高效催化氧还原及氧析出反应的掺杂石墨炔的设计与理论计算

Design and Theoretical Calculation of Heteroatoms Doped Graphdiyne Towards Efficiently Catalyzing Oxygen Reduction and Evolution Reactions

在清洁和可再生能源的转化过程中,氧还原反应和氧析出反应需要高效的电催化剂以克服其动力学限制.本文设计了一系列掺杂杂原子的无金属石墨二炔,以促进上述两类关键化学反应.为了评估电催化性能,利用密度泛函理论研究了反应路径和吉布斯自由能变化.计算结果表明,掺杂剂可以优化中间体的吸附,降低反应的过电位.本文还得到了将催化剂性质与催化剂结构相关联的内在描述符,该描述符可以加速开发和筛选新型电催化剂.研究结果可为清洁能源技术(如燃料电池、金属空气电池和电解水等)中碳基催化剂的设计提供指导.

In the process of clean and renewable energy conversion,oxygen reduction reaction and oxygen evolution reaction demand highly efficient electrocatalysts to overcome their kinetic bottlenecks.Herein,a series of metal-free graphdiyne doped with heteroatoms was designed for promoting these key chemical reactions.To evaluate electrocatalytic performance,the reaction pathways and free energies were investigated systematically with the density functional theory(DFT).The calculations indicated that the dopants can optimize the adsorption of intermediates,lowering the overpotential of the reactions.Particularly,an intrinsic descriptor was identified to correlate the catalytic properties with catalyst structures,from which rapid screening could be made for the development of new catalysts.The results may provide guidance for the construction of carbonbased catalysts in clean energy technologies(such as fuel cells,metal-air batteries,electrolyzing water and so on).