Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO<sub>2 </sub>Photoreduction

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摘要 Defect engineering has being regarded as one of the effective ways to regulate chemical and electronic structure of semiconductors. Recently, our collaborative work has shown experimentally that carbon vacancy on polymeric carbon nitride (CV) can greatly improve the CO2 to CO conversion with a 45-fold improvement over the polymeric carbon nitride (Angew. Chem. Int. Ed., 2019, 58, 1134). In order to clarify the detailed mechanism of promotion, we have systematically studied the electronic properties of CV and hydrogenated CV (CV+H) as well as the effective CO2 reduction reaction through density functional theory calculations. We found that it is the synergistic effect for the CO2 reduction reaction in the CV systems, as the onset potentials of several CVs are much lower than that of the polymeric carbon nitride. In particular, the onset potentials of CV1, CV2, and CV2+H are around 0.9～1.5 eV with a strong chemisorbed CO2 on them. Combined with the analysis of the electronic properties, our results confirm that defect engineering increases the lifetime of photo-generated charges, improves photocatalytic activity, and promotes the CO2 reduction reaction on the defected polymeric carbon nitrides.

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	刘少华
	李奕
	丁开宁
	陈文凯
	章永凡
	林伟

关键词 ： polymeric carbon nitride (PCN), carbon vacancy, reaction mechanism, CO₂ reduction, density functional theory (DFT)

Abstract：Defect engineering has being regarded as one of the effective ways to regulate chemical and electronic structure of semiconductors. Recently, our collaborative work has shown experimentally that carbon vacancy on polymeric carbon nitride (CV) can greatly improve the CO2 to CO conversion with a 45-fold improvement over the polymeric carbon nitride (Angew. Chem. Int. Ed., 2019, 58, 1134). In order to clarify the detailed mechanism of promotion, we have systematically studied the electronic properties of CV and hydrogenated CV (CV+H) as well as the effective CO2 reduction reaction through density functional theory calculations. We found that it is the synergistic effect for the CO2 reduction reaction in the CV systems, as the onset potentials of several CVs are much lower than that of the polymeric carbon nitride. In particular, the onset potentials of CV1, CV2, and CV2+H are around 0.9～1.5 eV with a strong chemisorbed CO2 on them. Combined with the analysis of the electronic properties, our results confirm that defect engineering increases the lifetime of photo-generated charges, improves photocatalytic activity, and promotes the CO2 reduction reaction on the defected polymeric carbon nitrides.

Key words： polymeric carbon nitride (PCN) carbon vacancy reaction mechanism CO2 reduction density functional theory (DFT)

收稿日期: 2020-10-22 出版日期: 2020-12-13

基金资助:This work was financially supported by the National Natural Science Foundation of China (21973014, 21773030).W. L. thanks the Award Program of Minjiang Scholar Professorship for financial support

通讯作者: 林伟：wlin@fzu.edu.cn E-mail: wlin@fzu.edu.cn

引用本文:

刘少华;李奕;丁开宁;陈文凯;章永凡;林伟. Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO₂Photoreduction[J]. 结构化学, 2020, 39(12): 2068-2076.
LIU Shao-Hua;LI Yi;DING Kai-Ning;CHEN Wen-Kai;ZHANG Yong-Fan;LIN Wei. Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO₂ Photoreduction. CHINESE JOURNAL OF STRUCTURAL CHEMISTRY, 2020, 39(12): 2068-2076.

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http://manu30.magtech.com.cn/jghx/CN/ 或 http://manu30.magtech.com.cn/jghx/CN/Y2020/V39/I12/2068

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