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Title: Mn- and N- doped carbon as promising catalysts for oxygen reduction reaction: Theoretical prediction and experimental validation

Journal Article · · Applied Catalysis. B, Environmental

Development of platinum group metal (PGM)-free as well as iron-free electrocatalysts is imperative to achieve low-cost and long-term durability of polymer electrolyte membrane fuel cells. Here in this paper, we combined computational and experimental studies to investigate the mechanism, activity, and durability of Mn and N co-doped carbon (denoted as Mn-N-C) as promising catalysts for oxygen reduction reaction (ORR) in challenging acid medium. The first-principles density functional theory calculations predict that it is favorable for O2 to be reduced into H2O via four-electron pathway on MnN4 sites embedded in carbon layer. Using the reaction energies calculated from DFT, microkinetic analysis predicts that the MnN4 sites could catalyze ORR with a half-wave potential only 60 mV lower than that of Pt (111) and 80 mV lower than that of the FeN4 sites embedded in carbon layer, assuming the same density of active sites in the catalysts. Motivated by the computational prediction, we synthesized a Mn-N-C catalyst using a polymer (i.e., polyaniline-PANI) hydrogel precursors via a high temperature approach. Structural characterization indicates that atomically dispersed Mn sites coordinated with N are very likely formed in the catalyst. Electrochemical measurements show that the synthesized Mn-N-C catalyst can promote four-electron ORR with a catalytic activity in acids comparable to that of the Fe-N-C catalyst prepared using the same procedure. More importantly, the Mn-N-C catalyst exhibits superior potential cyclic stability, only losing 20 mV after 10000 cycles (0.6 to 1.0 V in O2 saturated electrolyte). In comparison, the Fe-N-C catalyst would loss 80 mV after only 5000 cycles under the same testing conditions. Our computational and experimental results strongly suggest that the Mn and N co-doped carbon could be promising high-performance catalysts for ORR in acidic medium.

Research Organization:
Giner, Inc., Newton, MA (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
EE0008075; CBET-1804534; CMMI-1662615; CBET- 1604392; ACI-1053575; SC0012704
OSTI ID:
1886835
Alternate ID(s):
OSTI ID: 1480960
Report Number(s):
BNL-209359-2018-JAAM; 10124
Journal Information:
Applied Catalysis. B, Environmental, Vol. 243; ISSN 0926-3373
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 153 works
Citation information provided by
Web of Science

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Cited By (13)

Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis journal September 2019
Engineering Local Coordination Environments of Atomically Dispersed and Heteroatom‐Coordinated Single Metal Site Electrocatalysts for Clean Energy‐Conversion journal November 2019
Single‐Atom Cr−N 4 Sites Designed for Durable Oxygen Reduction Catalysis in Acid Media journal July 2019
Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction journal November 2019
Single‐Atom Iron Boosts Electrochemiluminescence journal January 2020
Single‐Atom Cr−N 4 Sites Designed for Durable Oxygen Reduction Catalysis in Acid Media journal September 2019
Single‐Atom Iron Boosts Electrochemiluminescence journal January 2020
Recent Progress in Precious Metal‐Free Carbon‐Based Materials towards the Oxygen Reduction Reaction: Activity, Stability, and Anti‐Poisoning journal November 2019
Metal‐Layer Assisted Growth of Ultralong Quasi‐2D MOF Nanoarrays on Arbitrary Substrates for Accelerated Oxygen Evolution journal November 2019
Oxygen Reduction Reaction book January 2020
Metal-Nitrogen-Carbon Catalysts for Oxygen Reduction in PEM Fuel Cells: Self-Template Synthesis Approach to Enhancing Catalytic Activity and Stability journal March 2019
Single-atom catalysts for electrochemical clean energy conversion: recent progress and perspectives journal January 2020
Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells journal January 2019

Figures / Tables (7)