High-Nuclearity Copper Molecular Catalysts for Electrocatalytic CO-to-Acetate Conversion
Ligand-modified metal nanoclusters (NCs) have emerged as candidate materials for catalysis owing to their well-defined yet tunable structure and their metal centers' high nuclearity. We posited that NC-based catalytic behavior will depend on ligand properties, the accessibility of active sites, and their atomic configuration. We synthesized a series of Cu NC-based catalysts, tuned local hydrophobicity through ligand adjustment, balanced the ligand coverage and active site exposure, and found that we were, in this way, able to engender efficient electrosynthesis of acetate via CO electroreduction. Computation and operando spectroscopy show that asymmetric Cu-Cu sites, which determine the CO binding strength, impact the bifurcation step after C-C coupling. The best of these catalysts, Cu<sub>13</sub>Nap, achieved an acetate Faradaic efficiency (FE) of 86% and an energy efficiency of 29% in a 5 bar system, exceeding the single C<sub>2+</sub> FE of <50% previously achieved by NC-based catalysts.
Authors
- Yurou Celine Xiao (ORCID: https://orcid.org/0000-0002-5855-5119)
- Mutalifu Abulikemu (ORCID: https://orcid.org/0000-0002-8848-6804)
- Omar F. Mohammed (ORCID: https://orcid.org/0000-0001-8500-1130)
- Osman M. Bakr (ORCID: https://orcid.org/0000-0002-3428-1002)
- Rui Kai Miao (ORCID: https://orcid.org/0000-0002-0542-0683)
- Lizhou Fan (ORCID: https://orcid.org/0000-0002-9398-4875)
- Husam Niman Alshareef (ORCID: https://orcid.org/0000-0001-5029-2142)
- Simil Thomas (ORCID: https://orcid.org/0000-0002-8069-4940)
- Edward Hartley Sargent (ORCID: https://orcid.org/0000-0003-0396-6495)
- Roham Dorakhan (ORCID: https://orcid.org/0000-0001-8104-7174)
- Mohammad Bodiuzzaman (ORCID: https://orcid.org/0000-0002-8316-9359)
- M. Naveen (ORCID: https://orcid.org/0000-0003-2632-6749)
- David Sinton (ORCID: https://orcid.org/0000-0003-2714-6408)
- Yiqing Chen (ORCID: https://orcid.org/0000-0002-2686-5593)
- Yushan Yan (ORCID: https://orcid.org/0000-0001-6616-4575)
- Jinhong Wu (ORCID: https://orcid.org/0000-0002-1554-3599)
- Omar El Tall
Institutions
- Northwestern University (US)
- University of Toronto (CA)
- Renewable Energy Systems (United States) (US)
- King Abdullah University of Science and Technology (SA)
- KTH Royal Institute of Technology (SE)
- Core Laboratories (United States) (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-08-19
- DOI
- https://doi.org/10.1021/jacs.5c08144
- Citations
- 1
- Primary Topic
- CO2 Reduction Techniques and Catalysts
- Type
- article
- Field-Weighted Citation Impact
- 0.36
Funders
- Government of Canada
- King Abdullah University of Science and Technology
- Vetenskapsrådet