Deciphering the selectivity descriptors of heterogeneous metal phthalocyanine electrocatalysts for hydrogen peroxide production

Yuan, Yubo; Li, Huan; Jiang, Zhan; Lin, Zhichao; Tang, Yirong; Wang, Hongxuan; Liang, Yongye

2022-09-01

10.1039/d2sc03714a

Chemical Science   Impact Factor & Quartile

2041-6520

2041-6539

The electrocatalytic 2e^- oxygen reduction reaction (2e^- ORR) provides an appealing pathway to produce hydrogen peroxide (H2O2) in a decentralized and clean manner, which drives the demand for developing high selectivity electrocatalysts. However, current understanding on selectivity descriptors of 2e^- ORR electrocatalysts is still insufficient, limiting the optimization of catalyst design. Here we study the catalytic performances of a series of metal phthalocyanines (MPcs, M = Co, Ni, Zn, Cu, Mn) for 2e^- ORR by combining density functional theory calculations with electrochemical measurements. Two descriptors (Delta G*O - Delta G*OOH and Delta G*H2O2) are uncovered for manipulating the selectivity of H2O2 production. Delta G*O - Delta G*OOH reflects the preference of O-O bond breaking of *OOH, affecting the intrinsic selectivities. Due to the high value of Delta G*O - Delta G*OOH, the molecularly dispersed electrocatalyst (MDE) of ZnPc on carbon nanotubes exhibits high selectivity, even superior to the previously reported NiPc MDE. Delta G*H2O2 determines the possibility of further H2O2 reduction to affect the measured selectivities. Enhancing the hydrophobicity of the catalytic layer can increase Delta G*H2O2, leading to selectivity improvement, especially under high H2O2 production rates. In the gas diffusion electrode measurements, both ZnPc and CoPc MDEs with polytetrafluoroethylene (PTFE) exhibit low overpotentials, high selectivities, and good stability. This study provides guidelines for rational design of 2e^- ORR electrocatalysts.

SCI

English

NI Journal Papers

First ; Corresponding

National Natural Science Foundation of China[22075125]

Chemistry

Chemistry, Multidisciplinary

WOS:000854203900001

ROYAL SOC CHEMISTRY

Web of Science

Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China

Yuan, Yubo,Li, Huan,Jiang, Zhan,et al. Deciphering the selectivity descriptors of heterogeneous metal phthalocyanine electrocatalysts for hydrogen peroxide production[J]. Chemical Science,2022.

Yuan, Yubo.,Li, Huan.,Jiang, Zhan.,Lin, Zhichao.,Tang, Yirong.,...&Liang, Yongye.(2022).Deciphering the selectivity descriptors of heterogeneous metal phthalocyanine electrocatalysts for hydrogen peroxide production.Chemical Science.

Yuan, Yubo,et al."Deciphering the selectivity descriptors of heterogeneous metal phthalocyanine electrocatalysts for hydrogen peroxide production".Chemical Science (2022).