电催化剂Pt的电子结构和催化性能

Electronic structures and catalytic performance of Pt-electrocatalyst

依据纯金属单原子(OA)理论确定面心立方结构(fcc)电催化剂Pt的电子结构为[xe](5dn)6．48(5dc)2．02- (6sc)1．48(6sf)0．02,与采用第一原理的FP-LMTO和CASTEP等方法所计算的电子结构相比较,其结果非常相近;由OA理论和第一原理方法计算的晶格常数、结合能、体弹性模量等物理参数进行比较,OA理论计算的结果与实验值较符合,而第一原理方法计算的结果与实验值相差较大;在此基础上用OA理论和第一原理方法研究了Pt的电子结构与催化性能的关系,由于d带空穴增多和费米能级附近态密度较高,导致金属Pt的催化性能很好。

Using the one-atom （OA） theory, the electronic structures of Pt-electrocatalyst with fcc structure was determined as follows： [Xe]（5dn）^6.48 （5dc）^2.02 （6sc）^1.48（6sf）^0.02. Compared to the result obtained by the first-principle method such as FP-LMTO, CASTEP, their results are in good agreement with each other. Comparing the calculations of physical properties such as lattice constants, cohesive energy and bulk modulus by OA method and first-principle method, the result obtained by OA method is in excellent agreement with experimental value, but the result obtained by first-principle method is not accordable. The relationship between the electronic structures and catalytic performance was explained qualitatively by OA method and first principle method according to its electronic structures. Because the d-orbital vacancies increases and static density is high around Fermi energy band, Pt has good catalytic performance.