新型具有电和光催化产氢双重功能催化剂的设计与研究

The replacement of fossil fuels by green and renewable solarenergy carriers is one of the most important challenges our society is facing today. Nature has been using sunlight to split water and generate carbohydrates (solar fuels) in photosynthesis. Artificial systems inspired by nature have been designed to capture solar light and extract protons and electrons from water to generate useful chemical fuels. Therefore, mastering and understanding water-reduction catalysis is one of the key elements needed for this strategy to succeed. Despite the current advances in this field, the design of photo- and electro-catalysts with high activity and stability in neutral media is a real challenge..On the basis of preliminary studies, this project puts forward: design and synthesis of new metal compounds are expected to resolve these issues. Several research topics proposed are as follows: (1) According to the characteristics and requirements of photo- and electro-catalytic water-reduction, design new metal compounds, which can improve the efficiency of H2 production; (2) Determine factors affecting the efficiency of H2 production by investigating the mechanism of photo- and electro-catalytic cycle and the nature of intermediate; (3) Reveal the relationship between the structure and activity of catalysts and find ways for improving the catalytic efficiency; (4) Based on a variety of factors, design new photo- and electro-catalytic catalysts for water-reduction with function of low cost, easy preparation, stable and efficient, and establish a new type of methods for photo- and electro-catalytic water-reduction.

用绿色和可再生光能载体替代化石燃料是当今我们的社会面临的最重要挑战。大自然一直在利用太阳光进行光合作用来分解水产生碳水化合物 (太阳能燃料)。模拟大自然的水还原系统旨在捕获太阳光，从水中捕获质子和电子去获取化学燃料。因此，掌握和理解光催化水还原机理是这一战略目标取得成功的关键。目前光和电催化制氢的研究已有一些进展，但要合成出在中性介质中具有高活性和高稳定性光和电催化剂仍面临着巨大挑战。在前期研究的基础上，该项目提出：新型金属化合物的设计与合成有望解决这些问题。该课题拟开展研究的主要内容包括：(1) 根据光和电催化水还原的特征与要求，优化有机体的电子性能，组装新型金属化合物；(2) 调查光和电催化机理及中间体的性质，确定产氢的影响因素；(3) 揭示催化剂的结构调控与其催化性能之间关系，找到提高催化效率的办法；(4) 综合多种因素，设计出价廉、稳定、易制备和高效的新型水还原催化剂，建立新型的光

在国家自然基金（No 21875074）的资助下，本课题研究进行得非常顺利，并取得了丰硕的成果。2019-2022年，课题组完成了7个系列20多种具有电催化或光催化产氢及水或氢氧化功能配合物的设计、合成及催化性能的研究工作。1）系统地研究了配合物中配体的变化对其催化性能的影响；2）探索不同金属对其催化性能的影响； 3）进一步探讨金属氧化态的不同对其催化性能的影响；4）深入研究设计出的分子催化剂的催化机理；5）揭示分子催化剂的设计规则。6）融学术成果入大学教学过程中，把该项目的研究成果编入三部教材。该课题的研究成果极大地丰富了分子催化剂设计领域的内容，指导高效电和光催化制氢系统的建立，提升了课题组在国际上的影响力。