Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts
Abstract
Ni, N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni, N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO¬2R to CO partial current density increased with increased Ni content before plateauing at 2 wt% which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft x-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.
- Authors:
-
[6];
- Stanford Univ., CA (United States). SUNCAT Center for Interface Science and Catalysis, Dept. of Chemical Engineering
- McMaster Univ., Hamilton, ON (Canada). Dept. of Chemical Engineering
- Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
- Department of Chemical Engineering, McMaster University, Hamilton ON Canada
- SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA 94305 USA
- SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA 94305 USA; SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA 94025 USA
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1592531
- Alternate Identifier(s):
- OSTI ID: 1595507
- Grant/Contract Number:
- AC02-76SF00515; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 10; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, and Jaramillo, Thomas F. Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts. United States: N. p., 2020.
Web. doi:10.1002/anie.201912857.
Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, & Jaramillo, Thomas F. Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts. United States. https://doi.org/10.1002/anie.201912857
Koshy, David M., Chen, Shucheng, Lee, Dong Un, Stevens, Michaela Burke, Abdellah, Ahmed M., Dull, Samuel M., Chen, Gan, Nordlund, Dennis, Gallo, Alessandro, Hahn, Christopher, Higgins, Drew C., Bao, Zhenan, and Jaramillo, Thomas F. Thu .
"Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts". United States. https://doi.org/10.1002/anie.201912857. https://www.osti.gov/servlets/purl/1592531.
@article{osti_1592531,
title = {Understanding the Origin of Highly Selective CO 2 Electroreduction to CO on Ni,N-doped Carbon Catalysts},
author = {Koshy, David M. and Chen, Shucheng and Lee, Dong Un and Stevens, Michaela Burke and Abdellah, Ahmed M. and Dull, Samuel M. and Chen, Gan and Nordlund, Dennis and Gallo, Alessandro and Hahn, Christopher and Higgins, Drew C. and Bao, Zhenan and Jaramillo, Thomas F.},
abstractNote = {Ni, N-doped carbon catalysts have shown promising catalytic performance for CO2 electroreduction (CO2R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni-N bonding and correlating CO2 reduction (CO2R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni, N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO¬2R to CO partial current density increased with increased Ni content before plateauing at 2 wt% which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft x-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal-porphyrin catalysts.},
doi = {10.1002/anie.201912857},
journal = {Angewandte Chemie (International Edition)},
number = 10,
volume = 59,
place = {United States},
year = {Thu Jan 09 00:00:00 EST 2020},
month = {Thu Jan 09 00:00:00 EST 2020}
}
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