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Molecular tuning of CO₂-to-ethylene conversion

Li, Fengwang and Thevenon, Arnaud and Rosas-Hernández, Alonso and Han, Zhiji and Agapie, Theodor and Peters, Jonas C. (2020) Molecular tuning of CO₂-to-ethylene conversion. Nature, 577 (7791). pp. 509-513. ISSN 0028-0836. https://resolver.caltech.edu/CaltechAUTHORS:20190917-154117893

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Abstract

The electrocatalytic carbon dioxide (CO₂) reduction reaction (CO₂RR) to value-added fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of intermittent renewable electricity. The highly selective generation of economically desirable C₂ products such as ethylene from CO₂RR remains a challenge. Tuning the stabilities of intermediates to favour a desired reaction pathway offers the opportunity to enhance selectivity, and this has recently been explored on copper (Cu) via control over morphology, grain boundaries7, facets, oxidation state and dopants. Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 mA cm⁻² in the best catalyst reported so far), resulting in a low energy efficiency. Here we present a molecular tuning strategy—the functionalization of the surface of electrocatalysts with organic molecules—that stabilizes intermediates for enhanced CO₂RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived via electro-dimerization of arylpyridiniums, on Cu. We find that the adhered molecules improve the stabilization of an atop-bound CO intermediate, thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO₂RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 mA cm⁻² in a liquid-electrolyte flow cell in neutral medium. We report stable ethylene electrosynthesis for 190 hours in a membrane-electrode-assembly-based system that provides a full-cell energy efficiency of 20 per cent. These findings indicate how molecular strategies can complement heterogeneous catalysts by stabilizing intermediates via local molecular tuning.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1038/s41586-019-1782-2DOIArticle
https://rdcu.be/b0ScGPublisherFree ReadCube access
ORCID:
AuthorORCID
Li, Fengwang0000-0003-1531-2966
Thevenon, Arnaud0000-0002-5543-6595
Rosas-Hernández, Alonso0000-0002-0812-5591
Han, Zhiji0000-0001-9349-1571
Agapie, Theodor0000-0002-9692-7614
Peters, Jonas C.0000-0002-6610-4414
Alternate Title:Intermediate stabilization via molecular tuning for CO₂-to-ethylene conversion
Additional Information:© 2019 Springer Nature Limited. Received 21 December 2018; Accepted 01 October 2019; Published 20 November 2019. This work was financially supported by the Ontario Research Fund: Research Excellence Program, the Natural Sciences and Engineering Research Council (NSERC) of Canada, the CIFAR Bio-Inspired Solar Energy program, and the Joint Centre of Artificial Synthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP). SOSCIP is funded by the Federal Economic Development Agency of Southern Ontario, the Province of Ontario, IBM Canada Ltd., Ontario Centres of Excellence, Mitacs and 15 Ontario academic member institutions. This research was enabled in part by support provided by Compute Ontario (www.computeontario.ca) and Compute Canada (www.computecanada.ca). This research used synchrotron resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, and the Canadian Light Source and its funding partners. We thank T. Wu and L. Ma for technical support at 9BM beamline of APS. D.S. acknowledges the NSERC E.W.R Steacie Memorial Fellowship. A.T. acknowledges Marie Skłodowska-Curie Fellowship H2020-MSCA-IF-2017 (793471). J.L. acknowledges the Banting postdoctoral fellowship. C.M.G. acknowledges NSERC for funding in the form of a postdoctoral fellowship from the government of Canada. J.P.E. thanks NSERC, Hatch and the Government of Ontario for their support through graduate scholarships. Author contributions: E.H.S., T.A. and J.C.P. supervised this project. F.L. and Y.L. carried out electrochemical experiments. A.T. and A.R.H. carried out molecule synthesis and characterizations. Z.W. carried out DFT calculations. C.M.G. and F.L. conducted in situ Raman measurement. F.L. and A.O. carried out the membrane-electrode-assembly experiments. J. L. and F.L. performed X-ray spectroscopy measurements. Y.W. carried out SEM and EIS measurements. J.P.E. measured the contact angle. C.M. carried out the Comsol modelling. L.T. carried out EPR measurement under the supervision of R.D.B.. M.L. performed part of electrochemical experiments. Z. Q. L., X.W. and H.L. provided help in NMR analysis. C.M.G., C.P.O. and Y.X. provided help in membrane-electrode-assembly measurements. C.S.T. carried out AFM measurement. D.H.N. conducted XRD measurement. R.Q.B. carried out XPS measurement. C.T.D., T.Z, Y.C.L. and Z.H. provided help in materials synthesis and characterizations. F.L. and E.H.S. wrote the manuscript. All authors discussed the results and assisted during manuscript preparation. The authors declare no competing interests.
Group:JCAP
Funders:
Funding AgencyGrant Number
Ontario Research Fund-Research ExcellenceUNSPECIFIED
Natural Sciences and Engineering Research Council of Canada (NSERC)UNSPECIFIED
Canadian Institute for Advanced Research (CIFAR)UNSPECIFIED
Joint Center for Artificial Photosynthesis (JCAP)UNSPECIFIED
Department of Energy (DOE)DE-SC0004993
Federal Economic Development Agency of Southern OntarioUNSPECIFIED
Province of OntarioUNSPECIFIED
IBM Canada Ltd.UNSPECIFIED
MITACSUNSPECIFIED
Compute OntarioUNSPECIFIED
Compute CanadaUNSPECIFIED
Department of Energy (DOE)DE-AC02-06CH11357
Canadian Light SourceUNSPECIFIED
Marie Curie FellowshipH2020-MSCA-IF-2017
European Research Council (ERC)793471
Subject Keywords:Catalysis; Renewable energy
Issue or Number:7791
Record Number:CaltechAUTHORS:20190917-154117893
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190917-154117893
Official Citation:Li, F., Thevenon, A., Rosas-Hernández, A. et al. Molecular tuning of CO2-to-ethylene conversion. Nature 577, 509–513 (2020). https://doi.org/10.1038/s41586-019-1782-2
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:98698
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:20 Nov 2019 18:29
Last Modified:28 Jan 2020 18:47

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