{\"name\":\"Chinese Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":15.7000,\"publicationDate\":\"2024-10-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chinese Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1872206724601099\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, APPLIED\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724601099","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
Unraveling the roles of atomically-dispersed Au in boosting photocatalytic CO2 reduction and aryl alcohol oxidation
Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity, abundant surface active sites, and efficient charge separation. Nevertheless, the roles of different forms of atomically-dispersed metals (i.e., single-atoms and atomic clusters) in photocatalytic reactions remain ambiguous. Herein, we developed an ethylenediamine (EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms (AuSA), Au clusters (AuC), and a mixed-phase of AuSA and AuC (AuSA+C) on CdS. In addition, we elucidate the synergistic effect of AuSA and AuC in enhancing the photocatalytic performance of CdS substrates for simultaneous CO2 reduction and aryl alcohol oxidation. Specifically, AuSA can effectively lower the energy barrier for the CO2→*COOH conversion, while AuC can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation. As a result, the AuSA and AuC co-loaded CdS show impressive overall photocatalytic CO2 conversion performance, achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g−1 h−1, with the selectivities of 93% and 99%, respectively. More importantly, the solar-to-chemical conversion efficiency of AuSA+C/CdS reaches 0.57%, which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature (ca. 0.1%). This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions, which is anticipated to pave a new avenue in energy and environmental applications.
期刊介绍:
The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.