Enhanced electroreduction of CO2 to C2+ products on heterostructured Cu/oxide electrodes

doi:10.1016/j.chempr.2022.04.004

Chem

Volume 8, Issue 8, 11 August 2022, Pages 2148-2162

https://doi.org/10.1016/j.chempr.2022.04.004 Get rights and content

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Highlights

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Correlating Cu/oxide heterostructures with electrocatalytic performance for CO₂RR
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Cu/ZrO₂ electrode demonstrates a high faradic efficiency of 85% for C₂₊ products
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Uncovering the origin of enhanced C₂₊ formation on Cu/ZrO₂ heterostructure

The bigger picture

As the world is seeking a carbon-neutral economy, there is an urgent need to reduce industrial CO₂ emissions. Converting CO₂ into chemical feedstocks is a promising way to transform CO₂ waste into usable products. Driven by renewable electricity, electroreduction of CO₂ could produce fuels and value-added chemicals including olefins, alcohols, oxygenates, and syngas with a negative carbon emissions footprint, which might reform the chemical and energy industries. Cu electrocatalysts are capable to produce high-value multicarbon products such as ethylene and ethanol, yet the catalytic performances are not satisfactory. In this study, we show that constructing heterostructures on Cu electrode with proper oxides offer unique interfacial boundaries for the CO₂ reduction reactions. By modulating the adsorption of intermediates and energy barriers of key reaction steps, the Cu/oxide heterostructured electrodes promote the conversion of CO₂ into multicarbon products.

Summary

Electrochemical reduction of CO₂ to value-added multicarbon products has been limited by the inefficiency of the C–C coupling process on Cu. Coupling metal oxides with Cu surfaces offers new freedom to break scaling relationships, thus regulating the product distribution on Cu. Herein, we show that metal oxides with the capability to stabilize the adsorbed CO₂∗/CO∗ and decrease the Gibbs free energies of the C–C coupling process can promote the formation of C₂₊ products on oxide-modified Cu electrodes. As a representative, ZrO₂-modified Cu (Cu/ZrO₂) electrode shows a high faradic efficiency of 85% for C₂₊ products. In situ surface-enhanced Raman spectra confirm the enhanced adsorption of CO∗ on the Cu/ZrO₂ electrode, while theoretical calculations reveal the decreased energy barriers of the C–C coupling process at the Cu-ZrO₂ interfacial boundaries. This study sheds light on the structure-property relationship of metal-oxide heterostructured electrocatalysts and accelerates the implementation of CO₂ electroreduction toward high-value products.

Graphical abstract

Keywords

CO₂ reduction

multicarbon products

interface

copper

heterostructure

zirconium oxide

ethylene

ethanol

UN Sustainable Development Goals

SDG7: Affordable and clean energy

SDG13: Climate action

Data and code availability

The datasets generated in this study are available from the lead contact upon request.

Cited by (0)

⁵: These authors contributed equally

⁶: Lead contact