标题: Electron transfer and energy barrier co-modulation: Unravelling the role of sequential fluorination in high-rate CO (2) photoreduction on conjugated organic polymers
作者: Chen, B (Chen, Bo); Tian, FY (Tian, Fengyu); Wang, M (Wang, Miao); Peng, C (Peng, Chuang)
来源出版物: APPLIED CATALYSIS A-GENERAL 卷: 638 文献号: 118618 DOI: 10.1016/j.apcata.2022.118618 出版年: MAY 25 2022
摘要: Water-assisted photoreduction of CO2 without using co-catalyst, photosensitizer or sacrificial reagent is similar to natural photosynthesis, thus offering a promising solution to CO2 emissions. In this work, conjugated organic polymers with un-, mono- and bi-fluorinated benzothiadiazole units are synthesized and studied for gas-solid mode CO2 photoreduction. Both the photoelectrical properties and photoreduction efficiency are markedly improved upon sequential fluorination. Theoretical calculations reveal that the sequential fluorination effectively reduces the energy barrier of the rate-determining step of *COOH formation, and promotes the desorption of CO. Benefiting from this, the CO2 photoreduction rates of the monofluorinated FBZTE and the bifluorinated DFBZTE are 1.93 and 3.34 times that of the unfluorinated BZTE, respectively. DFBZTE exhibits a record-high CO yield of 39.22 mu mol.g(-1).h(-1) and nearly 100% selectivity, superior to similar materials reported in the same reaction system. This strategy provides a novel approach for design of more efficient polymer-based catalysts for photoreduction of CO2.
作者关键词: CO2 photoreduction; Conjugated organic polymers; Fluorinated benzothiadiazole; Energy barrier modulation; Charge transfer
地址: [Chen, Bo; Tian, Fengyu; Wang, Miao; Peng, Chuang] Wuhan Univ, Sch Resource & Environm Sci, Wuhan 430072, Peoples R China.
通讯作者地址: Peng, C (通讯作者)，Wuhan Univ, Sch Resource & Environm Sci, Wuhan 430072, Peoples R China.
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