Elucidating the oxygen reduction reaction kinetics on defect engineered nanocarbon electrocatalyst: interplay between the N-dopant and defect sites

The active sites of electrocatalysts play a crucial role in the material design and mechanistic exploration of an electrocatalytic reaction. Defect-tailored heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction (ORR) have been much explored, but there is ambiguity in the predi...

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Veröffentlicht in:Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2023-08, Vol.11 (32), p.1745-1755
Hauptverfasser: Bhardwaj, Sakshi, Kapse, Samadhan, Dan, Soirik, Thapa, Ranjit, Dey, Ramendra Sundar
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container_end_page 1755
container_issue 32
container_start_page 1745
container_title Journal of materials chemistry. A, Materials for energy and sustainability
container_volume 11
creator Bhardwaj, Sakshi
Kapse, Samadhan
Dan, Soirik
Thapa, Ranjit
Dey, Ramendra Sundar
description The active sites of electrocatalysts play a crucial role in the material design and mechanistic exploration of an electrocatalytic reaction. Defect-tailored heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction (ORR) have been much explored, but there is ambiguity in the prediction of active sites responsible for the performance of the material. To find the origin of the activity of this class of catalysts towards ORR, in this work, we use the quantum mechanics/machine learning (QM/ML) approach to derive energy-optimized models with both N-atoms and 5-8-5 defect sites which manifest exemplary ORR activity. Following this approach, we synthesized defect-engineered graphene (DG) using the zinc template method at 1050 °C to achieve optimum N-dopants and intrinsic (5-8-5) defects. The obtained electrocatalyst exhibits hierarchical porosity, high surface area, low nitrogen content, good stability and a satisfying ORR performance with a half-wave potential ( E 1/2 ) of 0.82 V, comparable to that of commercial Pt/C ( E 1/2 = 0.82 V). Further, the full energy profile was deduced using density functional theory and the charge redistribution in the material cross-verified a reduced overpotential for ORR. This work provides a strategy for the synthesis of noble-metal-free high-performance electrocatalysts for energy conversion. For oxygen reduction reaction (ORR), the active sites of a defective N-doped graphene are predicted by a quantum mechanics/machine learning approach; the synthesized catalyst shows exemplary ORR activity that was further confirmed by a DFT study.
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Defect-tailored heteroatom-doped carbon-based electrocatalysts for oxygen reduction reaction (ORR) have been much explored, but there is ambiguity in the prediction of active sites responsible for the performance of the material. To find the origin of the activity of this class of catalysts towards ORR, in this work, we use the quantum mechanics/machine learning (QM/ML) approach to derive energy-optimized models with both N-atoms and 5-8-5 defect sites which manifest exemplary ORR activity. Following this approach, we synthesized defect-engineered graphene (DG) using the zinc template method at 1050 °C to achieve optimum N-dopants and intrinsic (5-8-5) defects. The obtained electrocatalyst exhibits hierarchical porosity, high surface area, low nitrogen content, good stability and a satisfying ORR performance with a half-wave potential ( E 1/2 ) of 0.82 V, comparable to that of commercial Pt/C ( E 1/2 = 0.82 V). Further, the full energy profile was deduced using density functional theory and the charge redistribution in the material cross-verified a reduced overpotential for ORR. This work provides a strategy for the synthesis of noble-metal-free high-performance electrocatalysts for energy conversion. 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source Royal Society Of Chemistry Journals 2008-
subjects Catalysts
Charge materials
Chemical reduction
Density functional theory
Design defects
Dopants
Electrocatalysts
Energy conversion
Graphene
Machine learning
Nitrogen
Noble metals
Oxygen reduction reactions
Porosity
Quantum mechanics
Reaction kinetics
Surface stability
title Elucidating the oxygen reduction reaction kinetics on defect engineered nanocarbon electrocatalyst: interplay between the N-dopant and defect sites
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