Vacancy Formation Energy as an Effective Descriptor for the Catalytic Oxidation of CO by Au Nanoparticles

Gold nanoparticles (AuNPs) have attracted wide attention in the field of catalysis because of their excellent stability and electrical properties. Herein, an accurate vacancy formation energy model based on nanothermodynamics theory is developed, the intrinsic correlation between vacancy formation energy and CO oxidation activity is investigated in detail, and the relationship between vacancy formation energy and activity-influencing factors such as particle size, temperature, and crystal surface is analyzed. The results show an excellent linear relationship between vacancy formation energy and CO oxidation activity, with an accuracy of up to 95%. In addition, the vacancy formation energy also corresponds well to the influencing factors of size, temperature, and crystal surface, and its correspondence is particularly accurate when the size is below 20 nm and the temperature is below 500 K. It can serve as a normalized expression of the three influencing factors. Moreover, the present research reveals that the essence of the vacancy formation energy descriptor is the chemical bond energy, and gives its correspondence with the coordination number, diffusion activation energy, and adsorption energy (with a decrease in vacancy formation energy, the adsorption effect of AuNPs is stronger), further demonstrating the feasibility and accuracy of the vacancy formation energy as a descriptor. This research not only overcomes the problem that traditional single-influence descriptors are difficult to apply in complex environments but also has considerable potential for defect modulation.