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Title: Anion-Regulated Selective Generation of Cobalt Sites in Carbon: Toward Superior Bifunctional Electrocatalysis

Journal Article · · Advanced Materials
 [1];  [2];  [1];  [1];  [1];  [2];  [2];  [3]; ORCiD logo [3]
  1. Chinese Academy of Sciences, Shanghai (China); University of Chinese Academy of Sciences, Beijing (China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. Chinese Academy of Sciences, Shanghai (China)
+ Show Author Affiliations

Abstract The introduction of active transition metal sites (TMSs) in carbon enables the synthesis of noble‐metal‐free electrocatalysts for clean energy conversion applications; however, there are often multiple existing forms of TMSs, which are of different natures and catalytic models. Regulating the evolution of distinctive TMSs is highly desirable but remains challenging to date. Anions, as essential elements involved in the synthesis, have been totally neglected previously in the construction of TMSs. Herein, the effects of anions on the creation of different types of TMSs are investigated for the first time. It is found that the active cobalt–nitrogen sites tend to be selectively constructed on the surface of N‐doped carbon by using chloride, while metallic cobalt nanoparticles encased in protective graphite layers are the dominant forms of cobalt species with nitrate ions. The obtained catalysts demonstrate cobalt‐sites‐dependent activity for oxygen reduction reaction and hydrogen evolution reaction in acidic media. The remarkably enhanced catalytic activities approaching that of benchmark Pt/C in an acidic medium have been obtained on the catalyst dominated with cobalt–nitrogen sites, confirmed by the advanced spectroscopic characterization. This finding demonstrates a general paradigm of anion‐regulated evolution of distinctive TMSs, providing a new pathway for enhancing performances of various targeted reactions related with TMSs.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE; National Key Basic Research Program of China
Grant/Contract Number:
AC02-06CH11357; DE‐AC02‐06CH11357
OSTI ID:
1416001
Alternate ID(s):
OSTI ID: 1407824
Journal Information:
Advanced Materials, Vol. 29, Issue 47; ISSN 0935-9648
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 111 works
Citation information provided by
Web of Science

References (42)

Molecular metal–Nx centres in porous carbon for electrocatalytic hydrogen evolution journal August 2015
Batteries and Fuel Cells: Leading the Way to a Cleaner and Brighter Future journal October 2015
Interfacing electrochemistry journal January 2013
Atomic cobalt on nitrogen-doped graphene for hydrogen generation journal October 2015
Heat-Treated Non-precious-Metal-Based Catalysts for Oxygen Reduction book January 2013
Catalytic activity of Co–N x /C electrocatalysts for oxygen reduction reaction: a density functional theory study journal January 2013
Enhanced Electron Penetration through an Ultrathin Graphene Layer for Highly Efficient Catalysis of the Hydrogen Evolution Reaction journal January 2015
In Situ CO 2 -Emission Assisted Synthesis of Molybdenum Carbonitride Nanomaterial as Hydrogen Evolution Electrocatalyst journal December 2014
Elucidating Oxygen Reduction Active Sites in Pyrolyzed Metal–Nitrogen Coordinated Non-Precious-Metal Electrocatalyst Systems journal April 2014
Influence of Sulfur on the Pyrolysis of CoTMPP as Electrocatalyst for the Oxygen Reduction Reaction journal January 2009
Molecule-Level g-C 3 N 4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions journal February 2017
Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces journal December 2011
Self-Supported Nanoporous Cobalt Phosphide Nanowire Arrays: An Efficient 3D Hydrogen-Evolving Cathode over the Wide Range of pH 0–14 journal May 2014
Earth-Abundant Metal Pyrites (FeS 2 , CoS 2 , NiS 2 , and Their Alloys) for Highly Efficient Hydrogen Evolution and Polysulfide Reduction Electrocatalysis journal September 2014
Metallic Iron–Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media journal September 2015
Bimetal–Organic Framework Self-Adjusted Synthesis of Support-Free Nonprecious Electrocatalysts for Efficient Oxygen Reduction journal October 2015
Nitrogen-doped carbon xerogel: A novel carbon-based electrocatalyst for oxygen reduction reaction in proton exchange membrane (PEM) fuel cells journal January 2011
Degradation by Hydrogen Peroxide of Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction journal January 2015
Cobalt Imidazolate Framework as Precursor for Oxygen Reduction Reaction Electrocatalysts journal January 2011
Molybdenum Boride and Carbide Catalyze Hydrogen Evolution in both Acidic and Basic Solutions journal November 2012
High-Performance Oxygen Reduction Electrocatalysts based on Cheap Carbon Black, Nitrogen, and Trace Iron journal September 2013
Electrochemical Surface Interrogation of a MoS 2 Hydrogen-Evolving Catalyst: In Situ Determination of the Surface Hydride Coverage and the Hydrogen Evolution Kinetics journal June 2016
High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt journal April 2011
Activating Cobalt Nanoparticles via the Mott–Schottky Effect in Nitrogen-Rich Carbon Shells for Base-Free Aerobic Oxidation of Alcohols to Esters journal January 2017
Poisoning the Oxygen Reduction Reaction on Carbon-Supported Fe and Cu Electrocatalysts: Evidence for Metal-Centered Activity journal January 2011
On an Easy Way To Prepare Metal–Nitrogen Doped Carbon with Exclusive Presence of MeN 4 -type Sites Active for the ORR journal January 2016
Highly active and durable non-precious-metal catalysts encapsulated in carbon nanotubes for hydrogen evolution reaction journal January 2014
Reaction Pathways of Hydrogen-Evolving Electrocatalysts: Electrochemical and Spectroscopic Studies of Proton-Coupled Electron Transfer Processes journal May 2016
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts journal February 2014
Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuelcells journal January 2011
Recent Progress in Cobalt-Based Heterogeneous Catalysts for Electrochemical Water Splitting journal November 2015
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells journal April 2009
Recent Development in Hydrogen Evolution Reaction Catalysts and Their Practical Implementation journal March 2015
From Bimetallic Metal-Organic Framework to Porous Carbon: High Surface Area and Multicomponent Active Dopants for Excellent Electrocatalysis journal July 2015
Co–N–C Catalyst for C–C Coupling Reactions: On the Catalytic Performance and Active Sites journal October 2015
Metallocorroles as Nonprecious-Metal Catalysts for Oxygen Reduction journal October 2015
Cross-Laboratory Experimental Study of Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction journal July 2009
Design of active and stable Co–Mo–Sx chalcogels as pH-universal catalysts for the hydrogen evolution reaction journal November 2015
Oxalate supported pyrolysis of CoTMPP as electrocatalysts for the oxygen reduction reaction journal July 2009
Enhanced Electron Penetration through an Ultrathin Graphene Layer for Highly Efficient Catalysis of the Hydrogen Evolution Reaction journal January 2015
Molybdenum Boride and Carbide Catalyze Hydrogen Evolution in both Acidic and Basic Solutions journal November 2012
Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts journal February 2014

Cited By (13)

Carbon-Rich Nanomaterials: Fascinating Hydrogen and Oxygen Electrocatalysts journal July 2018
Atomically Transition Metals on Self‐Supported Porous Carbon Flake Arrays as Binder‐Free Air Cathode for Wearable Zinc−Air Batteries journal February 2019
Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single‐Site Catalysts Made of 3d Transition Metals journal November 2019
Atomically Dispersed Binary Co‐Ni Sites in Nitrogen‐Doped Hollow Carbon Nanocubes for Reversible Oxygen Reduction and Evolution journal October 2019
Hierarchically Porous M-N-C (M = Co and Fe) Single-Atom Electrocatalysts with Robust MN x Active Moieties Enable Enhanced ORR Performance journal August 2018
Anion‐Regulated Hydroxysulfide Monoliths as OER/ORR/HER Electrocatalysts and their Applications in Self‐Powered Electrochemical Water Splitting journal May 2018
Nitrogen‐Doped Porous Carbon Supported Nonprecious Metal Single‐Atom Electrocatalysts: from Synthesis to Application journal May 2019
A review of anion-regulated multi-anion transition metal compounds for oxygen evolution electrocatalysis journal January 2018
Boosting the ORR performance of modified carbon black via C–O bonds journal January 2019
Hierarchical 3D macrosheets composed of interconnected in situ cobalt catalyzed nitrogen doped carbon nanotubes as superior bifunctional oxygen electrocatalysts for rechargeable Zn–air batteries journal January 2018
Constructing ultrathin CoP nanomeshes by Er-doping for highly efficient bifunctional electrocatalysts for overall water splitting journal January 2019
Aerobic selective oxidation of methylaromatics to benzoic acids over Co@N/Co-CNTs with high loading CoN 4 species journal January 2019
Hierarchical microsphere assembled by nanoplates embedded with MoS 2 and (NiFe)S x nanoparticles as low-cost electrocatalyst for hydrogen evolution reaction journal October 2019

Figures / Tables (5)

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Figure 3(p. 17)figure Figure 3
Figure 4(p. 18)figure Figure 4
Figure 5(p. 19)figure Figure 5

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
cobalt-sites-dependent activities
electrocatalysis
selective generation
transition metal sites