The influence of copper particle size on the electrochemical reduction of CO to products with C-C bonds

Floriane Rollier^a, Marta Costa Figueiredo^a, Emiel Hensen^a

^aDepartment of Chemical Engineering and Chemistry, Eindhoven University of Technology,, Building Helix P.O. Box 513 5600 MB Eindhoven, Netherlands

Materials for Sustainable Development Conference (MATSUS)
Proceedings of Materials for Sustainable Development Conference (MAT-SUS) (NFM22)

#OPCAT - Operando Characterization of Electrocatalytic Interfaces

Barcelona, Spain, 2022 October 24th - 28th

Organizer: Reshma Rao

Contributed talk, Floriane Rollier, presentation 074
DOI: https://doi.org/10.29363/nanoge.nfm.2022.074
Publication date: 11th July 2022

Growing environmental concerns, as a result of fossil fuel utilization, constitute a driving force towards the development of sustainable technologies to produce chemicals. The electroreduction of CO (CORR) or CO₂ (CO2RR) to fuels are part of these technologies as C₁ (methane, methanol) and C₂₊ products (ethylene, propylene, ethanol, propanol etc.) can be obtained [1]. CO is a particularly interesting reactant because it is present in CO-rich waste streams of common industries such as steel manufacture. For instance, it may be valuable to convert CO contained in blast furnaces’ flue gases, considered an irreducible source of COx, into chemical building blocks such as olefins or alcohols. Converting CO to light hydrocarbons and oxygenates by means of renewable electricity could help reducing our dependence on fossil resources. Moreover, CO can also be obtained from the widely studied CO2RR. CO constitutes a key intermediate in C₂₊ products formation in the aforementioned reaction [2]. Alternative to classical CO hydrogenation (Fischer-Tropsch synthesis), we considered here an electrochemical variant to obtain products with C-C bonds (C₂₊ products).

In this study, we focused on the electrosynthesis of C₂₊ products from CO on Cu-based catalysts. We studied the influence of catalyst particle size on the product distribution obtained during CO electroreduction. Particles ranging from smaller than 7 nm up to 45 nm were investigated. Intermediate sizes (20 nm – 30 nm) and a Cu foil have been reported to be the most selective for the formation of C-C bonds (ethanol, ethylene, propanol, etc..) during electroreduction of CO₂ [3]. Our results show a different selectivity trend when using CO as reactant. The chronoamperometry data show a clear dependency of the selectivity on the particle size of the Cu electrocatalyst (Figure 1) with intermediate sizes (11 to 27 nm) showing the highest selectivity towards C₂₊ products while smaller particles favor hydrogen evolution. Among the used characterization methods, in situ XRD was employed to investigate stability of the particles under electrochemical conditions.

References:

[1] Zhang H. et al., CO Electroreduction: Current development and Understanding of Cu-Based Catalysts, ACS catal. 2019, 9, 1, 49-65

[2] Nitopi A. et al., Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte, Chem. Rev. 2019, 119, 12, 7610-7672

[3] Reske R. et al., Particle Size Effects in the Catalytic Electroreduction of CO2 on Cu Nanoparticles, J. Am. Chem. Soc. 2014, 136, 19, 6978-6986

Acknowledgements:

We acknowledge NWO and industrial partners SHELL, TataSteel, Brightlands and Smartport for funding this project in the consortium E2CB.

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