Valence Band Tuning of Electrocatalysts for the CO2 Reduction Reaction

ended

Electrochemical carbon dioxide reduction is a promising technology for producing carbon-neutral fuels and chemicals using renewable electricity. Unfortunately, contemporary electrocatalysts lack the activity required to make the process commercially viable. The search for electrocatalysts with superior activity has been hindered by the fact that the electrocatalyst properties required to reduce carbon dioxide have not been definitively identified. Herein, I propose to utilize the d-band structure of a transition metal electrocatalysts as a descriptor for its electrocatalytic activity. The d-band structure of transition metals normally incapable of carbon dioxide reduction will be tuned to resemble those of known electrocatalysts via the formation of strong intermetallic bonds with ionic character. These intermetallic electrocatalysts will be synthesized in a thin film format and transferred into an ultra-high vacuum system where they will be pretreated, characterized, and tested in an inert and integrated environment, enabling the systematic elucidation of the impact of d-band structure on carbon dioxide reduction activity. Following this approach, novel electrocatalysts will be discovered with superior activity to the state-of-the-art electrocatalysts. Once promising intermetallic alloys are identified, their activity will be quantified as a function of their surface atomic density via epitaxial intermetallic thin film growth on crystallographically oriented Si wafers. If undercoordinated surfaces exhibit superior electrocatalytic activity, intermetallic mass-selected nanoparticles will be synthesized and their activity quantified as a function of partizle size. Thus, the proposed research project aims to develope a fundamental understanding of the electrocatalysts properties required to reduce carbon dioxide and exploit these insights to develope superior electrocatalysts that could be immediately employed in working devices.