Shape-controlled Cu2O Nanocrystals for Electrochemical Reduction of CO2

Bianca Ligt^a, Michelle Ho^a, Marta 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)

#Suschem- Materials and electrochemistry for sustainable fuels and chemicals

Barcelona, Spain, 2022 October 24th - 28th

Organizers: Marta Costa Figueiredo and Raffaella Buonsanti

Contributed talk, Bianca Ligt, presentation 096
DOI: https://doi.org/10.29363/nanoge.nfm.2022.096
Publication date: 11th July 2022

The electrochemical reduction of CO₂ (CO₂RR) with Cu-based catalysts has a rather poor selectivity towards C₂₊ molecules, such as ethylene and ethanol. Up to 16 different products can typically be formed during the process. [1] However, copper is the only known element with the ability to make C-C bonds and produce the desired C₂₊ products.[2] Therefore, it is key to gain a better understanding of the active sites of Cu-based electrocatalysts in order to improve the design and consequently the selectivity towards molecules such as ethylene and ethanol. This can be done, for example, by using well defined surfaces such as single crystals, providing insights into the reactivity of different exposed planes. It has beed shown that ethylene is mainly produced on Cu (111) facets while a higher selectivity for methane was observed for Cu (100) facets. [3],[4]

In this study, cubic and octahedral Cu₂O nanocrystals predominantly exposing (100) and (111) facets were synthesized, respectively. Polyvinylpyrrolidone (PVP) was added during the synthesis as a capping agent to delicately control the ratio of (111) over (100) planes, yielding different shape Cu₂O nanostructures. [5] The presence of preferential cubic or octahedral shapes on the different synthesis was also confirmed by X-ray poweder diffraction (XRD), Moreover, the ratio of diffraction intensity for the (111) and (200) reflections showed an increase for the octahedral structure. Additionally, the synthesis procedure allowed the control of the size of the nanostructures between 400 and 800 nm as confirmed by SEM. Chronoamperometric measurements revealed that the cubic Cu₂O nanocrystals are more selective towards ethylene compared to the octahedral shaped particles. The cubic Cu₂O nanocrystals achieved a Faradaic efficiency for C₂₊ products of approximately 60% at a potential of -1.0 V vs. RHE. These results are in agreement with the observations on Cu single crystals, showing that the surface structure dependence for CO₂RR is maintained for Cu₂O catalysts.

References:

[1] Kuhl, K.P.; Cave, E.R.; Abram, D.N.; Jaramillo, T.F. New Insights Into the Electrochemical Reduction of Carbon Dioxide on Metallic Copper Surfaces. Energy Environ. Sci., 2012, 5, 7050-7059.

[2] Bagger, A.; Ju, W.; Varela, A.S.; Strasser, P.; Rossmeisl, J. Electrochemical CO2 Reduction: A Classification Problem. ChemPhysChem, 2017, 18, 3266-3273.

[3] Loiudice, A.; Lobaccaro, P.; Kamaili, E.A.; Thao, T.; Huang, B.H.; Ager, J.W.; Buonsanti, R. Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction. Angew. Chem. Int. Ed. 2016, 55, 5789-5792.

[4] Gregorio, G.L.; Burdyny, T.; Loiudice,; Iyengar, P.; Smith, W.A.; Buonsanti, R. Facet-Dependent Selectivity of Cu catalysts in Electrochemical CO2 Reduction at Commercially Viable Current Densities. ACS Catal. 2020, 10, 4854-4862.

[5] Zhang, D.-F.; Zhang, H.; Guo, L.; Zheng, K.; Han, X.-D.; Zhang, Z. Delicate Control of Crystallographic Facet-Oriented Cu2O Nanocrystals and the Correlated Adsorption Ability. J. Mater. Chem. 2009, 19, 5220-5225.

Acknowledgements:

This publication is part of the research programme 'Reversible Large-scale Energy Storage' (RELEASE) with project number 17621 which is financed by the Dutch Research Council (NWO).

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