Abstract
Multicarbon alcohols produced by electrochemical CO2 reduction (CO2RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO2RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C2+ alcohols. At an industry-relevant current density of 400 mA cm−2, the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C2 intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon. [Figure not available: see fulltext.]
Original language | English (US) |
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Pages (from-to) | 1081-1088 |
Number of pages | 8 |
Journal | Nature Catalysis |
Volume | 5 |
Issue number | 12 |
DOIs | |
State | Published - Dec 2022 |
Funding
This work was financially supported by Suncor Energy, the Natural Sciences and Engineering Research Council (NSERC) of Canada and the CIFAR Bio-Inspired Solar Energy program. S.-F.H. acknowledges support from the Ministry of Science and Technology, Taiwan (contract nos MOST 110-2113-M-009-007-MY2, MOST 110-2628-M-A49-002 and MOST 111-2628-M-A49-007) and from the Yushan Young Scholar Program, Ministry of Education, Taiwan. This research used the synchrotron resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357. The authors thank T. Wu and G. Sterbinsky for technical support at the 9BM beamline of the APS. All DFT computations were performed on the Niflheim supercomputer at the Department of Physics, Technical University of Denmark. This work was financially supported by Suncor Energy, the Natural Sciences and Engineering Research Council (NSERC) of Canada and the CIFAR Bio-Inspired Solar Energy program. S.-F.H. acknowledges support from the Ministry of Science and Technology, Taiwan (contract nos MOST 110-2113-M-009-007-MY2, MOST 110-2628-M-A49-002 and MOST 111-2628-M-A49-007) and from the Yushan Young Scholar Program, Ministry of Education, Taiwan. This research used the synchrotron resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357. The authors thank T. Wu and G. Sterbinsky for technical support at the 9BM beamline of the APS. All DFT computations were performed on the Niflheim supercomputer at the Department of Physics, Technical University of Denmark.
ASJC Scopus subject areas
- Catalysis
- Bioengineering
- Biochemistry
- Process Chemistry and Technology