Issue 11, 2020

Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction

Abstract

The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) involves a variety of electron transfer pathways, resulting in poor reaction selectivity, limiting its use to meet future energy requirements. Polyoxometalates (POMs) can both store and release multiple electrons in the electrochemical process, and this is expected to be an ideal “electron switch” to match with catalytically active species, realize electron transfer modulation and promote the activity and selectivity of the electrocatalytic CO2RR. Herein, we report a series of new POM-based manganese-carbonyl (MnL) composite CO2 reduction electrocatalysts, whereby SiW12–MnL exhibits the most remarkable activity and selectivity for CO2RR to CO, resulting in an increase in the faradaic efficiency (FE) from 65% (MnL) to a record-value of 95% in aqueous electrolyte. A series of control electrochemical experiments, photoluminescence spectroscopy (PL), transient photovoltage (TPV) experiments, and density functional theory (DFT) calculations revealed that POMs act as electronic regulators to control the electron transfer process from POM to MnL units during the electrochemical reaction, enhancing the selectivity of the CO2RR to CO and depressing the competitive hydrogen evolution reaction (HER). This work demonstrates the significance of electron transfer modulation in the CO2RR and suggests a new idea for the design of efficient electrocatalysts towards CO2RR.

Graphical abstract: Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction

Supplementary files

Article information

Article type
Edge Article
Submitted
26 10 2019
Accepted
01 2 2020
First published
10 2 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2020,11, 3007-3015

Polyoxometalate-based electron transfer modulation for efficient electrocatalytic carbon dioxide reduction

J. Du, Z. Lang, Y. Ma, H. Tan, B. Liu, Y. Wang, Z. Kang and Y. Li, Chem. Sci., 2020, 11, 3007 DOI: 10.1039/C9SC05392A

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