TY - JOUR
T1 - Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction
AU - Esmaeilirad, Mohammadreza
AU - Baskin, Artem
AU - Kondori, Alireza
AU - Sanz-Matias, Ana
AU - Qian, Jin
AU - Song, Boao
AU - Tamadoni Saray, Mahmoud
AU - Kucuk, Kamil
AU - Belmonte, Andres Ruiz
AU - Delgado, Pablo Navarro Munoz
AU - Park, Junwon
AU - Azari, Rahman
AU - Segre, Carlo U.
AU - Shahbazian-Yassar, Reza
AU - Prendergast, David
AU - Asadi, Mohammad
N1 - Funding Information:
Mohammad Asadi’s work was supported by Illinois Institute of Technology start-up funding, Wanger Institute for Sustainable Energy Research (WISER) Institute for Sustainable Energy Research (WISER) seed fund (262029 221E 2300), American Institute of Architects (AIA) Upjohn Development Research Grant (387523 240 M 2301) and the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-152205) funding at Northwestern University. This work was also supported by the Molecular Foundry and its compute cluster (vulcan), managed by the High-Performance Computing Services Group, at Lawrence Berkeley National Laboratory (LBNL), and by the National Energy Research Scientific Computing Center (NERSC) at LBNL. LBML resources are provided by the Office of Science of the US Department of Energy under contract No. DE-AC02-05CH11231. Reza Shahbazian-Yassar efforts were supported by NSF (DMR-1809439). We acknowledge the EPIC facility (NUANCE Center, North-western University), which has received support from the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the Nanoscale Science and Engineering Center (NSF EEC−0647560) at the International Institute for Nanotechnology; and the State of Illinois, through the International Institute for Nanotechnology. The authors acknowledge Dr. Rao Tatavarti from Micro-Link Device, Inc. at Chicago for providing the triple junction PV cell. This work made use of instruments in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM200CF was supported by an MRI-R2 grant from the National Science Foundation (Award No. DMR-0959470).
Publisher Copyright:
© 2021, The Author(s).
PY - 2021/12/1
Y1 - 2021/12/1
N2 - An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO2RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO2RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH4) current density of −421.63 mA/cm2 and a CH4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W2C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO2 to produce CH4 in a 700-h process under one sun illumination with a CO2RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.
AB - An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO2RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO2RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH4) current density of −421.63 mA/cm2 and a CH4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W2C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO2 to produce CH4 in a 700-h process under one sun illumination with a CO2RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO2 and cleavage of the C-O bond—the most energy consuming elementary steps in other catalysts such as copper—become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO—an important reaction intermediate—and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.
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U2 - 10.1038/s41467-021-25295-y
DO - 10.1038/s41467-021-25295-y
M3 - Article
C2 - 34417447
AN - SCOPUS:85113203520
VL - 12
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 5067
ER -