Pt-O Bond as An Active Site Superior to Pt0 in Hydrogen Evolution Reaction
Fei-Yang Yu,1,# Zhong-Ling Lang,1,# Li-Ying Yin,1 Kun Feng,2 Yu-Jian Xia,2 Hua-Qiao Tan,1,* Hao-Tian Zhu,1 Jun Zhong,2 Zhen-Hui Kang2,* & Yang-Guang Li1,*
1Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China.
2Jiangsu Key Laboratory for Carbon-based Functional Materials and Devices, Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China.
The oxidized platinum (Pt) can exhibit better electrocatalytic activity than metallic Pt0 in the hydrogen evolution reaction (HER), which has aroused great interest in exploring the role of oxygen in Pt-based catalysts. Herein, we select two structurally well-defined polyoxometalates Na5[H3Pt(IV)W6O24] (PtW6O24) and Na3K5[Pt(II)2(W5O18)2] (Pt2(W5O18)2) as the platinum oxide model to investigate the HER performance. Electrocatalytic experiments show the mass activities of PtW6O24/C and Pt2(W5O18)2/C are 20.175 Amg-1 and 10.976 Amg-1 at 77 mV, respectively, which are better than that of commercial 20% Pt/C (0.398 Amg-1). The in situ synchrotron radiation experiments and DFT calculations suggest that the elongated Pt-O bond acts as the active site during the HER process, which can accelerate the coupling of proton and electron and the rapid release of H2. This work complements the knowledge boundary of Pt-based electrocatalytic HER, and suggests another way to update the state-of-the-art electrocatalyst.