Issue 48, 2020

Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H2 production from water

Abstract

Metal oxide cluster models of catalyst materials offer a powerful platform for probing the molecular-scale features and interactions that govern catalysis. This perspective gives an overview of studies implementing the combination of anion photoelectron (PE) spectroscopy and density functional theory calculations toward exploring cluster models of metal oxides and metal-oxide supported Pt that catalytically drive the hydrogen evolution reaction (HER) or the water–gas shift reaction. The utility in the combination of these experimental and computational techniques lies in our ability to unambiguously determine electronic and molecular structures, which can then connect to results of reactivity studies. In particular, we focus on the activity of oxygen vacancies modeled by suboxide clusters, the critical mechanistic step of forming proximal metal hydride and hydroxide groups as a prerequisite for H2 production, and the structural features that lead to trapped dihydroxide groups. The pronounced asymmetric oxidation found in heterometallic group 6 oxides and near-neighbor group 5/group 6 results in higher activity toward water, while group 7/group 6 oxides form very specific stoichiometries that suggest facile regeneration. Studies on the trans-periodic combination of cerium oxide and platinum as a model for ceria supported Pt atoms and nanoparticles reveal striking negative charge accumulation by Pt, which, combined with the ionic conductivity of ceria, suggests a mechanism for the exceptionally high activity of this system towards the water–gas shift reaction.

Graphical abstract: Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H2 production from water

Article information

Article type
Perspective
Submitted
24 set 2020
Accepted
12 nov 2020
First published
12 nov 2020

Phys. Chem. Chem. Phys., 2020,22, 27936-27948

Author version available

Using anion photoelectron spectroscopy of cluster models to gain insights into mechanisms of catalyst-mediated H2 production from water

A. J. McMahon and C. C. Jarrold, Phys. Chem. Chem. Phys., 2020, 22, 27936 DOI: 10.1039/D0CP05055E

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