基于量子化学的团簇Co4P非晶态合金析氢反应研究

为寻找在团簇Co₄P中具有最优催化析氢性能的构型,该文根据密度泛函理论于B3LYP/lanl2dz水平下对团簇Co₄P分别进行在二、四重态下的计算,根据前线轨道理论对优化后团簇Co₄P的HOMO图、水分子的LUMO图以及能级差进行分析,发现构型1⁽²⁾、2⁽²⁾的β电子与构型1⁽⁴⁾、2⁽⁴⁾的α电子的HOMO负相位对催化析氢反应的第1步提供了较大的贡献.此外,综合分析析氢反应的各步骤发现:构型2⁽²⁾具有较好的吸附能力,且该构型在吸附1个氢原子后在电化学解吸和化学重组解吸中均具有最优解析性质.因此,构型2⁽²⁾是在团簇Co₄P各优化构型中最优的催化析氢构型.

The Study on Hydrogen Evolution Reaction of Cluster Co4P Amorphous Alloy Based on Quantum Chemistry

In order to find the configuration with the optimal catalytic hydrogen evolution performance in the cluster Co₄P,according to the density functional theory at the B3LYP/lanl2dz level,the cluster Co₄P is calculated in the double and quartet states,and then the optimized cluster is calculated according to the frontier orbit theory.The HOMO diagram of cluster Co₄P,the LUMO diagram of water molecules and the energy level difference are analyzed,and it is found that the HOMO is generated by the β electrons of configuration 1⁽²⁾ and 2⁽²⁾ and α electrons of configuration 1⁽⁴⁾ and 2⁽⁴⁾.The negative phase provides a greater contribution to the first step of the catalytic hydrogen evolution reaction.In addition,comprehensive analysis of the various steps of the hydrogen evolution reaction finds that configuration 2⁽²⁾ has better adsorption capacity,and this configuration has the best desorption properties in both electrochemical desorption and chemical recombination desorption after adsorbing a hydrogen atom.Therefore,configuration 2⁽²⁾ is the optimal catalytic hydrogen evolution configuration among the optimized configurations of cluster Co₄P.