TiO2调控非铂金属原子催化氢氧化

The development of a high-efficiency and low-cost non-Pt anode electrocatalyst for hydrogen oxidation reaction (HOR) is urgently needed in order to ultimately solve the Pt-reliance of fuel cell technology, which requires a fine regulation of H & OH adsorption-desorption properties on the catalytic interface, an enhancement of resistance to the catalyst electro-oxidation, and a promotion of acidic/alkaline etching tolerance. Herein, for the first time, we propose a regulation of atomic dispersed non-Pt metal clusters/atoms via the interfacial interaction of nano-TiO2 for the high efficient electrocatalysis of hydrogen oxidation reaction in fuel cell. We plan to regulate the valence bond structure and geometrical structure of metal clusters or atoms by the nano-TiO2 dangling bonds which produced during the hydrolysis of TiO2, and then to regulate the H & OH adsorption-desorption properties. The electric charge effect of TiO2 would strengthen catalyst oxidation resistance and corrosion resistance. We plan to reveal the structure-activity relationship between the geometric & valence bond structure and HOR activity, to theoretical study the mechanism of metal-TiO2 catalyst controllable synthesis, and ultimately to invent a low cost Pt-free fuel cell anode catalyst with high efficient, high stability, and abundant resources.

开发高效、稳定且资源丰富的非铂燃料电池阳极催化剂，突破阳极非铂化技术瓶颈，需精确调控催化剂氢/氢氧吸附性质、强化电化学氧化耐受性、提高酸碱耐腐蚀性。基于此，本申请首次提出“TiO2调控非铂金属原子催化氢氧化”的思路。通过Ni、Mo、W、Ru等金属盐或金属簇与TiO2共同水解反应，利用所产生的大量悬空键结合固熔体气氛还原，实现金属原子级分散强化相互作用，调控金属-TiO2催化剂价键结构和几何结构，调控催化界面的氢、氢氧吸附性质，利用电荷效应强化催化剂电氧化耐受性和耐腐蚀性。构建几何结构、价键结构与氢氧化活性的构效关系，形成可控制备理论基础，开发基于金属-TiO2的高效、低成本、资源丰富的非铂燃料电池阳极催化剂。

开发高效、稳定且资源丰富的非铂燃料电池阳极催化剂，突破阳极非铂化技术瓶颈，需精确调控催化剂氢/氢氧吸附性质、强化电化学氧化耐受性、提高酸碱耐腐蚀性。研究提出“TiO2调控非铂金属原子催化氢氧化”的思路，通过利用TiO2水解所产生的大量悬空键结合固熔体气氛还原，实现金属原子级分散强化相互作用，调控金属-TiO2催化剂价键结构和几何结构，调控催化界面的氢、氢氧吸附性质，利用电荷效应强化催化剂电氧化耐受性和耐腐蚀性。取得了如下主要成果：（1）揭示了OH在金属表面吸附强度与氢氧化活性的火山型关系；（2）通过TiO2界面调控实现Ru的d带电子结构的全填充或半填充；（3）揭示Ru-Ti 键的电子转移可大幅减少了CO的σ电子向金属d控轨道转移的概率，赋予了 Ru 簇 CO 抗毒化特性和抗氧化性；（4）开发了高活性的Ni基非铂阳极催化剂，电池功率超过200 mW cm-2。依托于国家自然科学基金项目“TiO2调控非铂金属原子催化氢氧化”项目（批准号：2177604），发表 SCI 论文共计 20 篇，其中一区论文 13 篇，包括Nature Catalysis（1 篇），Angew. Chem. Int. Ed.（1篇），ACS Energy Lett.（1 篇），中文核心期刊2 篇。