{"title":"共价三嗪框架/ZnIn2S4 核壳结构上光催化二氧化碳还原和选择性氧化的空间耦合","authors":"Qi Li, Xiang Li, Mang Zheng, Fanqi Luo, Liping Zhang, Bin Zhang, Baojiang Jiang","doi":"10.1002/adfm.202417279","DOIUrl":null,"url":null,"abstract":"Photocatalytic CO<sub>2</sub> reduction coupled with alcohol oxidation to aldehyde presents a promising strategy for the simultaneous production of fuels and valuable chemicals. The efficiency of the coupled photocatalytic reactions remains low due to poor charge separation, difficulty in CO<sub>2</sub> activation, and uncontrolled compatibility between reactions. This work presents S-bridged covalent triazine framework (SCTF) core-ZnIn<sub>2</sub>S<sub>4</sub> shell photocatalysts for simultaneous CO<sub>2</sub> reduction and selective furfural synthesis at distinct active sites. As evidenced by in situ X-ray photoelectron spectroscopy and Kelvin probe force microscopy, photogenerated electrons in the composite photocatalysts transfer from the ZnIn<sub>2</sub>S<sub>4</sub> shell to the SCTF core, improving charge separation. Experimental and theoretical results confirm that the presence of pyridine N atoms (Lewis basic sites) in SCTF enhances CO<sub>2</sub> adsorption, thereby reducing the energy barrier for *COOH generation and promoting *CO production. Meanwhile, furfuryl alcohol oxidation and deprotonation occur on ZnIn<sub>2</sub>S<sub>4</sub> by consuming photogenerated holes, which in turn benefits the conversion of CO<sub>2</sub> to CO. As a result, the optimized SCTF/ZnIn<sub>2</sub>S<sub>4</sub>-0.2 core/shell photocatalyst exhibited a superior CO production yield of 263.5 µmol g<sup>−1</sup> and 95% conversion of furfuryl alcohol to aldehyde under simulated sunlight irradiation.","PeriodicalId":112,"journal":{"name":"Advanced Functional Materials","volume":"80 1","pages":""},"PeriodicalIF":18.5000,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Spatial Coupling of Photocatalytic CO2 Reduction and Selective Oxidation on Covalent Triazine Framework/ZnIn2S4 Core–Shell Structures\",\"authors\":\"Qi Li, Xiang Li, Mang Zheng, Fanqi Luo, Liping Zhang, Bin Zhang, Baojiang Jiang\",\"doi\":\"10.1002/adfm.202417279\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Photocatalytic CO<sub>2</sub> reduction coupled with alcohol oxidation to aldehyde presents a promising strategy for the simultaneous production of fuels and valuable chemicals. The efficiency of the coupled photocatalytic reactions remains low due to poor charge separation, difficulty in CO<sub>2</sub> activation, and uncontrolled compatibility between reactions. This work presents S-bridged covalent triazine framework (SCTF) core-ZnIn<sub>2</sub>S<sub>4</sub> shell photocatalysts for simultaneous CO<sub>2</sub> reduction and selective furfural synthesis at distinct active sites. As evidenced by in situ X-ray photoelectron spectroscopy and Kelvin probe force microscopy, photogenerated electrons in the composite photocatalysts transfer from the ZnIn<sub>2</sub>S<sub>4</sub> shell to the SCTF core, improving charge separation. Experimental and theoretical results confirm that the presence of pyridine N atoms (Lewis basic sites) in SCTF enhances CO<sub>2</sub> adsorption, thereby reducing the energy barrier for *COOH generation and promoting *CO production. Meanwhile, furfuryl alcohol oxidation and deprotonation occur on ZnIn<sub>2</sub>S<sub>4</sub> by consuming photogenerated holes, which in turn benefits the conversion of CO<sub>2</sub> to CO. As a result, the optimized SCTF/ZnIn<sub>2</sub>S<sub>4</sub>-0.2 core/shell photocatalyst exhibited a superior CO production yield of 263.5 µmol g<sup>−1</sup> and 95% conversion of furfuryl alcohol to aldehyde under simulated sunlight irradiation.\",\"PeriodicalId\":112,\"journal\":{\"name\":\"Advanced Functional Materials\",\"volume\":\"80 1\",\"pages\":\"\"},\"PeriodicalIF\":18.5000,\"publicationDate\":\"2024-11-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Advanced Functional Materials\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1002/adfm.202417279\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Advanced Functional Materials","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1002/adfm.202417279","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
光催化二氧化碳还原与酒精氧化成醛反应是一种同时生产燃料和有价值化学品的可行策略。由于电荷分离不良、二氧化碳活化困难以及反应之间的兼容性不可控,耦合光催化反应的效率仍然很低。本研究提出了 S 桥接共价三嗪框架(SCTF)核-ZnIn2S4 壳光催化剂,可在不同的活性位点同时进行二氧化碳还原和选择性糠醛合成。原位 X 射线光电子能谱和开尔文探针力显微镜证明,复合光催化剂中的光生电子从 ZnIn2S4 外壳转移到 SCTF 内核,从而改善了电荷分离。实验和理论结果证实,SCTF 中吡啶 N 原子(路易斯碱性位点)的存在增强了对 CO2 的吸附,从而降低了 *COOH 生成的能量障碍,促进了 *CO 的生成。同时,糠醇在 ZnIn2S4 上通过消耗光生空穴而发生氧化和去质子化,这反过来又有利于 CO2 向 CO 的转化。因此,优化的 SCTF/ZnIn2S4-0.2 核/壳光催化剂在模拟太阳光照射下的 CO 产率高达 263.5 µmol g-1,糠醇到醛的转化率高达 95%。
Spatial Coupling of Photocatalytic CO2 Reduction and Selective Oxidation on Covalent Triazine Framework/ZnIn2S4 Core–Shell Structures
Photocatalytic CO2 reduction coupled with alcohol oxidation to aldehyde presents a promising strategy for the simultaneous production of fuels and valuable chemicals. The efficiency of the coupled photocatalytic reactions remains low due to poor charge separation, difficulty in CO2 activation, and uncontrolled compatibility between reactions. This work presents S-bridged covalent triazine framework (SCTF) core-ZnIn2S4 shell photocatalysts for simultaneous CO2 reduction and selective furfural synthesis at distinct active sites. As evidenced by in situ X-ray photoelectron spectroscopy and Kelvin probe force microscopy, photogenerated electrons in the composite photocatalysts transfer from the ZnIn2S4 shell to the SCTF core, improving charge separation. Experimental and theoretical results confirm that the presence of pyridine N atoms (Lewis basic sites) in SCTF enhances CO2 adsorption, thereby reducing the energy barrier for *COOH generation and promoting *CO production. Meanwhile, furfuryl alcohol oxidation and deprotonation occur on ZnIn2S4 by consuming photogenerated holes, which in turn benefits the conversion of CO2 to CO. As a result, the optimized SCTF/ZnIn2S4-0.2 core/shell photocatalyst exhibited a superior CO production yield of 263.5 µmol g−1 and 95% conversion of furfuryl alcohol to aldehyde under simulated sunlight irradiation.
期刊介绍:
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