Microenvironment Effect of Graphene‐Based Single‐Atom Iron Catalysts on Adsorption Characteristics of Flue Gases

ABSTRACT Due to its high catalytic activity and high selectivity, graphene‐based single‐atom materials have attracted widespread attention in various fields, such as adsorbent, catalyst, and sensor. The regulation of adsorption characteristics is the foundation of the above applications. Current research on adsorption characteristics is primarily focused on tuning metal species while neglecting the effect of microenvironment for metal centers. Herein, this work systematically investigates the adsorption characteristics of graphene‐based single‐atom iron catalysts through density functional theory calculation. Through doping different coordinated atoms (B, C, N, O, S, P, and Cl), we analyze the effect of the microenvironment on adsorption configuration, electron transfer mechanism, and adsorption energy for various flue gases (NH 3 , H 2 O, NO, NO 2 , SO 2 , and O 2 ). The differences in stable adsorption configurations of various graphene‐based single‐atom iron catalysts can be well‐understood by the analysis of frontier molecular orbitals. In addition, the system electronegativity is a reliable descriptor of adsorption energy. Therefore, our study has established a correlation between electronic structure and adsorption energy, laying a foundation for further study of the adsorption characteristics of microenvironment‐regulated catalysts and providing guidance for the development and design of new nonnoble metal single‐atom catalysts for complex flue gas components.