Electrocatalytic oxygen reduction kinetics on Fe-center of nitrogen-doped graphene
Literature Information
Jing Sun, Zhi-Pan Liu
The Fe/N/C catalysts have emerged recently as a representative class of non-Pt catalysts for oxygen electrocatalytic reduction, which could have a competitive catalytic performance to Pt. However, the nature of the catalyst remains elusive, especially on the active site structure and the electrocatalytic kinetics. Here we examine two kinds of Fe/N active sites for Fe/N/C catalysts, namely, the four-coordinated FeN4 and the five-coordinated Fe(CN)N4 centers embedded in graphene layers. By using large-scale first principles calculations with a periodic continuum solvation model based on the Modified-Poisson–Boltzmann equation (CM-MPB), we identified the four (4e) and two electron (2e) oxygen reduction pathways under acidic conditions. We find that both 4e and 2e pathways involves the formation of an OOH intermediate, which breaks its O–OH bond in the 4e pathway but is reduced to H2O2 in the 2e pathway. We show that at 0.8 V vs. SHE, the 4e pathway is preferred at both FeN4 and Fe(CN)N4 centers, but the 2e pathway is kinetically also likely on the Fe(CN)N4 center. The O–OH bond breaking of OOH is the key kinetic step, which has a similar free energy barrier to the OH reduction on the FeN4 center, and is the rate-determining step on the Fe(CN)N4 center. Due to the high adsorption energy of Fe towards the fifth ligand, such as OH and CN, we expect that the active site of the real Fe/N/C catalyst is the five coordinated Fe center. We found that the barrier of the O–OH bond breaking step is not sensitive to potential and a Tafel slope of 60 mV is predicted for the ORR on the Fe(CN)N4 center, which is consistent with experimental observation.
Recommended Journals

Journal of Physical Organic Chemistry

Advanced Materials

Main Group Metal Chemistry

Journal of Computer-Aided Molecular Design

Cement and Concrete Composites

Advanced Powder Technology

Bio-Medical Materials and Engineering

Current Medicinal Chemistry

Advances in Cement Research

Computational Materials Science
Related Literature
Quantitative evaluation of positive ϕ angle propensity in flexible regions of proteins from three-bond J couplings
Jung Ho Lee, Jinfa Ying, Ad Bax
DOI: 10.1039/C5CP04542H
Selective adsorption of arsenate and the reversible structure transformation of the mesoporous metal–organic framework MIL-100(Fe)
Li Jiang, Chunru Wang
DOI: 10.1039/C6CP00249H
Electrochemical synthesis of poly(3-aminophenylboronic acid) in ethylene glycol without exogenous protons
Feifan Wang, Feixue Zou, Xinxin Yu, Zhenyu Feng, Na Du, Yaohua Zhong
DOI: 10.1039/C6CP00800C
Structural determination of niobium-doped silicon clusters by far-infrared spectroscopy and theory
Xiaojun Li, Pieterjan Claes, Marko Haertelt, Peter Lievens, Ewald Janssens
DOI: 10.1039/C5CP07298K
Spectroscopic properties and location of the Ce3+ energy levels in Y3Al2Ga3O12 and Y3Ga5O12 at ambient and high hydrostatic pressure
S. Mahlik, A. Lazarowska, J. Ueda, S. Tanabe, M. Grinberg
DOI: 10.1039/C5CP07732J
Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films
Benjamin W. Caplins, Tyler K. Mullenbach, Russell J. Holmes, David A. Blank
DOI: 10.1039/C6CP00958A
Linkage-specific conformational ensembles of non-canonical polyubiquitin chains
Carlos A. Castañeda, Apurva Chaturvedi, Christina M. Camara, Joseph E. Curtis, Susan Krueger, David Fushman
DOI: 10.1039/C5CP04601G
Effect of environment on iodine oxidation state and reactivity with aluminum
Dylan K. Smith, Jena McCollum, Michelle L. Pantoya
DOI: 10.1039/C5CP06998J
Interaction between copper and carbon nanotubes triggers their mutual role in the enhanced photodegradation of p-chloroaniline
N. F. Khusnun, S. Triwahyono, N. W. C. Jusoh
DOI: 10.1039/C5CP08068A
Defect structure and optical phonon confinement in ultrananocrystalline BixSn1−xO2 (x = 0, 0.03, 0.05, and 0.08) synthesized by a sonochemical method
L. Aswaghosh, Divinah Manoharan, N. Victor Jaya
DOI: 10.1039/C5CP06214D
You might also like
What are the main uses of 1-(3-Aminophenyl)-3-[(3R)-1-(3,3-dimethyl-2-oxobutyl)-2-oxo-5-(2-pyridinyl)-2,3-dihydro-1H-1,4-benzodiazepin-3-yl]urea (CAS: 155412-88-7)?
This compound is mainly used as an intermediate in the synthesis of antipsychoti...
How should waste containing 1-(D-Ribofuranosyl)-1,4-dihydro-3-pyridinecarboxamide (CAS: 19132-12-8) be handled?
Waste containing 1-(D-Ribofuranosyl)-1,4-dihydro-3-pyridinecarboxamide (CAS: 191...
What regulatory guidelines apply to 2-Methyl-2-propanyl 3-bromo-3-(hydroxymethyl)-1-azetidinecarboxylate (CAS: 2007919-81-3)?
2-Methyl-2-propanyl 3-bromo-3-(hydroxymethyl)-1-azetidinecarboxylate (CAS: 20079...
What is N-(4-Chloro-2-pyridinyl)acetamide (CAS: 245056-66-0)?
N-(4-Chloro-2-pyridinyl)acetamide (CAS: 245056-66-0) is a chemical compound with...
What is 5-Chloro-2-hydroxybenzoic acid (CAS: 321-14-2)?
5-Chloro-2-hydroxybenzoic acid, also known as 5-chlorosalicylic acid, is an arom...
What precautions should be taken when handling 1,1-Dichloro-1-fluoroethane (CAS: 1717-00-6)?
When handling 1,1-Dichloro-1-fluoroethane (CAS: 1717-00-6), it is important to u...
What are the physical and chemical properties of Fmoc-(2S,3R)-3-phenylpyrrolidine-2-carboxylic acid (CAS: 281655-32-1)?
Fmoc-(2S,3R)-3-phenylpyrrolidine-2-carboxylic acid is a white crystalline solid ...
What are the main uses of 4-Amino-5-bromo-2-pyridinecarboxylic acid (CAS: 1363381-01-4)?
4-Amino-5-bromo-2-pyridinecarboxylic acid is primarily used as a precursor in th...
What precautions should be taken when handling (S)-tert-butyl 2-((2-(4-bromophenyl)-2-oxoethyl)carbamoyl)pyrrolidine-1-carboxylate (CAS: 1007881-98-2)?
Handling this compound should be done with personal protective equipment (PPE) i...
What precautions should be taken when handling 8-bromo-2,2-dimethyl-3,4-dihydro-2H-1,4-benzoxazin-3-one (CAS: 688363-73-7)?
When handling 8-bromo-2,2-dimethyl-3,4-dihydro-2H-1,4-benzoxazin-3-one, use prop...
Source Journal
Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

![6-Benzyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-c]pyridin-3(2H)-one structure 6-Benzyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-c]pyridin-3(2H)-one structure](https://static.chemtradehub.com/structs/909/909187-64-0-f54f.webp)
![Methyl 4-({[(2-methyl-2-propanyl)oxy]carbonyl}amino)bicyclo[2.2.2]octane-1-carboxylate structure Methyl 4-({[(2-methyl-2-propanyl)oxy]carbonyl}amino)bicyclo[2.2.2]octane-1-carboxylate structure](https://static.chemtradehub.com/structs/943/943845-74-7-b7e5.webp)
![Pyrazolo[1,5-a]pyridine-3-carbothioamide structure Pyrazolo[1,5-a]pyridine-3-carbothioamide structure](https://static.chemtradehub.com/structs/885/885275-44-5-aae0.webp)
![tert-Butyl N-[(2-chloropyridin-4-yl)methyl]carbamate structure tert-Butyl N-[(2-chloropyridin-4-yl)methyl]carbamate structure](https://static.chemtradehub.com/structs/916/916210-27-0-9f95.webp)