Electrochemical CO2 and CO reduction on oxide-derived copper catalysts
Abstract/Contents
- Abstract
- The recycling of CO2 to liquid fuel using renewable energy is a longstanding problem that has been stymied by the lack of efficient electrocatalysts for this reaction. We demonstrate here that the reduction of metal oxide layers to generate "oxide-derived nanocrystalline metals" is a general method to increase the energetic efficiency of CO2 reduction and suppress the competitive H2 evolution reaction. Copper is the only metal with appreciable CO electroreduction activity, but requires extreme overpotentials to reduce CO in preference to H2O. Oxide-derived Cu (OD-Cu) lowers this overpotential requirement by at least 500 mV, producing ethanol and acetate with a combined Faradaic efficiency of 57% at --0.3 V vs the reversible hydrogen electrode. Commercial Cu nanoparticles of the same size and morphology exhibit very low selectivity for CO reduction under identical conditions, implicating the participation of surface defects or grain boundaries in the catalysis on oxide-derived nanocrystalline Cu. Using TEM electron diffraction and temperature-programmed desorption, we build grain boundary structure-activity relationships and probe the adsorption energy of CO to the oxide-derived Cu surface. Based on these data, we hypothesize that grain boundary surfaces provide active sites that bind CO more strongly than conventional Cu terrace or stepped facets, and these active sites are implicated in CO reduction catalysis.
Description
| Type of resource | text |
|---|---|
| Form | electronic; electronic resource; remote |
| Extent | 1 online resource. |
| Publication date | 2015 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Associated with | Li, Christina W |
|---|---|
| Associated with | Stanford University, Department of Chemistry. |
| Primary advisor | Kanan, Matthew William, 1978- |
| Thesis advisor | Kanan, Matthew William, 1978- |
| Thesis advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Thesis advisor | Stack, T. (T. Daniel P.), 1959- |
| Advisor | Chidsey, Christopher E. D. (Christopher Elisha Dunn) |
| Advisor | Stack, T. (T. Daniel P.), 1959- |
Subjects
| Genre | Theses |
|---|
Bibliographic information
| Statement of responsibility | Christina W. Li. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis (Ph.D.)--Stanford University, 2015. |
| Location | electronic resource |
Access conditions
- Copyright
- © 2015 by Christina Wenshin Li
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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