Evaluating the role of microenvironments in electrochemical CO2 reduction via multiscale modeling
Francesca Lorenzutti a, Ranga R. Seemakurthi b, Evan F. Johnson a, Santiago Morandi b c, Pavle Nikačević b, Núria López b, Sophia Haussener a
a Laboratory of Renewable Energy Science and Engineering, Institute of Mechanical Engineering, EPFL, Station 9, 1015 Lausanne, Switzerland.
b Institute of Chemical Research of Catalonia (ICIQ-CERCA), Avinguda Països Catalans 16, 43007 Tarragona, Spain.
c Department of Physical and Inorganic Chemistry, Universitat Rovira i Virgili, Campus Sescelades, N4 Block, C. Marcel·lí Domingo 1, 43007, Tarragona, Spain.
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)
#PECCO2 - Advances in (Photo)Electrochemical CO2 Conversion to Chemicals and Fuels
Lausanne, Switzerland, 2024 November 12th - 15th
Organizers: Deepak PANT, Adriano Sacco and juqin zeng
Oral, Francesca Lorenzutti, presentation 183
DOI: https://doi.org/10.29363/nanoge.matsusfall.2024.183
Publication date: 28th August 2024

It is experimentally known that electrochemical CO2 reduction (eCO2R) does not take place on Cu, Ag and Au without a cation near the electrode surface, and that both organic and inorganic cations modulate eCO2R activity and selectivity. The rational optimization of microenvironments in eCO2R requires understanding of the intricate chemical and transport phenomena taking place across length scales.

We modeled CO2 reduction to CO on Ag via a multiscale approach, accounting for the role of the cation at all scales. The transport is modeled by generalized modified Poisson-Nernst-Planck equations and a microkinetic model is used to calculate the current densities of CO2 reduction to CO and the competing reduction of water (H2OR) and H+ to H2 based on the local conditions. Kinetic rate constants are obtained from atomic-scale calculations (DFT and AIMD). In particular, the number of active sites (the microenvironments) depends on the local cation concentration.

We considered different buffers, including alkali (Li+, K+ and Cs+), alkali-earth (Mg2+ and Ba2+) and organic (tetramethylammonium - TMA+) cations, and we evaluated different concentrations (from 1 mM to 2 M) over a large potential window (-0.4 to -1.6 V vs RHE). We observed consistent behaviors across cations of different nature: at slightly negative applied potentials, higher cation concentration leads to improved activity, despite the lower CO2 solubility in higher ionic strength buffers. At strongly negative applied potentials, cation accumulation due to double layer charging leads to transport limitations and the CO current density is lower at higher cation concentrations. Cs+ leads to higher CO current density and high CO selectivity for a combination of favorable chemical and transport properties. We applied the same framework to a TMA+ - based anion exchange membrane (AEM) in the vicinity of an Ag electrode and evaluated the effect of a fixed background charge at different hydration levels on eCO2R activity and selectivity. We showed that, when the AEM is in contact with an electrolyte, the inorganic cation is still present at the AEM-electrolyte interface and contributes to the CO2R and H2OR microenvironments.

The model consistently reproduces experimental trends and helps to elucidate optimal local condition for eCO2R on Ag in aqueous electrolytes and ionomers. Our work paves the way for a coupled multiscale electrolyte and ionomer design for electrochemical interfaces.

F.L., R.R.S and P.N. acknowledge the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 861151 (F.L. and P.N.) and no. 754510 (R.R.S). F.L., E.F.J., S.M., N.L. and S.H. acknowledge funding from NCCR Catalysis (grant number 180544), a National Centre of Competence in Research funded by the Swiss National Science Foundation. N.L. and R.R.S. thank the Spanish Ministry of Science and Innovation (PID2021-122516OBI00) and Severo Ochoa (CEX2019-000925-S) for their financial support. The Barcelona Supercomputing Center (BSC-RES) is further acknowledged for providing generous computational resources and technical support.

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