光催化
氮化碳
材料科学
电子结构
太阳能燃料
氮化物
电子转移
催化作用
光化学
化学
纳米技术
计算化学
生物化学
图层(电子)
作者
Peng Chen,Ben Lei,Xing’an Dong,Hong Wang,Jianping Sheng,Wen Cui,Jieyuan Li,Yanjuan Sun,Zhiming Wang,Fan Dong
出处
期刊:ACS Nano
[American Chemical Society]
日期:2020-11-03
卷期号:14 (11): 15841-15852
被引量:283
标识
DOI:10.1021/acsnano.0c07083
摘要
Photocatalytic CO2 conversion into valuable solar fuels is highly appealing, but lack of directional charge-transfer channel and insufficient active sites resulted in limited CO2 reduction efficiency and selectivity for most photocatalytic systems. Herein, we designed and fabricated rare-earth La single-atoms on carbon nitride with La-N charge-transfer bridge as the active center for photocatalytic CO2 reaction. The formation of La single-atoms was certified by spherical aberration-corrected HAADF-STEM, STEM-EELS, EXAFS, and theoretical calculations. The electronic structure of the La-N bridge enables a high CO-yielding rate of 92 μmol·g-1·h-1 and CO selectivity of 80.3%, which is superior to most g-C3N4-based photocatalytic CO2 reductions. The CO production rate remained nearly constant under light irradiation for five cycles of 20 h, indicating its stability. The closely combined experimental and DFT calculations clearly elucidated that the variety of electronic states induced by 4f and 5d orbitals of the La single atom and the p-d orbital hybridization of La-N atoms enabled the formation of charge-transfer channel. The La-N charge bridges are found to function as the key active center for CO2 activation, rapid COOH* formation, and CO desorption. The present work would provide a mechanistic understanding into the utilization of rare-earth single-atoms in photocatalysis for solar energy conversion.
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