Hu Jundie, Yang Tingyu, Yang Xiaogang, Qu Jiafu, Cai Yahui, Li Chang Ming
School of Materials Science and Engineering, Suzhou University of Science and Technology, Suzhou, 215009, China.
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing, 210037, China.
Small. 2022 Feb;18(7):e2105376. doi: 10.1002/smll.202105376. Epub 2021 Dec 5.
Renewable solar-driven carbon dioxide (CO ) conversion to highly valuable fuels is an economical and prospective strategy for both the energy crisis and ecological environment disorder. However, the selectivity and activity of current photocatalysts have great room for improvement due to the diversification and complexity of products. Here, an ambient-stable 2D/2D Co P@BP/g-C N heterojunction is designed for highly selective and efficient photocatalytic CO reduction reaction. The resulting Co P@BP/g-C N material has a remarkable conversion of CO to carbon monoxide (CO) with an ≈96% selectivity, coupled with a dramatically increased CO generation rate of 16.21 µmol g h , which is 5.4 times higher than pristine graphitic carbon nitride (g-C N ). In addition, this photocatalyst exhibits good ambient stability of black phosphorus (BP) without oxidation even over 180 days. The excellent photocatalytic selectivity and activity of Co P@BP/g-C N heterojunction are attributed to its lower energy barriers of *COOH, *CO, and *+CO in the process of CO reduction, coupled with rapid charge transfer at the heterointerfaces of BP/g-C N and Co P/BP. This is solidly verified by both density functional theory calculation and mechanism experiments. Therefore, this work holds great promise for an ambient-stable efficient and high selectivity photocatalyst in solar-driven CO conversion.
将可再生太阳能驱动的二氧化碳（CO₂）转化为高价值燃料，对于解决能源危机和生态环境紊乱而言，是一种经济且具有前景的策略。然而，由于产物的多样性和复杂性，当前光催化剂的选择性和活性仍有很大的提升空间。在此，设计了一种环境稳定的二维/二维Co₂P@BP/g-C₃N₄异质结，用于高选择性和高效的光催化CO₂还原反应。所得的Co₂P@BP/g-C₃N₄材料具有将CO₂显著转化为一氧化碳（CO）的能力，选择性约为96%，同时CO生成速率大幅提高，达到16.21 μmol g⁻¹ h⁻¹，这比原始的石墨相氮化碳（g-C₃N₄）高出5.4倍。此外，这种光催化剂展现出黑磷（BP）良好的环境稳定性，即使超过180天也不会氧化。Co₂P@BP/g-C₃N₄异质结优异的光催化选择性和活性归因于其在CO₂还原过程中*COOH、CO和+CO的较低能垒，以及BP/g-C₃N₄和Co₂P/BP异质界面处的快速电荷转移。密度泛函理论计算和机理实验均有力地证实了这一点。因此，这项工作对于太阳能驱动的CO₂转化中环境稳定、高效且高选择性的光催化剂具有巨大的潜力。
