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Lattice-Hydride Mechanism in Electrocatalytic CO2 Reduction by Structurally Precise Copper-Hydride Nanoclusters
- Source :
- Journal of the American Chemical Society. 139:9728-9736
- Publication Year :
- 2017
- Publisher :
- American Chemical Society (ACS), 2017.
-
Abstract
- Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of CO2 reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is a dithiophosphate ligand), offer unique selectivity for electrocatalytic CO2 reduction at low overpotentials. Our density functional theory (DFT) calculations predict that the presence of the negatively charged hydrides in the copper cluster plays a critical role in determining the selectivity of the reduction product, yielding HCOOH over CO with a lower overpotential. The HCOOH formation proceeds via the lattice-hydride mechanism: first, surface hydrides reduce CO2 to HCOOH product, and then the hydride vacancies are readily regenerated by the electrochemical proton reduction. DFT calculations further predict that hydrogen evolution is less competitive than HCOOH formation at the low overpotential. Confirming the pr...
- Subjects :
- Hydride
Inorganic chemistry
chemistry.chemical_element
02 engineering and technology
General Chemistry
Overpotential
010402 general chemistry
021001 nanoscience & nanotechnology
Electrochemistry
Photochemistry
01 natural sciences
Biochemistry
Copper
Catalysis
0104 chemical sciences
Nanoclusters
chemistry.chemical_compound
Colloid and Surface Chemistry
chemistry
Copper hydride
Density functional theory
0210 nano-technology
Selectivity
Subjects
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 139
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi...........d153a31a9274eb8747c666390444ec98