团簇Fe_(3)Ni_(3)稳定性及催化析氢性能

Study on the Catalytic Performance of Cluster Fe_(3)Ni_(3)for Hydrogen Evolution

为探究团簇Fe_(3)Ni_(3)优化构型的热力学稳定性,并研究其催化析氢性能,在密度泛函理论中的B3LYP/Lanl2dz(level)下,利用Gaussian软件对构型进行全参数优化计算后,从各优化构型的热力学能量分析中发现:团簇Fe_(3)Ni_(3)共有9种优化稳定构型,包括5种三重态构型与4种单重态构型,并且三重态优化构型均相较于单重态构型具有更高的稳定性。设计团簇Fe_(3)Ni_(3)催化析氢具体反应机理,利用前线轨道理论在两步反应中进行分析发现,团簇Fe_(3)Ni_(3)所有构型均能参与水分子的催化反应,其中Fe原子是催化的主要活性位点,且构型1^((1))与构型2^((1))反应活性最好。

In order to explore the thermodynamic stability of the optimized configuration of cluster Fe_(3)Ni_(3)and study its catalytic hydrogen evolution performance,under the B3 LYP/Lanl2 dz(level)of density functional theory,the configuration is optimized by using Gaussian software.After the calculation,the thermodynamic energy analysis of each optimized configuration shows that:ClusterFe_(3)Ni_(3)has 9 optimized stable configurations,including 5 triplet configurations and 4 singlet configurations,and the triplet optimized configurations have higher stability than the singlet configuration.The specific reaction mechanism of cluster Fe_(3)Ni_(3)catalyzing hydrogen evolution was designed,and the front-line orbital theory was used to analyze the two-step reaction.It was found that all configurations of cluster Fe_(3)Ni_(3)could participate in the catalytic reaction of water molecules,among which Fe atom was the main active site,and the reaction activity of configuration 1^((1)) and configuration 2^((1)) was the best.