Addressing the uncertainty of DFT-determined hydrogenation mechanisms over coinage metal surfaces

Density functional theory (DFT) has been considered as a powerful tool for the identification of reaction mechanisms. However, it is still unclear whether the error of DFT calculations would lead to mis-identification of mechanisms. Here, taking the hydrogenation of acetylene and 1,3-butadiene as model reactions and employing a well-trained Bayesian error estimation functional with van der Waals correlation (BEEF-vdW), we try to estimate the error of DFT calculation results statistically, and therefore predict the reliability of the hydrogenation mechanisms identified. With an ensemble of 2000 functionals obtained around the BEEF-vdW functional as well as a descriptor developed to represent the possibility of different mechanisms, we found that the non-Horiuti-Polanyi mechanism is preferred on Ag(211) and Au(211), while the Horiuti-Polanyi mechanism is dominant on Cu(211). We further discovered that the descriptor is linearly correlated with the adsorption energies of reaction intermediates during acetylene and butadiene hydrogenation, and the hydrogenation of strongly adsorbed species are more likely to follow the Horiuti-Polanyi mechanism. We found the probability of following the non-HP mechanism obeys the order Cu(211) < Au(211) < Ag(211). Our work gives a more comprehensive explanation for the mechanisms of coinage metal catalyzed hydrogenation reactions, and also provides more theoretical insights into the development of new high-performance catalysts for selective hydrogenation reactions.

Automated summary

The study estimated the error of DFT calculation results using statistical methods and predicted the reliability of hydrogenation mechanisms. The results indicated different hydrogenation mechanisms for acetylene and butadiene on different metal surfaces, with a strong correlation between adsorption energies of reaction intermediates and mechanisms.