近常压XPS原位研究钨原子团簇的组装及其碱性电催化析氢反应机制

碳嵌入钨晶格中使得碳化钨材料在费米面附近具有较高的d-band电子态密度，非常类似于贵金属铂，因此，被预测在电催化产氢（HER）领域具有取代贵金属铂的属性。目前通过形貌调控、掺杂、界面工程、相调控、单原子等手段，虽然已经使得碳化钨基材料在碱性环境中的HER性能逐步逼近贵金属铂，但是离理论预测仍存在差距。主要原因是碳化钨对碱性HER反应中间产物H*和OH*的吸附太强导致的析氢过电位增大和深度氧化腐蚀难题。本项目采用单原子钨作为母材，通过热迁移团聚策略，主要聚焦于类铂结构钨原子团簇材料的可控制备及其碱性HER催化反应的应用。拟借助近常压XPS（NAP-XPS）的变温测试技术和与手套箱互联的功能实现对钨原子团簇从组装到碱性HER反应机理的一体化原位研究，为廉价、高效、稳定的类铂碳化钨基碱性HER催化剂的精细设计提供坚实的实验依据。

The intercalation of carbon atoms into the lattice of the tungsten can afford tungsten carbide materials with higher d-band electronic density of states (DOS) near the Fermi level and hence characteristics resembling those of noble Pt, endowing them with Pt-like behavior in electrocatalytic hydrogen evolution reaction (HER). The alkaline HER performance of tungsten carbide-based materials synthesized by morphology control, doping, interface engineering, phase regulation, tungsten single atoms and so forth, is close to that of commercial Pt catalysts, but the gap still exists based on the theoretic prediction due to the strong interaction between active sites within tungsten carbide materials and the HER intermediates (H* and OH*), which gives rise to the larger hydrogen evolution overpotentials and the deep oxidation corrosion problem. Herein, we mainly focus on the the synthesis of tungsten atomic clusters using tungsten single atoms as parent materials via thermal migration strategy, as well as their application of alkaline HER electrocatalysis. In-situ study of the assembly mechanism and alkaline HER process of tungsten atomic clusters is performed by the variable temperature XPS measurement and the operando electrocatalysis in glove box, respectively, which provides solid experimental evidence towards the synthesis of low-cost, highly efficient, stable and Pt-like tungsten carbide-based alkaline HER catalysts.