skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Highly active oxygen evolution integrated with efficient CO 2 to CO electroreduction

Abstract

Electrochemical reduction of CO 2to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO 2reduction reaction (CO 2RR) at a cathode is always paired with the oxygen evolution reaction (OER) at an anode, the overall efficiency of electrical energy to chemical fuel conversion must consider the large energy barrier and sluggish kinetics of OER, especially in widely used electrolytes, such as the pH-neutral CO 2-saturated 0.5 M KHCO 3. OER in such electrolytes mostly relies on noble metal (Ir- and Ru-based) electrocatalysts in the anode. Here, we discover that by anodizing a metallic Ni–Fe composite foam under a harsh condition (in a low-concentration 0.1 M KHCO 3solution at 85 °C under a high-current ~250 mA/cm 2), OER on the NiFe foam is accompanied by anodic etching, and the surface layer evolves into a nickel–iron hydroxide carbonate (NiFe-HC) material composed of porous, poorly crystalline flakes of flower-like NiFe layer-double hydroxide (LDH) intercalated with carbonate anions. The resulting NiFe-HC electrode in CO 2-saturated 0.5 M KHCO 3exhibited OER activity superior to IrO 2, with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm 2, respectively, and highmore » stability for >120 h without decay. We paired NiFe-HC with a CO 2 RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO 2 electrolyzer, achieving selective cathodic conversion of CO 2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O 2. The device showed a low cell voltage of 2.13 V and high electricity-to-chemical fuel efficiency of 59% at a current density of 10 mA/cm 2.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [6];  [7];  [8];  [8];  [9];  [4];  [10];  [11];  [6]
  1. Shandong Univ. of Science and Technology, Qingdao (China). College of Electrical Engineering and Automation; Stanford Univ., Stanford, CA (United States). Dept. of Chemistry
  2. Stanford Univ., Stanford, CA (United States). Dept. of Chemistry; South Univ. of Science and Technology of China, Shenzhen (China). Dept. of Materials Science and Engineering
  3. Stanford Univ., Stanford, CA (United States). Dept. of Chemistry; National Central Univ., Taoyuan (Taiwan). Inst. of Materials Science and Engineering
  4. Univ. of Connecticut, Storrs, CT (United States). Inst. of Materials Science
  5. National Central Univ., Taoyuan (Taiwan). Inst. of Materials Science and Engineering
  6. Stanford Univ., Stanford, CA (United States). Dept. of Chemistry
  7. Academia Sinica, Taipei (Taiwan)
  8. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  9. Stanford Univ., CA (United States)
  10. Shandong Univ. of Science and Technology, Qingdao (China). College of Electrical Engineering and Automation
  11. South Univ. of Science and Technology of China, Shenzhen (China). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Connecticut, Storrs, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1596288
Alternate Identifier(s):
OSTI ID: 1598226
Grant/Contract Number:  
AC02-76SF00515; MOST-106-2918-I-035-002; FG02-86ER13622
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 116; Journal Issue: 48; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxygen evolution; CO2 reduction; CO2 electrolyzer; electrocatalysis; pH-neutral electrolyte

Citation Formats

Meng, Yongtao, Zhang, Xiao, Hung, Wei-Hsuan, He, Junkai, Tsai, Yi-Sheng, Kuang, Yun, Kenney, Michael J., Shyue, Jing-Jong, Liu, Yijin, Stone, Kevin H., Zheng, Xueli, Suibe, Steven L., Lin, Meng-Chang, Liang, Yongye, and Dai, Hongjie. Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction. United States: N. p., 2019. Web. doi:10.1073/pnas.1915319116.
Meng, Yongtao, Zhang, Xiao, Hung, Wei-Hsuan, He, Junkai, Tsai, Yi-Sheng, Kuang, Yun, Kenney, Michael J., Shyue, Jing-Jong, Liu, Yijin, Stone, Kevin H., Zheng, Xueli, Suibe, Steven L., Lin, Meng-Chang, Liang, Yongye, & Dai, Hongjie. Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction. United States. https://doi.org/10.1073/pnas.1915319116
Meng, Yongtao, Zhang, Xiao, Hung, Wei-Hsuan, He, Junkai, Tsai, Yi-Sheng, Kuang, Yun, Kenney, Michael J., Shyue, Jing-Jong, Liu, Yijin, Stone, Kevin H., Zheng, Xueli, Suibe, Steven L., Lin, Meng-Chang, Liang, Yongye, and Dai, Hongjie. Wed . "Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction". United States. https://doi.org/10.1073/pnas.1915319116. https://www.osti.gov/servlets/purl/1596288.
@article{osti_1596288,
title = {Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction},
author = {Meng, Yongtao and Zhang, Xiao and Hung, Wei-Hsuan and He, Junkai and Tsai, Yi-Sheng and Kuang, Yun and Kenney, Michael J. and Shyue, Jing-Jong and Liu, Yijin and Stone, Kevin H. and Zheng, Xueli and Suibe, Steven L. and Lin, Meng-Chang and Liang, Yongye and Dai, Hongjie},
abstractNote = {Electrochemical reduction of CO2to useful chemicals has been actively pursued for closing the carbon cycle and preventing further deterioration of the environment/climate. Since CO2reduction reaction (CO2RR) at a cathode is always paired with the oxygen evolution reaction (OER) at an anode, the overall efficiency of electrical energy to chemical fuel conversion must consider the large energy barrier and sluggish kinetics of OER, especially in widely used electrolytes, such as the pH-neutral CO2-saturated 0.5 M KHCO3. OER in such electrolytes mostly relies on noble metal (Ir- and Ru-based) electrocatalysts in the anode. Here, we discover that by anodizing a metallic Ni–Fe composite foam under a harsh condition (in a low-concentration 0.1 M KHCO3solution at 85 °C under a high-current ~250 mA/cm2), OER on the NiFe foam is accompanied by anodic etching, and the surface layer evolves into a nickel–iron hydroxide carbonate (NiFe-HC) material composed of porous, poorly crystalline flakes of flower-like NiFe layer-double hydroxide (LDH) intercalated with carbonate anions. The resulting NiFe-HC electrode in CO2-saturated 0.5 M KHCO3exhibited OER activity superior to IrO2, with an overpotential of 450 and 590 mV to reach 10 and 250 mA/cm2, respectively, and high stability for >120 h without decay. We paired NiFe-HC with a CO2 RR catalyst of cobalt phthalocyanine/carbon nanotube (CoPc/CNT) in a CO2 electrolyzer, achieving selective cathodic conversion of CO2 to CO with >97% Faradaic efficiency and simultaneous anodic water oxidation to O2. The device showed a low cell voltage of 2.13 V and high electricity-to-chemical fuel efficiency of 59% at a current density of 10 mA/cm2.},
doi = {10.1073/pnas.1915319116},
url = {https://www.osti.gov/biblio/1596288}, journal = {Proceedings of the National Academy of Sciences of the United States of America},
issn = {0027-8424},
number = 48,
volume = 116,
place = {United States},
year = {2019},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Electrochemical CO 2 Reduction: Recent Advances and Current Trends
journal, September 2014


Effect of interlayer anions on [NiFe]-LDH nanosheet water oxidation activity
journal, January 2016


Tunable Cu Enrichment Enables Designer Syngas Electrosynthesis from CO 2
journal, June 2017


An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen
journal, August 2013


Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption
journal, November 2017


Electrocatalytic Production of C3-C4 Compounds by Conversion of CO 2 on a Chloride-Induced Bi-Phasic Cu 2 O-Cu Catalyst
journal, October 2015


Nickel–iron hydroxide carbonate precursors in the synthesis of high-dispersity oxides
journal, January 1994


Anodized Indium Metal Electrodes for Enhanced Carbon Dioxide Reduction in Aqueous Electrolyte
journal, June 2014


An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation
journal, May 2013


Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting
journal, January 2015


Characterization of the Cell–Nanopillar Interface by Transmission Electron Microscopy
journal, October 2012


Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics
journal, June 2015


Infrared and Raman study of interlayer anions CO 3 2− , NO 3 , SO 4 2− and ClO 4 in Mg/Al-hydrotalcite
journal, May 2002


Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction
journal, February 2018


Highly selective plasma-activated copper catalysts for carbon dioxide reduction to ethylene
journal, June 2016


Formation of hydrocarbons in the electrochemical reduction of carbon dioxide at a copper electrode in aqueous solution
journal, January 1989

  • Hori, Yoshio; Murata, Akira; Takahashi, Ryutaro
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 8
  • https://doi.org/10.1039/f19898502309

Degree of Geometric Tilting Determines the Activity of FeO 6 Octahedra for Water Oxidation
journal, June 2018


IrO x /CN x NTs as electrocatalysts for oxygen evolution reaction in a HCO3 −/CO2 system at neutral pH
journal, December 2017


Structure–Activity Correlations in a Nickel–Borate Oxygen Evolution Catalyst
journal, April 2012

  • Bediako, D. Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 134, Issue 15
  • https://doi.org/10.1021/ja301018q

Importance of Ag–Cu Biphasic Boundaries for Selective Electrochemical Reduction of CO 2 to Ethanol
journal, November 2017


Non-3d Metal Modulation of a Cobalt Imidazolate Framework for Excellent Electrocatalytic Oxygen Evolution in Neutral Media
journal, December 2018


Tin Oxide Dependence of the CO 2 Reduction Efficiency on Tin Electrodes and Enhanced Activity for Tin/Tin Oxide Thin-Film Catalysts
journal, January 2012


Aqueous CO 2 Reduction at Very Low Overpotential on Oxide-Derived Au Nanoparticles
journal, November 2012


Ni-Based Electrocatalyst for Water Oxidation Developed In-Situ in a HCO 3 /CO 2 System at Near-Neutral pH
journal, March 2014


Achieving Selective and Efficient Electrocatalytic Activity for CO 2 Reduction Using Immobilized Silver Nanoparticles
journal, October 2015