Corrosion and Enhanced Hydrogen Evolution in Electrochemical Reduction of Ammonium Carbamate on Transition Metal Surfaces

• Published in: The journal of physical chemistry letters 2024-08, Vol.15 (31), p.8007-8017
• Main Authors: Choi, Jounghwan, Chiu, Shawn, Banerjee, Avishek, Sacci, Robert L., Veith, Gabriel M., Stieber, Chantal, Hahn, Christopher, Alexandrova, Anastassia N., Morales-Guio, Carlos G.
• Format: Article
• Language: English
• Subjects: electrodes; gold; inorganic carbon compounds; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; metals; oxides; Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.4c01638

Experiments and theory are combined to search for catalyst activity and stability descriptors for the direct reactive capture and conversion (RCC) of CO2 in ammonia capture solutions using Cu, Ag, Au, Sn, and Ti electrodes. Two major phenomena emerge in RCC that are not predominant in the electrochemical CO2 reduction (CO2R) reaction, namely, the rapid corrosion and restructuring of the catalyst in the presence of the CO2-ammonia adducts and the promotion of the competing hydrogen evolution reaction (HER). The prevalence of HER in RCC is correlated to the electrostatic attraction of the protonated amine to the electrode and the repulsion of the captured CO2, using the potential of zero charge (PZC). The stability of catalysts under RCC conditions is a function of the applied potential and cannot be readily predicted using binding energy descriptors commonly used in the prediction of CO2R activity. A direct correlation between calculated binding energies of CO2R intermediates, atomic oxygen, hydrogen, and ammonia and the activity and stability of transition metals for RCC cannot be found, highlighting the need for descriptors beyond those known for CO2R.