Issue 28, 2022

Reaction-driven selective CO2 hydrogenation to formic acid on Pd(111)

Abstract

Conversion of CO2 to useful fuels and chemicals has gained great attention in the past decades; yet the challenge persists due to the inert nature of CO2 and the wide range of products formed. Pd-based catalysts are extensively studied to facilitate CO2 hydrogenation to methanol via a reverse water gas shift (rWGS) pathway or formate pathway where formic acid may serve as an intermediate species. Here, we report the selective production of formic acid on the stable Pd(111) surface phase under CO2 hydrogenation conditions, which is fully covered by chemisorbed hydrogen, using combined Density Functional Theory (DFT) and Kinetic Monte Carlo (KMC) simulations. The results show that with the full coverage of hydrogen, instead of producing methanol as reported for Pd(111), the CO2 activation is highly selective to formic acid via a multi-step process involving the carboxyl intermediate. The high formic acid selectivity is associated with surface hydrogen species on Pd(111), which not only acts as a hydrogen reservoir to facilitate the hydrogenation steps, but also enables the formation of confined vacancy sites to facilitate the production and removal of formic acid. Our study highlights the importance of reactive environments, which can transform the surface structures and thus tune the activity/selectivity of catalysts.

Graphical abstract: Reaction-driven selective CO2 hydrogenation to formic acid on Pd(111)

Supplementary files

Article information

Article type
Paper
Submitted
29 Apr 2022
Accepted
08 Jun 2022
First published
09 Jun 2022

Phys. Chem. Chem. Phys., 2022,24, 16997-17003

Reaction-driven selective CO2 hydrogenation to formic acid on Pd(111)

H. Zhang, X. Wang and P. Liu, Phys. Chem. Chem. Phys., 2022, 24, 16997 DOI: 10.1039/D2CP01971J

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