反向钼化法调控二硫化钼催化位点及电解水产氢活性研究

Regulation of the surface molecular structure to improve the revealed catalytic sites is the focus of MoS2 electrocatalysts. In the "Mo→S" conventional synthetic process, the Mo catalytic sites are susceptible to S atoms to reduce the catalytic activity of MoS2. In order to address this problem, the inverted molybdenum reaction "S→Mo" was proposed in this project. The surface molecular structure of MoS2 was regulated to increase the exposure of Mo catalytic sites, then obtained high catalytic activity for hydrogen evolution reaction. The main contents of this project are: the synthesis of MoS2 with high revealed catalytic sites by reversed molybdenum reactions. The kinds, nanostructures and the presence form (microemulsions and metal sulfide compound, etc.) of S-phase were studied to regulate surface molecular structure of MoS2. Especially, transition metal sulfides were used as a template, S-phase and metal doping sources to synchronously achieve the control of catalytic sites and doping of metal elements. Combining the simulated calculation, the relationship among the reversed molybdenum reaction, surface molecular structure and electrocatalytic activity for hydrogen evolution reaction was explored. The project is expected to provide new ways for regulating the surface catalytic sites of MoS2, and scientific theory for the synthesis of highly active MoS2 electrocatalysts.

如何调控MoS2催化剂表面分子结构，增加Mo催化位点显露率，是提高MoS2电解水产氢活性的重要科学问题。针对二硫化钼的S-Mo-S三明治层状结构特点，本项目拟提出“Mo离子向S模板扩散反应”的反向钼化反应，调控MoS2的表面原子排布，解决Mo催化位点暴露率低的问题，以期获得高催化活性的MoS2电催化剂。主要研究内容涵盖：控制S相的化学组成、纳米结构和存在形式（微乳液和金属硫化合物等），通过S相模板与Mo离子的界面可控反应，实现MoS2表面非化学计量比的原子排布，充分暴露Mo催化活性位点，获得高电解水催化活性的电催化剂；特别是利用过渡金属硫化物作为模板、S相和金属掺杂源，通过反向钼化反应同步实现Mo催化位点调控和元素掺杂；结合模拟理论计算，探讨反向钼化反应-Mo催化活性位点-电解水产氢活性三者之间的内在关系，有望为调控MoS2表面催化位点提供新途径和科学理论根据。

如何调控MoS2催化剂表面分子结构，增加Mo催化位点显露率，是提高MoS2电解水产氢活性的重要科学问题。因此，本项目一方面是利用反向钼化反应，获得高催化活性的MoS2电催化剂，为调控MoS2表面催化位点提供新途径和科学理论根据；另一方面是在反向钼化反应方向获得的成果的基础上，继续对钼基材料进行了深入的研究，为制备比表面积大、富含表面活性位点的高效 催化剂提供了具有普遍意义的有益启发和可靠途径。