溴氧铋负载的单原子钌用于室温常压下光电化学固氮反应研究

The widely used Haber-Bosch method in ammonia synthesis industry needs high temperature and pressure which leads to huge energy consumption and environment contamination. Therefore, developing highly efficient, low-cost and environment friendly new method for nitrogen fixation can effectively ease the energy crisis and environment contamination. Photoelectrochemical nitrogen fixation can not only drives nitrogen reduction reaction with light, reduces energy consumption, but also improves the separation efficiency of electron/holes pairs in semiconductors and then greatly enhances the nitrogen fixation rate. This project intends to combine atomic dispersed ruthenium (Ru) (catalytic center) with p-type BiOBr (light absorption center) nanosheets as a catalyst for photoelectrochemical nitrogen fixation reaction at ambient temperature and normal pressures. We dedicate the optimal matching between catalytic center and light absorption center from the angle of coordination environment of atomic dispersed Ru. Combined with synchrotron radiation characterization technology and theoretical calculation, we will make an in-depth understanding the reaction mechanism of single atom catalyst in photoelectrochemical nitrogen fixation and formulate the designing rules for photoelectrochemical nitrogen fixation catalyst. This project will provides guidance for achieving to design highly efficient, low-cost, environment friendly catalyst for nitrogen fixation.

合成氨工业广泛采用的哈伯法由于需要较为苛刻的高温高压条件造成了巨大的能源消耗和环境污染，因此，发展高效、低成本、条件温和的固氮新方法能有效缓解能源短缺和环境污染问题。发展室温常压下的光电化学固氮不仅能利用太阳能驱动氮气（N2）到氨（NH3）的转化，有效地降低能源消耗，而且能提高半导体电子/空穴分离能力从而大大提高固氮反应速率。本项目拟通过将具有优异催化性能的Ru单原子催化剂（催化中心）与p-型BiOBr纳米片（吸光中心）结合用于室温常压下光电化学固氮反应，从Ru原子表面配位环境的角度调控催化剂表界面结构实现催化中心和吸光中心的最优匹配。结合同步辐射表征技术以及理论模拟深入理解单原子催化剂在光电化学固氮中的反应机制，总结出光电化学固氮反应催化剂的设计原则，为发展高效、低成本、条件温和的固氮反应催化剂提供借鉴作用。

工业中氨合成广泛使用的是哈伯-博施法，该方法需要消耗大量的化石燃料，带来严重的环境污染和能源危机。将空气中的氮气或者水体中广泛存在的硝酸盐在光/电驱动下转化成有价值的氨被认为是哈伯法的有效替代。然而光/电驱动下的固氮反应普遍面临着活性低、反应选择性差等问题。催化剂的理性设计，构建高活性位点是解决该瓶颈问题的关键。本项目从催化剂的表界面调控角度，通过原位掺杂、表界面改性、构建原子级活性位点等方式来提高载流子分离效率、光/电化学制氨活性和选择性。结合先进表征、原位谱学测试以及理论计算，详细解析催化反应机理，构建从反应物、中间物种转变以及产物之间变化关系。深入总结光/电化学制氨反应催化剂的设计原则，为制备高活性、高选择性的光/电固氮催化剂提供新见解。