Abstract
The electrochemical CO2 reduction reaction (CO2RR) has progressed but suffers an energy penalty from CO2 loss due to carbonate formation and crossover. Cascade CO2 to CO conversion followed by CO reduction addresses this issue, but the combined figures of carbon efficiency (CE), energy efficiency (EE), selectivity, and stability require improvement. We posited that increased CO availability near active catalytic sites could maintain selectivity even under CO-depleted conditions. Here, we present a heterojunction carbon reservoir catalyst (CRC) architecture that combines copper nanoparticles with porous carbon nanoparticles. The pyridinic and pyrrolic functionalities of CRC can absorb CO enabling high CE under CO-depleted conditions. With CRC catalyst, we achieve ethanol FE and CE of 50% and 93% (CE∗Faradaic efficiency [FE] = 47%) in flow cell at 200 mA cm−2, fully doubling the best prior CE∗FE to ethanol. In membrane electrode assembly (MEA) system, we show sustained efficiency over 85 h at 100 mA cm−2.
Original language | English (US) |
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Pages (from-to) | 2335-2348 |
Number of pages | 14 |
Journal | Joule |
Volume | 7 |
Issue number | 10 |
DOIs | |
State | Published - Oct 18 2023 |
Funding
This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada (number RGPIN-2017-06477 , E. Sargent) and the Ontario Research Fund—Research Excellence Program (number ORF-RE08-034 , E. Sargent). D.S. acknowledges the NSERC E.W.R. Steacie Memorial Fellowship. T.A. acknowledges funding through an NSERC scholarship. I.G. acknowledges the European Union’s Horizon 2020 research and innovation program under Marie Sklodowska-Curie grant (agreement no 846107 ). This research used resources of the European Synchrotron Radiation Facility (ESRF) at beamline ID26 during the experimental session MA5352 ( https://doi.org/10.15151/ESRF-ES-744180074 ). We thank R. Wolowiec and D. Kopilovic for their kind technical assistance, Ontario Centre for the Characterization of Advanced Materials (OCCAM) of the University of Toronto, and the National Synchrotron Radiation Research Center. This work was supported by the Natural Sciences and Engineering Research Council (NSERC) of Canada (number RGPIN-2017-06477, E. Sargent) and the Ontario Research Fund—Research Excellence Program (number ORF-RE08-034, E. Sargent). D.S. acknowledges the NSERC E.W.R. Steacie Memorial Fellowship. T.A. acknowledges funding through an NSERC scholarship. I.G. acknowledges the European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie grant (agreement no 846107). This research used resources of the European Synchrotron Radiation Facility (ESRF) at beamline ID26 during the experimental session MA5352 (https://doi.org/10.15151/ESRF-ES-744180074). We thank R. Wolowiec and D. Kopilovic for their kind technical assistance, Ontario Centre for the Characterization of Advanced Materials (OCCAM) of the University of Toronto, and the National Synchrotron Radiation Research Center. E. Sargent supervised the project. S.P. I.G. and E. Sargent conceived the idea. S.P. and I.G synthesized catalyst, carried out the experiments, and performed characterization. F.B. and J.K. performed N2 and CO adsorption and desorption experiments. I.G. and T.A. performed theoretical calculations. B.-H.L. E. Shirzadi, R.D. G.L. Y.L. A.S.Z. D.S. and D.K. contributed to the manuscript editing. S.P. I.G. T.A. and E. Sargent co-wrote the manuscript. J.A performed in situ XAS measurements. B.-H.L. J.K. E.D.J. and D.K. assisted with the discussions. The authors declare no competing interests.
Keywords
- CO electroreduction
- CO electroreduction
- CO valorization
- carbon monoxide
- carbon utilization
- electrocatalysis
- ethanol
- nitrogen-doped carbon
- porosity control
- renewable fuels
ASJC Scopus subject areas
- General Energy