环加成
碳酸盐
光催化
电子转移
催化作用
电子顺磁共振
傅里叶变换红外光谱
漫反射红外傅里叶变换
光谱学
化学
环氧化物
密度泛函理论
材料科学
光化学
化学工程
计算化学
有机化学
核磁共振
物理
量子力学
工程类
作者
Lei Li,Haibo Liu,Tian Shi,Shu Shang,Xiaodong Zhang,Hui Wang,Ziqi Tian,Liang Chen,Yi Xie
出处
期刊:ACS materials letters
[American Chemical Society]
日期:2023-03-20
卷期号:5 (4): 1219-1226
被引量:12
标识
DOI:10.1021/acsmaterialslett.3c00069
摘要
It is attractive but challenging to produce high-value-added cyclic carbonates at ambient condition by the 100% atom-economic photocatalytic cycloaddition of CO2, which is limited by the insufficient understanding of the catalytic mechanism. Here, by taking Mg-MOF-74 as a model system, we propose the photoexcited catalyst can generally activate CO2 via single-electron-transfer mechanism, leading to the rapid formation of •CO2– radical. Subsequently, beneficial for the activation of inert CO2, the energy barrier of the rate-determining step (RDS) of the whole cycloaddition, i.e., the CO2 attacking step, significantly decreases, resulting in the feasible synthesis of cyclic carbonates under ambient condition. With the combination of synchrotron radiation in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), in situ electron spin resonance (ESR) spectroscopy, and the density functional theory calculation, the reaction process and corresponding key intermediates are systematically investigated, revealing the CO2 activation to be the most energy consumption steps in cyclic carbonate production, rather than the ring-opening of epoxide, thus furnishing new insights into photocatalytic CO2 cycloaddition.
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