Taming Electrons in Pt/C Catalysts to Boost the Mesokinetics of Hydrogen Production. (July 2022)

• Record Type: Journal Article
• Authors: Chen, Wenyao; Fu, Wenzhao; Duan, Xuezhi; Chen, Bingxu; Qian, Gang; Si, Rui; Zhou, Xinggui; Yuan, Weikang; Chen, De
• Is Part Of: Engineering. Volume 14(2022)
• Page Start: 124
• Page End: 133
• Publication Date: 2022-07
• Subjects: Mesokinetics model -- Catalyst descriptor -- Pt charge state -- Carbon surface chemistry -- Hydrogen generation activity; Engineering -- Periodicals; Engineering -- China -- Periodicals; 620.005
• DOI: 10.1016/j.eng.2020.11.014
• Languages: English
• ISSNs: 2095-8099

Abstract

Abstract: Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties. Herein, we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is, for the electron-withdrawing/donating oxygen-containing groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles. Taking the ammonia borane hydrolysis as an example, a combination of density functional theory (DFT) calculations, advanced characterizations, and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry, Pt charge state and binding energy, activation entropy/enthalpy, and resultant catalytic activity. After decoupling the influences of other factors, the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site, contributing to a 15-fold increment in the hydrogen generation rate. Further incorporating the Pt charge with the number of Pt active sites, a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance. Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.