Formulating the bonding contribution equation in heterogeneous catalysis: a quantitative description between the surface structure and adsorption energy

Abstract

The relation between surface structure and adsorption energy of adsorbate is of great importance in heterogeneous catalysis. Based on density functional theory calculations, we propose an explicit equation with three chemically meaningful terms, namely the bonding contribution equation, to quantitatively account the surface structures and the adsorption energies. Successful predictions of oxygen adsorption energies on complex alloy surfaces containing up to 4 components are demonstrated, and the generality of this equation is also tested using different surface sizes and other adsorbates. This work not only may offer a powerful tool to understand the structureadsorption relation, but also may be used to inversely design novel catalysts.

High-Entropy Alloys as a Discovery Platform for Electrocatalysis

“…With our model for the fast prediction of per-site activities, the HEA surface can be tailored to promote sites with optimal catalytic properties. relating surface structure with adsorption energy are already established, namely the d-band model presented by Hammer and Nørskov, 18 the generalized coordination number model presented by Calle-Vallejo and colleagues, 19 the bonding contribution model proposed by Wang and Hu, 20 and the Orbitalwise coordination number model proposed by Xin and Ma. 21 However, none of these models can easily be extended to the multicomponent surface of an HEA.…”

Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys

“…53 For example, a RhAg SAA is predicted to bind CO more strongly than pure Rh(111) itself. 53,90 Interestingly for SAAs, the host-like or dopant-like strength of the bonding is not generally discerned through some linear combination of pure-host or pure-dopant adsorption energies, [96][97][98] nor do these surfaces adhere to the d-band adsorption model. 53,92 This makes SAA catalysts novel and exciting; by not following the scaling models of other pure and alloy transition metal surfaces, SAAs can offer unique adsorption properties that, when understood, can be employed in the design of superior catalysts.…”

A rational catalyst design of CO oxidation using the bonding contribution equation

“…More details in the defination and chemical meaning of these parameters can be found in the original work 18 . We calculated the volcano diagram of CO oxidation ( Figure 2) based on the BEP relation and micro-kinetic modelling, similar to the one reported by Nørskov and co-workers 29 .…”

“…In their work, they introduced a coordination-activity plots to determine the geometric structure of optimal active sites of platinum for oxygen reduction reaction. Herein, we propose a catalyst design approach applicable to a more complicated system namely alloy surfaces based on the bonding contribution equation 18 , which is a relation between surface structures and the corresponding adsorption energies introduced in our previous work. Using this equation, several outstanding catalysts of CO oxidation are rationally designed using a simple yet powerful scheme, which are several orders of magnitude more active than traditional platinum catalysts based on the DFT calculations and microkinetic modellings.…”

“…Therefore, a relation to link the hundreds of thousands of alloy surface structures to the corresponding adsorption energies is the key. In our previous work, an explicit equation was proposed to quantitatively account the surface structures and the adsorption energies, namely the bonding contribution equation 18 . Successful predictions of oxygen adsorption energies on complex alloy surfaces containing up to 4 components were demonstrated, and the generality of this equation was also tested for CO adsorption.…”