Volume 1, 2023

An unexplored role of the CrOx shell in an elaborated Rh/CrOx core–shell cocatalyst for photocatalytic water splitting: a selective electron transport pathway from semiconductors to core metals, boosting charge separation and H2 evolution

Abstract

A core–shell structured Rh/CrOx cocatalyst has endowed various semiconductors with high efficiency in water-splitting photocatalysis, where thin CrOx layers on Rh have been assumed to be physical blockers of O2 to the metal surface to suppress unfavorable reverse reactions (e.g., catalytic H2O formation from H2 and O2). Herein, we propose another unexplored but favorable function of CrOx layers: a selective electron transport pathway from photocatalysts to the Rh core boosting charge separation and H2 production. The subsequent loading of CrOx layers onto Rh increased the rate of visible light H2 evolution of a Bi4NbO8Cl photocatalyst, even in a half reaction with a hole scavenger where O2 does not evolve. Transient absorption spectroscopy revealed that the CrOx layer increases the electron path from Bi4NbO8Cl to Rh. Importantly, the highest H2-evolution activity was obtained by simultaneous photodeposition using CrIII and RhIII precursors, which had not yet been examined. In this sample, Rh nanoparticles were enclosed by an amorphous CrOx shell, where Rh particles were less directly attached to the semiconductor. Therein, CrOx inserted between Bi4NbO8Cl and Rh effectively suppresses undesirable hole transfer from Bi4NbO8Cl to Rh, while such hole transfer partially occurs when they are in direct contact. These results indicated that CrOx functions as a selective electron transport pathway and improves the H2 evolution activity. Although the development strategy of cocatalysts has so far focused on surface redox reactions, this study offers a new approach for the design of highly efficient cocatalysts based on the carrier transfer process, especially at semiconductor–cocatalyst interfaces.

Graphical abstract: An unexplored role of the CrOx shell in an elaborated Rh/CrOx core–shell cocatalyst for photocatalytic water splitting: a selective electron transport pathway from semiconductors to core metals, boosting charge separation and H2 evolution

Supplementary files

Article information

Article type
Paper
Submitted
20 12 2022
Accepted
15 3 2023
First published
18 3 2023
This article is Open Access
Creative Commons BY-NC license

EES. Catal., 2023,1, 255-262

An unexplored role of the CrOx shell in an elaborated Rh/CrOx core–shell cocatalyst for photocatalytic water splitting: a selective electron transport pathway from semiconductors to core metals, boosting charge separation and H2 evolution

T. Kotani, K. Ogawa, H. Suzuki, K. Kato, O. Tomita, A. Yamakata and R. Abe, EES. Catal., 2023, 1, 255 DOI: 10.1039/D2EY00109H

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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