Edited by Jean-Michel Savéant, Université Paris Diderot, Paris, France, and approved April 10, 2017 (received for review November 16, 2016)
Anthropogenic global warming necessitates the development of renewable carbon-free and carbon-neutral technologies for the future. Electrochemical CO2 reduction is one such technology that has the potential to impact climate change by enabling sustainable routes for the production of fuels and chemicals. Whereas the field of CO2 reduction has attracted great interest, current state-of-the-art electrocatalysts must be improved in product selectivity and energy efficiency to make this pathway viable for the future. Here, we investigate how controlling the surface structure of copper electrocatalysts can guide CO2 reduction activity and selectivity. We show how the coordination environment of Cu surfaces influences oxygenate vs. hydrocarbon formation, providing insights on how to improve selectivity and energy efficiency toward more valuable CO2 reduction products.
In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C–C coupling than Cu(111), Cu(751) is the most selective for >2e− oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction.
↵1C.H. and T.H. contributed equally to this work.
Author contributions: C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. designed research; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., and S.A.N. performed research; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. analyzed data; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. wrote the paper.
The authors declare no conflict of interest.
This article is a PNAS Direct Submission.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1618935114/-/DCSupplemental.
Edited by Jean-Michel Savéant, Université Paris Diderot, Paris, France, and approved April 10, 2017 (received for review November 16, 2016)
Anthropogenic global warming necessitates the development of renewable carbon-free and carbon-neutral technologies for the future. Electrochemical CO2 reduction is one such technology that has the potential to impact climate change by enabling sustainable routes for the production of fuels and chemicals. Whereas the field of CO2 reduction has attracted great interest, current state-of-the-art electrocatalysts must be improved in product selectivity and energy efficiency to make this pathway viable for the future. Here, we investigate how controlling the surface structure of copper electrocatalysts can guide CO2 reduction activity and selectivity. We show how the coordination environment of Cu surfaces influences oxygenate vs. hydrocarbon formation, providing insights on how to improve selectivity and energy efficiency toward more valuable CO2 reduction products.
In this study we control the surface structure of Cu thin-film catalysts to probe the relationship between active sites and catalytic activity for the electroreduction of CO2 to fuels and chemicals. Here, we report physical vapor deposition of Cu thin films on large-format (∼6 cm2) single-crystal substrates, and confirm epitaxial growth in the <100>, <111>, and <751> orientations using X-ray pole figures. To understand the relationship between the bulk and surface structures, in situ electrochemical scanning tunneling microscopy was conducted on Cu(100), (111), and (751) thin films. The studies revealed that Cu(100) and (111) have surface adlattices that are identical to the bulk structure, and that Cu(751) has a heterogeneous kinked surface with (110) terraces that is closely related to the bulk structure. Electrochemical CO2 reduction testing showed that whereas both Cu(100) and (751) thin films are more active and selective for C–C coupling than Cu(111), Cu(751) is the most selective for >2e− oxygenate formation at low overpotentials. Our results demonstrate that epitaxy can be used to grow single-crystal analogous materials as large-format electrodes that provide insights on controlling electrocatalytic activity and selectivity for this reaction.
↵1C.H. and T.H. contributed equally to this work.
Author contributions: C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. designed research; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., and S.A.N. performed research; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. analyzed data; C.H., T.H., Y.-G.K., A.V., J.H.B., D.C.H., S.A.N., M.P.S., and T.F.J. wrote the paper.
The authors declare no conflict of interest.
This article is a PNAS Direct Submission.
This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1618935114/-/DCSupplemental.
