Deciphering the selectivity descriptors of heterogeneous metal phthalocyanine electrocatalysts for hydrogen peroxide production. Issue 37 (16th September 2022)

• Record Type: Journal Article
• Authors: Yuan, Yubo; Li, Huan; Jiang, Zhan; Lin, Zhichao; Tang, Yirong; Wang, Hongxuan; Liang, Yongye
• Is Part Of: Chemical science. Volume 13:Issue 37(2022)
• Page Start: 11260
• Page End: 11265
• Publication Date: 2022-09-16
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc03714a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Two selectivity descriptors for the 2e − oxygen reduction reaction are found on molecularly dispersed electrocatalysts of metal phthalocyanines anchored on carbon nanotubes. The optimized catalysts can produce H2 O2 with high selectivity at high rates. Abstract : The electrocatalytic 2e − oxygen reduction reaction (2e − ORR) provides an appealing pathway to produce hydrogen peroxide (H2 O2 ) 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 (Δ G *O − Δ G *OOH and Δ G *H2 O2 ) are uncovered for manipulating the selectivity of H2 O2 production. Δ G *O − Δ G *OOH reflects the preference of O–O bond breaking of *OOH, affecting the intrinsic selectivities. Due to the high value of Δ G *O − Δ G *OOH, the molecularly dispersed electrocatalyst (MDE) of ZnPc on carbon nanotubes exhibits high selectivity, even superior to the previously reported NiPc MDE. Δ G *H2 O2 determines the possibility of further H2 O2 reduction to affect the measured selectivities. Enhancing the hydrophobicity of the catalytic layer can increase Δ G *H2 O2, leading to selectivity improvement, especially under high H2 O2 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.