Zhao Yanyan, Zhou Si, Zhao Jijun, Du Yi, Dou Shi Xue
Key Laboratory of Materials Modification by Laser, Ion and Electron Beams (Dalian University of Technology), Ministry of Education, Dalian 116024, China.
Institute for Superconducting and Electronic Materials (ISEM), Australian Institute for Innovative Materials (AIIM), University of Wollongong, Wollongong, New South Wales 2500, Australia.
J Phys Chem Lett. 2020 Nov 5;11(21):9304-9312. doi: 10.1021/acs.jpclett.0c02480. Epub 2020 Oct 21.
Developing high-efficiency photocatalysts for clean energy generation is a grand challenge, which requires simultaneously steering photocarrier dynamics and chemical activity for a specific reaction. To this end, here for the first time, we explore the real-time photocarrier transport property and catalytic mechanism of nitrogen reduction reaction (NRR) at the interface of bismuth oxyhalides (BiOX, X = Cl, Br, and I), an inexpensive and green semiconductor. By time-dependent non-adiabatic molecular dynamics simulations, we show that the separation and recombination processes of excited carriers as well as the catalytic activity can be concurrently optimized by precise band structure engineering. The exact influence of impurity states and heterojunction on the reduction power and lifetime of photogenerated carriers, light absorbance, and NRR activity/selectivity of BiOX are clearly unveiled, to provide essential physical insights for improving the photocatalytic efficiency of semiconductors for practical solar energy conversion and hydrogen fuel storage.
开发用于清洁能源生成的高效光催化剂是一项巨大挑战，这需要同时调控光载流子动力学和特定反应的化学活性。为此，我们首次探索了卤氧化铋（BiOX，X = Cl、Br和I）（一种廉价且绿色的半导体）界面处氮还原反应（NRR）的实时光载流子传输特性和催化机制。通过含时非绝热分子动力学模拟，我们表明，精确的能带结构工程可以同时优化激发载流子的分离和复合过程以及催化活性。杂质态和异质结对BiOX光生载流子的还原能力和寿命、光吸收以及NRR活性/选择性的确切影响被清晰揭示，为提高半导体用于实际太阳能转换和氢燃料存储的光催化效率提供了重要的物理见解。
