Metal Doping Activation of Anion-Mediated Electron Transfer in Catalytic Reactions
Chaoyue Zhang, Jing Yu, Chenyang Huang, Guowen Sun, Ll. Balcells, Jiayue Li, Xuede Qi, Yi Cheng, Javier Herrero‐Martín, Laura Simonelli, François Fauth, Ren He, Xiaobo Pan, Junshan Li, Jordi Arbiol, Jinyuan Zhou, Andreu Cabot
Abstract
Heteroatom-doping has emerged as a transformative approach to producing high-performance catalysts, yet the current trial-and-error approach to optimize these materials remains ineffective. To enable the rational design of more efficient catalysts, models grounded in a deeper understanding of catalytic mechanisms are essential. Existing models, such as d -band center theory, fall short in explaining the role of dopants, particularly when these dopants do not directly interact with reactants. In this study, we synthesize various heteroatom-doped catalysts to explore the correlation between the electronic effects of the dopants and catalyst activity. Using Co-MoS 2 as a model catalyst and the Li–S redox reaction within the cathode of Li–S batteries as a test system, we show the interaction between cobalt sites and adjacent lattice sulfur atoms disrupts the intrinsic structural and electronic symmetry of MoS 2 . This disruption enhances the transfer of spin-polarized electrons from metal centers to lattice sulfur and promotes the adsorption of reactant intermediates. Furthermore, by analyzing 20 different dopant elements, we establish a linear relationship between the electron density in the lattice sulfur and catalyst activity toward the reduction of sulfur species, a relationship that extends to other catalytic systems, such as the hydrogen evolution reaction.