Volume 229, 2021

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

Abstract

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.

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

Associated articles

Supplementary files

Article information

Article type
Paper
Submitted
18 พ.ย. 2562
Accepted
22 ม.ค. 2563
First published
22 ม.ค. 2563

Faraday Discuss., 2021,229, 50-61

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

K. Yang and B. Yang, Faraday Discuss., 2021, 229, 50 DOI: 10.1039/C9FD00122K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements