Jump to main content
Jump to site search
SCHEDULED MAINTENANCE Close the message box

Maintenance work is planned for Monday 16 August 2021 from 07:00 to 23:59 (BST).

Website performance may be temporarily affected and you may not be able to access some PDFs or images. If this does happen, refreshing your web browser should resolve the issue. We apologise for any inconvenience this might cause and thank you for your patience.


Issue 4, 2020

Insight into the active site and reaction mechanism for selective oxidation of methane to methanol using H2O2 on a Rh1/ZrO2 catalyst

Author affiliations

Abstract

Direct methane conversion into value-added products has become increasingly important. However, it remains a great challenge to effectively activate methane and simultaneously suppress its over-oxidation. In this study, we performed a combined ab initio thermodynamics and DFT+U study to investigate the selective oxidation of methane to methanol on a ZrO2-supported Rh single-atom catalyst. The most preferred local environment of a Rh single atom was proposed according to the ab initio thermodynamics results. The DFT calculation results show that the five-coordinated Rh structure leads to the over-oxidation of CH3 species and thus prevents the formation of methanol. In contrast, the four-coordinated Rh can effectively stabilize the CH3 species by suppressing its further dehydrogenation. This is attributed to the fact that the geometric configuration of CH3 species at the four-coordinated Rh hinders the interaction between H in CH3 species and neighboring O. Two different methanol formation mechanisms at the four-coordinated Rh, namely the direct pathway and the CH3OOH intermediate pathway, were studied. It was found that the four-coordinated Rh facilitates the activation of H2O2 and the formation of CH3OOH, and thus the CH3OOH intermediate pathway plays a dominant role in methanol formation, in which CH3O species reacts with the OH group in H2O2 to form the CH3OOH intermediate and subsequently the deoxygenation of CH3OOH leads to the formation of methanol. This study provides atomic-scale insights into the active site and reaction mechanism for selective oxidation of methane to methanol on Rh1/ZrO2 catalysts.

Graphical abstract: Insight into the active site and reaction mechanism for selective oxidation of methane to methanol using H2O2 on a Rh1/ZrO2 catalyst

Article information


Submitted
15 Nov 2019
Accepted
29 Dec 2019
First published
31 Dec 2019

New J. Chem., 2020,44, 1632-1639
Article type
Paper

Insight into the active site and reaction mechanism for selective oxidation of methane to methanol using H2O2 on a Rh1/ZrO2 catalyst

Q. Zhao, B. Liu, Y. Xu, F. Jiang and X. Liu, New J. Chem., 2020, 44, 1632 DOI: 10.1039/C9NJ05667J

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

Search articles by author

Spotlight

Advertisements