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

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)
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. https://doi.org/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. https://doi.org/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},
url = {https://www.osti.gov/biblio/1397236}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 12,
volume = 5,
place = {United States},
year = {2015},
month = {10}
}

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

Citation Metrics:
Cited by: 145 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019


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


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


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


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


High-performance fuel cell cathodes exclusively containing atomically dispersed iron active sites
journal, January 2019


Multifunctional Mo-N/C@MoS 2 Electrocatalysts for HER, OER, ORR, and Zn-Air Batteries
journal, September 2017


From 3D ZIF Nanocrystals to Co-N x /C Nanorod Array Electrocatalysts for ORR, OER, and Zn-Air Batteries
journal, November 2017


Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal-Organic Frameworks
journal, December 2016


Strategies for Improving the Functionality of Zeolitic Imidazolate Frameworks: Tailoring Nanoarchitectures for Functional Applications
journal, August 2017


Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis
journal, November 2017


Complex Nanostructures from Materials based on Metal-Organic Frameworks for Electrochemical Energy Storage and Conversion
journal, September 2017


Metal-Organic Frameworks as Platforms for Catalytic Applications
journal, November 2017


Metal Organic Framework Derived Materials: Progress and Prospects for the Energy Conversion and Storage
journal, July 2018


Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells
journal, January 2018


Iron‐Free Cathode Catalysts for Proton‐Exchange‐Membrane Fuel Cells: Cobalt Catalysts and the Peroxide Mitigation Approach
journal, December 2018


Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction
journal, December 2018


Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals
journal, November 2019


Proliferating Oxygen Reduction Reaction by High Volume of Mesopores in Regular Nickel–Nitrogen Codoped Carbon Nanocubes
journal, August 2019


Advanced Hierarchical Vesicular Carbon Co-Doped with S, P, N for High-Rate Sodium Storage
journal, May 2018


Enhanced Hydrogenation Performance over Hollow Structured Co‐CoO x @N‐C Capsules
journal, September 2019


Metal-Organic Framework-Derived Non-Precious Metal Nanocatalysts for Oxygen Reduction Reaction
journal, May 2017


Design Strategies toward Advanced MOF-Derived Electrocatalysts for Energy-Conversion Reactions
journal, June 2017


Alkaline-Acid Zn-H 2 O Fuel Cell for the Simultaneous Generation of Hydrogen and Electricity
journal, January 2018


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


Nitrogen, Phosphorus, and Sulfur Co-Doped Hollow Carbon Shell as Superior Metal-Free Catalyst for Selective Oxidation of Aromatic Alkanes
journal, February 2016


Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016


Cobalt and Nitrogen Codoped Carbon Nanosheets Templated from NaCl as Efficient Oxygen Reduction Electrocatalysts
journal, September 2018


Recent Approaches to Design Electrocatalysts Based on Metal–Organic Frameworks and Their Derivatives
journal, September 2019


Recent Progress of Carbon-Based Materials in Oxygen Reduction Reaction Catalysis
journal, January 2018


Bimetal/Metal Oxide Encapsulated in Graphitic Nitrogen Doped Mesoporous Carbon Networks for Enhanced Oxygen Electrocatalysis
journal, January 2019


Key Single-Atom Electrocatalysis in Metal-Organic Framework (MOF)-Derived Bifunctional Catalysts
journal, August 2018


Microporous Solids En Route to Heterogeneous Electrocatalysis: The Oxygen Reduction Reaction
journal, December 2019


Metal–Organic Frameworks for Electrocatalysis
book, January 2020


Strategies for Enhancing the Electrocatalytic Activity of M–N/C Catalysts for the Oxygen Reduction Reaction
journal, May 2018


Metal-organic framework based nanomaterials for electrocatalytic oxygen redox reaction
journal, March 2019


Metal–Organic Frameworks (MOFs) and MOF-Derived Materials for Energy Storage and Conversion
journal, November 2018


Switching effective oxygen reduction and evolution performance by controlled graphitization of a cobalt–nitrogen–carbon framework system
journal, January 2016


Advancements in rationally designed PGM-free fuel cell catalysts derived from metal–organic frameworks
journal, January 2017


Recent advances in air electrodes for Zn–air batteries: electrocatalysis and structural design
journal, January 2017


Metal organic frameworks as precursors for the manufacture of advanced catalytic materials
journal, January 2017


In situ directional formation of Co@CoO x -embedded 1D carbon nanotubes as an efficient oxygen electrocatalyst for ultra-high rate Zn–air batteries
journal, January 2017


Hierarchically porous Fe–N–C nanospindles derived from a porphyrinic coordination network for oxygen reduction reaction
journal, January 2018


Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy
journal, January 2019


Multi-heteroatom doped graphene-like carbon nanospheres with 3D inverse opal structure: a promising bisphenol-A remediation material
journal, January 2019


Mesoporous-silica induced doped carbon nanotube growth from metal–organic frameworks
journal, January 2018


Uniquely integrated Fe-doped Ni(OH) 2 nanosheets for highly efficient oxygen and hydrogen evolution reactions
journal, January 2018


Integrating MXene nanosheets with cobalt-tipped carbon nanotubes for an efficient oxygen reduction reaction
journal, January 2019


Carbon quantum dots enhanced the activity for the hydrogen evolution reaction in ruthenium-based electrocatalysts
journal, January 2020


Harnessing MOF materials in photovoltaic devices: recent advances, challenges, and perspectives
journal, January 2019


A KCl-assisted pyrolysis strategy to fabricate nitrogen-doped carbon nanotube hollow polyhedra for efficient bifunctional oxygen electrocatalysts
journal, January 2019


Cobalt/zinc dual-sites coordinated with nitrogen in nanofibers enabling efficient and durable oxygen reduction reaction in acidic fuel cells
journal, January 2020


From IR to x-rays: gaining molecular level insights on metal-organic frameworks through spectroscopy
journal, August 2019


Effective Oxygen Reduction and Evolution Catalysts Derived from Metal Organic Frameworks by Optimizing Active Sites
journal, January 2018