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Title: Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction

Abstract

The development of low-cost catalysts with oxygen reduction reaction (ORR) activity superior to that of Pt for fuel cells is highly desirable but remains challenging. Herein, we report a bimetal-organic framework (bi-MOF) self-adjusted synthesis of support-free porous Co-N-C nanopolyhedron electrocatalysts by pyrolysis of a Zn/Co bi-MOF without any post-treatments. The presence of initial Zn forms a spatial isolation of Co that suppresses its sintering during pyrolysis, and Zn evaporation also promotes the surface area of the resultant catalysts. The composition, morphology, and hence ORR activity of Co-N-C could be tuned by the Zn/Co ratio. The optimal Co-N-C exhibited remarkable ORR activity with a half-wave potential of 0.871 V versus the reversible hydrogen electrode (RHE) (30 mV more positive than that of commercial 20 wt % Pt/C) and a kinetic current density of 39.3 mA cm -2 at 0.80 V versus RHE (3.1 times that of Pt/C) in 0.1 M KOH, and excellent stability and methanol tolerance. It also demonstrated ORR activity comparable to and stability much higher than those of Pt/C in acidic and neutral electrolytes. Various characterization techniques, including X-ray absorption spectroscopy, revealed that the superior activity and strong stability of Co-N-C originated from the intense interaction between Comore » and N, the high content of ORR active pyridinic and pyrrolic N, and the large specific surface area.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [1]
  1. Utah State Univ., Logan, UT (United States)
  2. Joint Center of Artificial Photosynthesis, Berkeley, CA (United States)
  3. Joint Center of Artificial Photosynthesis, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1397236
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 5; Journal Issue: 12; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; electrocatalyst; metal−organic framework; nonprecious; oxygen reduction; self-adjusted

Citation Formats

You, Bo, Jiang, Nan, Sheng, Meili, Drisdell, Walter S., Yano, Junko, and Sun, Yujie. Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction. United States: N. p., 2015. Web. doi:10.1021/acscatal.5b02325.
You, Bo, Jiang, Nan, Sheng, Meili, Drisdell, Walter S., Yano, Junko, & Sun, Yujie. Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction. United States. doi:10.1021/acscatal.5b02325.
You, Bo, Jiang, Nan, Sheng, Meili, Drisdell, Walter S., Yano, Junko, and Sun, Yujie. Thu . "Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction". United States. doi:10.1021/acscatal.5b02325. https://www.osti.gov/servlets/purl/1397236.
@article{osti_1397236,
title = {Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction},
author = {You, Bo and Jiang, Nan and Sheng, Meili and Drisdell, Walter S. and Yano, Junko and Sun, Yujie},
abstractNote = {The development of low-cost catalysts with oxygen reduction reaction (ORR) activity superior to that of Pt for fuel cells is highly desirable but remains challenging. Herein, we report a bimetal-organic framework (bi-MOF) self-adjusted synthesis of support-free porous Co-N-C nanopolyhedron electrocatalysts by pyrolysis of a Zn/Co bi-MOF without any post-treatments. The presence of initial Zn forms a spatial isolation of Co that suppresses its sintering during pyrolysis, and Zn evaporation also promotes the surface area of the resultant catalysts. The composition, morphology, and hence ORR activity of Co-N-C could be tuned by the Zn/Co ratio. The optimal Co-N-C exhibited remarkable ORR activity with a half-wave potential of 0.871 V versus the reversible hydrogen electrode (RHE) (30 mV more positive than that of commercial 20 wt % Pt/C) and a kinetic current density of 39.3 mA cm-2 at 0.80 V versus RHE (3.1 times that of Pt/C) in 0.1 M KOH, and excellent stability and methanol tolerance. It also demonstrated ORR activity comparable to and stability much higher than those of Pt/C in acidic and neutral electrolytes. Various characterization techniques, including X-ray absorption spectroscopy, revealed that the superior activity and strong stability of Co-N-C originated from the intense interaction between Co and N, the high content of ORR active pyridinic and pyrrolic N, and the large specific surface area.},
doi = {10.1021/acscatal.5b02325},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 12,
volume = 5,
place = {United States},
year = {2015},
month = {10}
}

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Works referencing / citing this record:

Enhanced Electrocatalytic Hydrogen Oxidation on Ni/NiO/C Derived from a Nickel-Based Metal-Organic Framework
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Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019


Enhanced Electrocatalytic Hydrogen Oxidation on Ni/NiO/C Derived from a Nickel-Based Metal-Organic Framework
journal, June 2019

  • Yang, Yang; Sun, Xiaodong; Han, Guanqun
  • Angewandte Chemie International Edition, Vol. 58, Issue 31
  • DOI: 10.1002/anie.201905430

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

  • Yang, Shuliang; Peng, Li; Bulut, Safak
  • Chemistry - A European Journal, Vol. 25, Issue 9
  • DOI: 10.1002/chem.201803157

Achievements, challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation
journal, July 2019