Collaborative integration of ultrafine Fe2P nanocrystals into Fe, N, P-codoped carbon nanoshells for highly-efficient oxygen reduction

Rui Ma; Xun Cui; Xiaoxue Xu; Yonglin Wang; Gaoqiang Xiang; Likun Gao; Zhiqun Lin; Yingkui Yang

doi:10.1016/j.nanoen.2023.108179

Collaborative integration of ultrafine Fe₂P nanocrystals into Fe, N, P-codoped carbon nanoshells for highly-efficient oxygen reduction

Rui Ma, Xun Cui, Xiaoxue Xu, Yonglin Wang, Gaoqiang Xiang, Likun Gao, Zhiqun Lin, Yingkui Yang

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

The rational design and facile synthesis of cost-effective and high-performance carbon-based catalysts for oxygen reduction reaction (ORR) is of great significance but remain challenging. Herein, we report the crafting of a robust Fe,N,P-codoped, ultrafine Fe₂P nanocrystals decorated, highly hierarchical porous carbon nanoshells (denoted Fe,N,P-CNSs/Fe₂P) via a simple yet robust one-step synergetic phosphorization and pyrolysis approach for highly-efficient ORR. Specifically, well-defined polypyrrole-co-polyaniline hollow nanospheres with a shell thickness of ≈ 43 nm (PPy-co-PANI-HNs) are first elaborately synthesized via a facile soft-templating (Triton X-100 micelles) copolymerization of pyrrole and aniline monomers. Subsequent one-step synergetic phosphorization and pyrolysis of PPy-co-PANI-HNs pre-impregnated with NaH₂PO₂·H₂O and FeCl₃ (H₂PO₂^-,Fe³⁺@PPy-co-PANI-HNs) yields Fe,N,P-CNSs/Fe₂P with a well-crafted ultrathin nanoshell (shell thickness of ≈13 nm) architecture containing abundant hierarchical porosity. Remarkably, an alkaline electrolyte capitalizing on the resulting Fe,N,P-CNSs/Fe₂P manifests excellent ORR performance with the half-wave and onset potentials (E_1/2 of 0.854 V and E_onset of 0.955 V) comparable to Pt/C, diffusion limited current density (J_L of −5.98 mA cm⁻²) higher than Pt/C, and long-time durability and methanol resistance better than Pt/C, demonstrating great potential as air cathode in zinc-air batteries (maximum power density of 170 mW cm⁻² and specific capacity of 824.5 mA h g⁻¹). Combined experimental and theoretical studies reveal that the impressive ORR performance of Fe,N,P-CNSs/Fe₂P originates from simultaneous compositional (i.e., Fe,N,P-codoping and ultrafine Fe₂P nanocrystals decorating) and structural (i.e., hierarchically porous ultrathin nanoshell architecture) tailoring enabled by the judicious one-step synergetic phosphorization and pyrolysis.

Original language	English
Article number	108179
Journal	Nano Energy
Volume	108
DOIs	https://doi.org/10.1016/j.nanoen.2023.108179
State	Published - Apr 2023

Bibliographical note

Publisher Copyright:
© 2023

Keywords

Carbon-based catalysts
Fe,N,P-codoping
Oxygen reduction reaction
Ultrafine FeP nanocrystals
Ultrathin nanoshell architecture

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10.1016/j.nanoen.2023.108179

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@article{35955a7f798343bcb9758eeb965df779,

title = "Collaborative integration of ultrafine Fe2P nanocrystals into Fe, N, P-codoped carbon nanoshells for highly-efficient oxygen reduction",

abstract = "The rational design and facile synthesis of cost-effective and high-performance carbon-based catalysts for oxygen reduction reaction (ORR) is of great significance but remain challenging. Herein, we report the crafting of a robust Fe,N,P-codoped, ultrafine Fe2P nanocrystals decorated, highly hierarchical porous carbon nanoshells (denoted Fe,N,P-CNSs/Fe2P) via a simple yet robust one-step synergetic phosphorization and pyrolysis approach for highly-efficient ORR. Specifically, well-defined polypyrrole-co-polyaniline hollow nanospheres with a shell thickness of ≈ 43 nm (PPy-co-PANI-HNs) are first elaborately synthesized via a facile soft-templating (Triton X-100 micelles) copolymerization of pyrrole and aniline monomers. Subsequent one-step synergetic phosphorization and pyrolysis of PPy-co-PANI-HNs pre-impregnated with NaH2PO2·H2O and FeCl3 (H2PO2-,Fe3+@PPy-co-PANI-HNs) yields Fe,N,P-CNSs/Fe2P with a well-crafted ultrathin nanoshell (shell thickness of ≈13 nm) architecture containing abundant hierarchical porosity. Remarkably, an alkaline electrolyte capitalizing on the resulting Fe,N,P-CNSs/Fe2P manifests excellent ORR performance with the half-wave and onset potentials (E1/2 of 0.854 V and Eonset of 0.955 V) comparable to Pt/C, diffusion limited current density (JL of −5.98 mA cm−2) higher than Pt/C, and long-time durability and methanol resistance better than Pt/C, demonstrating great potential as air cathode in zinc-air batteries (maximum power density of 170 mW cm−2 and specific capacity of 824.5 mA h g−1). Combined experimental and theoretical studies reveal that the impressive ORR performance of Fe,N,P-CNSs/Fe2P originates from simultaneous compositional (i.e., Fe,N,P-codoping and ultrafine Fe2P nanocrystals decorating) and structural (i.e., hierarchically porous ultrathin nanoshell architecture) tailoring enabled by the judicious one-step synergetic phosphorization and pyrolysis.",

keywords = "Carbon-based catalysts, Fe,N,P-codoping, Oxygen reduction reaction, Ultrafine FeP nanocrystals, Ultrathin nanoshell architecture",

author = "Rui Ma and Xun Cui and Xiaoxue Xu and Yonglin Wang and Gaoqiang Xiang and Likun Gao and Zhiqun Lin and Yingkui Yang",

note = "Publisher Copyright: {\textcopyright} 2023",

year = "2023",

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doi = "10.1016/j.nanoen.2023.108179",

language = "English",

volume = "108",

journal = "Nano Energy",

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TY - JOUR

T1 - Collaborative integration of ultrafine Fe2P nanocrystals into Fe, N, P-codoped carbon nanoshells for highly-efficient oxygen reduction

AU - Ma, Rui

AU - Cui, Xun

AU - Xu, Xiaoxue

AU - Wang, Yonglin

AU - Xiang, Gaoqiang

AU - Gao, Likun

AU - Lin, Zhiqun

AU - Yang, Yingkui

PY - 2023/4

Y1 - 2023/4

N2 - The rational design and facile synthesis of cost-effective and high-performance carbon-based catalysts for oxygen reduction reaction (ORR) is of great significance but remain challenging. Herein, we report the crafting of a robust Fe,N,P-codoped, ultrafine Fe2P nanocrystals decorated, highly hierarchical porous carbon nanoshells (denoted Fe,N,P-CNSs/Fe2P) via a simple yet robust one-step synergetic phosphorization and pyrolysis approach for highly-efficient ORR. Specifically, well-defined polypyrrole-co-polyaniline hollow nanospheres with a shell thickness of ≈ 43 nm (PPy-co-PANI-HNs) are first elaborately synthesized via a facile soft-templating (Triton X-100 micelles) copolymerization of pyrrole and aniline monomers. Subsequent one-step synergetic phosphorization and pyrolysis of PPy-co-PANI-HNs pre-impregnated with NaH2PO2·H2O and FeCl3 (H2PO2-,Fe3+@PPy-co-PANI-HNs) yields Fe,N,P-CNSs/Fe2P with a well-crafted ultrathin nanoshell (shell thickness of ≈13 nm) architecture containing abundant hierarchical porosity. Remarkably, an alkaline electrolyte capitalizing on the resulting Fe,N,P-CNSs/Fe2P manifests excellent ORR performance with the half-wave and onset potentials (E1/2 of 0.854 V and Eonset of 0.955 V) comparable to Pt/C, diffusion limited current density (JL of −5.98 mA cm−2) higher than Pt/C, and long-time durability and methanol resistance better than Pt/C, demonstrating great potential as air cathode in zinc-air batteries (maximum power density of 170 mW cm−2 and specific capacity of 824.5 mA h g−1). Combined experimental and theoretical studies reveal that the impressive ORR performance of Fe,N,P-CNSs/Fe2P originates from simultaneous compositional (i.e., Fe,N,P-codoping and ultrafine Fe2P nanocrystals decorating) and structural (i.e., hierarchically porous ultrathin nanoshell architecture) tailoring enabled by the judicious one-step synergetic phosphorization and pyrolysis.

AB - The rational design and facile synthesis of cost-effective and high-performance carbon-based catalysts for oxygen reduction reaction (ORR) is of great significance but remain challenging. Herein, we report the crafting of a robust Fe,N,P-codoped, ultrafine Fe2P nanocrystals decorated, highly hierarchical porous carbon nanoshells (denoted Fe,N,P-CNSs/Fe2P) via a simple yet robust one-step synergetic phosphorization and pyrolysis approach for highly-efficient ORR. Specifically, well-defined polypyrrole-co-polyaniline hollow nanospheres with a shell thickness of ≈ 43 nm (PPy-co-PANI-HNs) are first elaborately synthesized via a facile soft-templating (Triton X-100 micelles) copolymerization of pyrrole and aniline monomers. Subsequent one-step synergetic phosphorization and pyrolysis of PPy-co-PANI-HNs pre-impregnated with NaH2PO2·H2O and FeCl3 (H2PO2-,Fe3+@PPy-co-PANI-HNs) yields Fe,N,P-CNSs/Fe2P with a well-crafted ultrathin nanoshell (shell thickness of ≈13 nm) architecture containing abundant hierarchical porosity. Remarkably, an alkaline electrolyte capitalizing on the resulting Fe,N,P-CNSs/Fe2P manifests excellent ORR performance with the half-wave and onset potentials (E1/2 of 0.854 V and Eonset of 0.955 V) comparable to Pt/C, diffusion limited current density (JL of −5.98 mA cm−2) higher than Pt/C, and long-time durability and methanol resistance better than Pt/C, demonstrating great potential as air cathode in zinc-air batteries (maximum power density of 170 mW cm−2 and specific capacity of 824.5 mA h g−1). Combined experimental and theoretical studies reveal that the impressive ORR performance of Fe,N,P-CNSs/Fe2P originates from simultaneous compositional (i.e., Fe,N,P-codoping and ultrafine Fe2P nanocrystals decorating) and structural (i.e., hierarchically porous ultrathin nanoshell architecture) tailoring enabled by the judicious one-step synergetic phosphorization and pyrolysis.

KW - Carbon-based catalysts

KW - Fe,N,P-codoping

KW - Oxygen reduction reaction

KW - Ultrafine FeP nanocrystals

KW - Ultrathin nanoshell architecture

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