Mechanism of C-N bonds formation in electrocatalytic urea production revealed by ab initio molecular dynamics simulation

Electrosynthesis of urea from CO2 and NOX provides an exceptional opportunity for human society, given the increasingly available renewable energy. To raise the overall electrosynthesis efficiency, the most critical reaction step for such electrosynthesis, C-N coupling, needs to be significantly improved. The C-N coupling can only happen at a narrow potential window, generally in the low overpotential region, and a fundamental understanding of the C-N coupling is needed for further development of this strategy. In this regard, we performed ab initio Molecular Dynamics (AIMD) simulations to reveal the origin of C-N coupling under a small electrode potential window with both the dynamic nature of water as a solvent, and the electrode potentials considered. We explored the key reaction networks for urea formation on Cu(100) surface in neutral electrolytes. Our work shows excellent agreement with experimentally observed selectivity under different potentials on the Cu electrode. We discovered that the NH and CO are the key precursors for C-N bonds formation at low overpotential, while at high overpotential the C-N coupling occurs between adsorbed *NH and solvated CO. These insights provide vital information for future spectroscopic measurements and enable us to design new electrochemical systems for more value-added chemicals.

Identifier
Source https://archive.materialscloud.org/record/2022.120
Metadata Access https://archive.materialscloud.org/xml?verb=GetRecord&metadataPrefix=oai_dc&identifier=oai:materialscloud.org:1463
Provenance
Creator Liu, Xin; Jiao, Yan; Zheng, Yao; Jaroniec, Mietek; Qiao, Shi-Zhang
Publisher Materials Cloud
Publication Year 2022
Rights info:eu-repo/semantics/openAccess; Creative Commons Attribution 4.0 International https://creativecommons.org/licenses/by/4.0/legalcode
OpenAccess true
Contact archive(at)materialscloud.org
Representation
Language English
Resource Type Dataset
Discipline Materials Science and Engineering