Abstract
Electrochemical reduction of CO2 (CO2ER) has the potential to advance carbon neutrality and renewable energy storage. Advanced CO2ER catalysts can selectively produce a wide array of products. Their importance is amplified when coreducing CO2 with nitrate/nitrite ions (NO3-/NO2-) to generate organic compounds containing C-N bonds, enhancing product diversity and value. Some transition metals effectively catalyze the coreduction of CO2 and NO3-/NO2- to yield urea. However, a disparity exists between the experimental observations that underscore the significance of CO production in urea synthesis and the theoretical perspectives that dismiss the role of CO in C-N bond creation. To reconcile this disparity, we utilized density functional theory combined with a constant electrode potential model to investigate four facile CO2 + *N1 (the intermediates from NO3-/NO2- reduction to NH3) couplings─representing the primary C-N formation pathways on a range of transition metal surfaces. Our comprehensive study elucidates the relationships among C-N coupling barriers, *N1, and CO adsorption energies. Notably, we found that while CO is not involved in C-N formation, a catalyst’s proficiency in generating CO from CO2ER is indicative of its reduced adsorption strength. This result indicates a heightened reactivity in forming C-N bonds via the CO2 + *N1 couplings. Our theoretical exploration adeptly bridges the discrepancies observed between earlier experimental and theoretical studies.
Original language | English |
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Pages (from-to) | 1058-1067 |
Number of pages | 10 |
Journal | Journal of Physical Chemistry C |
Volume | 128 |
Issue number | 3 |
DOIs | |
Publication status | Published - 2024 Jan 25 |
All Science Journal Classification (ASJC) codes
- Electronic, Optical and Magnetic Materials
- General Energy
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films