Abstract
The electroreduction of C1 feedgas to high-energy-density fuels provides an attractive avenue to the storage of renewable electricity. Much progress has been made to improve selectivity to C1 and C2 products, however, the selectivity to desirable high-energy-density C3 products remains relatively low. We reason that C3 electrosynthesis relies on a higher-order reaction pathway that requires the formation of multiple carbon-carbon (C-C) bonds, and thus pursue a strategy explicitly designed to couple C2 with C1 intermediates. We develop an approach wherein neighboring copper atoms having distinct electronic structures interact with two adsorbates to catalyze an asymmetric reaction. We achieve a record n-propanol Faradaic efficiency (FE) of (33 ± 1)% with a conversion rate of (4.5 ± 0.1) mA cm−2, and a record n-propanol cathodic energy conversion efficiency (EEcathodic half-cell) of 21%. The FE and EEcathodic half-cell represent a 1.3× improvement relative to previously-published CO-to-n-propanol electroreduction reports.
| Original language | English |
|---|---|
| Article number | 5186 |
| Journal | Nature Communications |
| Volume | 10 |
| Issue number | 1 |
| DOIs | |
| State | Published - Dec 1 2019 |
Funding
This work was 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 University of Toronto Connaught grant. The STEM imaging part of this research was completed at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. Synchrotron measurements were carried out at APS, an Office of Science User Facility operated for U.S. DOE Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, the Canadian Light Source and its funding partners, and CMS beamline of the National Synchrotron Light Source II, a U.S. DOE Office of the Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory. All DFT computations were performed on the IBM BlueGene/Q supercomputer with support from the Southern Ontario Smart Computing Innovation Platform (SOSCIP) and Niagara supercomputer at the SciNet HPC Consortium. 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. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, Ontario Research Fund - Research Excellence, and the University of Toronto. J.L. acknowledges the Banting Postdoctoral Fellowships Program and the receipt of support from the CLSI Graduate and Post-Doctoral Student Travel Support Program. The authors thank T.P.W., Y.Z.F., L.M., and G.S. for technical support at the 9BM beamline of APS. C. M.G. acknowledges support from NSERC in the form of a postdoctoral fellowship. A.R.K. and L.J.R. would like to thank R.L. and M.F. for their assistance in WAXS measurements.
| Funders | Funder number |
|---|---|
| CIFAR Bio-Inspired Solar Energy program | |
| CLSI | |
| DOE Office of Science | |
| DOE Office of the Science User Facility operated | |
| Federal Economic Development Agency of Southern Ontario | |
| National Synchrotron Light Source II | |
| Office of Science User Facility operated | |
| Ontario Research Fund Research-Excellence Program | |
| U.S. DOE | DE-AC02-06CH11357 |
| U.S. DOE Office of the Science User Facility | |
| Argonne National Laboratory | |
| Brookhaven National Laboratory | |
| Canadian Light Source | |
| Academy of Pharmaceutical Sciences | |
| Ontario Research Foundation | |
| IBM Canada | |
| Natural Sciences and Engineering Research Council of Canada | |
| Canadian Mathematical Society | |
| Toronto Rehab, University of Toronto | |
| Canada Foundation for Innovation | |
| University of Toronto | |
| Canada First Research Excellence Fund |