(17c) Novel Approach to Synthesize the Cu-Based Selective Electrocatalysts for CO2 Electroreduction

Novel Approach to Synthesize the Cu-based Selective Electrocatalysts for CO₂ Electroreduction

Monica Padilla¹, Alexey Serov¹, Kateryna Artyushkova¹, Olga A. Baturina² and Plamen Atanassov¹

¹University of New Mexico, Albuquerque, NM 87131

²Naval Research Laboratory, Washington DC 20375

CO₂ is a major green-house gas that can be used for production of useful value added products such as alcohols, methane or ethane [1]. Carbon dioxide can be electrochemically reduced to hydrocarbon fuels under ambient temperature and pressure. This technology currently in development stage and therefore it can benefit from knowledge obtained from research in the field of the proton exchange membrane fuel cell (PEMFC).  The design principles for CO₂ systems (electrolyzers) are similar to those of PEMFCs or anion-exchange membrane fuel cells. Similar to the oxygen reduction reaction (ORR) in PEMFCs, the reaction at the cathode of a CO₂ electrolyzer requires a carefully designed electrocatalyst. On the other side, it should be mentioned that contrary to the ORR, CO₂ electroreduction reaction results in multiple reaction products that are generated both in liquid and gas phase. In order to make the CO₂electroreduction systems viable and prevent cost-heavy separation of products step the catalysts selective to only one product should be designed, synthesized and scaled-up.

Here we report our results on synthetic method development – based on Sacrificial Support Method (SSM) for preparation of Cu-based materials [2-5]. The method of the evaluation of electrocatalytic activity of un-supported Cu catalysts for the CO₂ electroreduction reaction was based on the rotating disk electrode (RDE) technique and online gas chromatography (GC). The sealed RDE cell was specially designed and it was demonstrated that the reaction products generated on small surface area thin RDE films can be quantified by online GC. Liquid reaction products are separated and identified ex-situ  by liquid chromatography or NMR.

               It was shown that controlling the SSM parameters it was possible to synthesize the Cu-based electrocatalyst with selectivity to C₂products close to 90%.

Acknowledgements

OAB is grateful to the Office of Naval Research for financial support of this project.

References

[1] Y. Hori, Electrochemical CO₂reduction on metal electrodes, in: C.e.a. Vayenas (Ed.) Modern Aspects of Electrochemistry, vol. 42, Springer, New York, 2008.

[2] A. Serov, K. Artyushkova, N. I. Andersen, S. Stariha, P. Atanassov "Original Mechanochemical Synthesis of Non-Platinum Group Metals Oxygen Reduction Reaction Catalysts Assisted by Sacrificial Support Method", Electrochim. Acta (2015) doi:10.1016/j.electacta.2015.02.108

[3] A. Serov, N. I. Andersen, A. J. Roy, I. Matanovic, K. Artyushkova, P. Atanassov, “CuCo2O4 ORR/OER Bi-Functional Catalyst: Influence of Synthetic Approach on Performance”, J. of The Electrochem. Soc., 162 (4) (2015) F449-F454

[4] C. Santoro, A. Serov, C. W. Narvaez Villarrubia, S. Stariha, S. Babanova, A. J. Schuler, K. Artyushkova, P. Atanassov. “Double‐Chamber Microbial Fuel Cell with a Non‐Platinum‐Group Metal Fe–N–C Cathode Catalyst”, ChemSusChem, 8 (2015), 828-834.

[5] N. I. Andersen, A. Serov, P. Atanassov “Metal Oxides/CNT Nano-Composite Catalysts for Oxygen Reduction/Oxygen Evolution in Alkaline Media”, Appl. Catal. B: Environmental, 163 (2015), 623-627.

[6] Z. Zhang, K.L. More, K. Sun, Z. Wu, W. Li, Chemistry of Materials, 23 (2011) 1570.

[7] S. Trasatti, O.A. Petrii, Pure and Applied Chemistry, 63 (1991) 711.