Well-defined hybrid Copper-based nanoreactors for electrocatalytic CO2 reduction

Federico Franco^a, Joan Marc Bondia Pedra^a, Beatriu Domingo-Tafalla^a^,^c, Carlos Puerto^a, Tamal Chatterjee^a, Emilio Palomares-Gil^a^,^b

^aInstitute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), and University Rovira i Virgili (URV), Avinguda dels Països Catalans, Tarragona, Spain

^bICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain

^cDepartament d’Enginyeria Electrònica, Elèctrica i Automàtica, Universitat Rovira i Virgili, Avinguda dels Països Catalans, 26, Tarragona, Spain

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

Poster, Federico Franco, 303
Publication date: 11th July 2022

In the perspective of drastically reducing anthropogenic CO₂ emissions and mitigating the effects of global warming, the electrochemical CO₂ reduction reaction (CO₂RR) powered by renewable sources and catalyzed by transition metal-based catalysts represents an attractive strategy to produce fuels and commodity chemicals. However, further improvement in the catalyst design is required to tackle the main bottlenecks that currently limit the performances of the state-of-the-art catalysts. Although several transition metal-based systems have been reported to catalyze CO₂RR,[1]-[2]catalyst durability and selectivity still represent major challenges to achieve an efficient CO₂RR, mainly due to catalyst deactivation and to competitive Hydrogen evolution reaction (HER) and/or alternative pathways leading to multiple carbon-based products.

The combination of molecular chemistry and heterogeneous catalysis has recently revealed to be an effective strategy to improve the overall efficiency and selectivity of the CO₂RR process.[3] In particular, the formation of hybrid catalysts based on the integration of organic molecules or reticular frameworks with heterogeneous metal or metal-oxide surfaces allowed to tune the stability of key reaction intermediates or the local microenvironment of the catalyst, resulting in a significant improvement of the CO₂RR performances.[4]-[5]

In this contribution, we highlight a modular and versatile strategy to synthesize well-defined hybrid nanomaterials, based on the in situ growth of polymeric matrices around a well-defined metal nanoparticle core in a controlled manner. For instance, well-defined Cu₂O nanocubes (NCs) are used as both templates and catalysts for an in situ polymerization based on a Cu-catalyzed azide–alkyne cycloaddition reaction (CuAAC) in the presence of the corresponding monomeric building blocks.[6] This approach results in a series of hybrid nanoreactors with well-defined shape and size, which are active electrocatalysts for CO₂ reduction in neutral-pH electrolyte. The composition of the molecular layer was found to be critical for the catalytic performances. The data herein presented provide a proof-of-concept of the potential offered by a molecular perspective towards a rational design of heterogeneous electrocatalysts.

References:

[1] Franco, F.; Rettenmaier, C.; Jeon, H. S.; Roldan Cuenya, B.; Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials, Chem. Soc. Rev., 2020, 49, 6884

[2] Domingo-Tafalla, B.; Martínez-Ferrero, E.; Franco, F.; Palomares-Gil, E.; Applications of Carbon Dots for the Photocatalytic and Electrocatalytic Reduction of CO2, Molecules 2022, 27(3), 108

[3] Nam , D.-H.; De Luna, P.; Rosas-Hernández , A.; Thevenon, A.; Li, F.; Agapie, T.; Peters, J. C.; Shekhah, O.; Eddaoudi, M.; Sargent, E. H.; Molecular enhancement of heterogeneous CO2 reduction, Nature Materials, 2020, 19, 266

[4] Nam , D.-H.; Shekhah, O.; Lee, G.; Mallick, A.; Jiang, H.; Li, F.; Chen, B.; Wicks, J.; Eddaoudi, M.; Sargent, E. H.; Intermediate Binding Control Using Metal–Organic Frameworks Enhances Electrochemical CO2 Reduction, J. Am. Chem. Soc. 2020, 142, 21513

[5] Thevenon, A.; Rosas-Hernández , A.; Peters, J. C.; Agapie, T.; In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO2 Reduction to Ethylene, Angew. Chem. 2019, 131, 17108

[6] Chassaing, S.; Bénéteaub, V.; Pale, P.; When CuAAC 'Click Chemistry' goes heterogeneous, Catal. Sci. Technol., 2016, 6, 923

Acknowledgements:

F.F. thanks MCIN/AEI/10.13039/501100011033 for a Juan de la Cierva-Incorporación fellowship (IJC2019-042363-I). E.P.-G. acknowledges financial support from MINECO (project PID2019-109389RB-I00), SGR-AGAUR 2017SGR00978, ICIQ, CERCA, and ICREA.

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