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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:
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. 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, and Dai, Hongjie. Wed . "Highly active oxygen evolution integrated with efficient CO2 to CO electroreduction". United States. doi:10.1073/pnas.1915319116.
@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},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = [48],
volume = [116],
place = {United States},
year = {2019},
month = {11}
}

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