Electronic and geometric determinants of adsorption: fundamentals and applications

Abstract

Abstract Adsorption is an essential phenomenon in surface science and is closely related to many applications such as catalysis, sensors, energy storage, biomedical applications and so on. It is widely accepted that the adsorption properties are determined by the electronic and geometric structures of substrates and adsorbates. The d-band model and the generalized coordination number model take the electronic and geometric structures of substrates into consideration respectively, successfully rationalizing the trends of adsorption on transition metals (TMs), TM nanoparticles (NPs) and some TM alloys. The linear scaling relationship (LSR) uncovers the role of the electronic structures of adsorbates in adsorption and allow the ascertainment of the trend of adsorption between different adsorbates. Recently, we develop an effective model to correlate adsorption energy with the easily accessible intrinsic electronic and geometric properties of substrates and adsorbates which holds for TMs, TM NPs, near-surface alloys and oxides. This intrinsic model can naturally derive the LSR and its generalized form, indicates the efficiency and limitation of engineering the adsorption energy and reaction energy, and enables rapid screening of potential candidates and designing of catalysts since all parameters are accessible and predictable. In this comprehensive review, we summarize these models to clarify their development process and uncover their connection and distinction, thereby drawing an explicit and overall physical picture of adsorption. Consequently, we provide a more comprehensive understanding about the broad applications of these models in catalysis. The theoretical part introduces necessary theoretical foundations and several well-built models with respect to the electronic models, the geometric models, the LSR and the intrinsic model. The application section describes their broad scope in catalysis, including oxygen reduction reaction, CO2 reduction reaction and nitrogen reduction reaction. We believe this review will provide necessary and fundamental background knowledge to further understand the underlying mechanism of adsorption and offer beneficial guidance for the rapid screening of catalysts and materials design.