Molecular Fe-N4 Moieties Coupled with Atomic Co-N4 Sites Toward Improved Oxygen Reduction Performance

Xie, Peng‐Fei; Zhong, Hong; Fang, Lingzhe; Lyu, Zhaoyuan; Yu, Wan‐Jing; Li, Tao; Lee, Jiyoung; Shin, Hamin; Beckman, Scott P.; Lin, Yuehe; Ding, Shichao; Kim, Il‐Doo; Li, Jin‐Cheng

doi:10.1002/adfm.202314554

Molecular Fe-N₄ Moieties Coupled with Atomic Co-N₄ Sites Toward Improved Oxygen Reduction Performance

Journal Article · Thu Mar 28 00:00:00 EDT 2024 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.202314554· OSTI ID:2473653

Xie, Peng‐Fei ^[1]; Zhong, Hong ^[2]; Fang, Lingzhe ^[3]; Lyu, Zhaoyuan ^[2]; Yu, Wan‐Jing ^[4]; Li, Tao ^[5]; Lee, Jiyoung ^[6]; Shin, Hamin ^[7]; Beckman, Scott P. ^[2]; Lin, Yuehe ^[2]; Ding, Shichao ^[2]; ^[7]; Li, Jin‐Cheng ^[1]

Kunming University of Science and Technology (China)
Washington State Univ., Pullman, WA (United States)
Northern Illinois Univ., DeKalb, IL (United States)
Central South University, Changsha (China)
Northern Illinois Univ., DeKalb, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)

Research on high-efficiency and cost-efficient catalysts for oxygen reduction reaction (ORR) is still a vital but challenging issue for commercializing metal–air batteries. Herein, a single-molecule/atom hybrid catalyst is developed to boost the ORR, in which iron phthalocyanine molecules containing molecular Fe-N₄ moieties couple with atomic Co-N₄ sites on the surface of polyhedral carbon. Density functional theory calculations reveal that face-to-face laminated construction of Fe-N₄ and Co-N₄ in the hybrid catalyst can effectively modulate the electronic structure of active iron atoms and reduce the energy barrier of the rate-determining step for ORR. As a result, this hybrid catalyst demonstrates excellent ORR performance, featuring a half-wave potential of 0.904 V, a peak power density of 238.3 mW cm^-2 for zinc–air battery, and outstanding electrocatalytic stability. Here, this work offers a distinctive and robust molecular/atomic engineering approach to creating efficient electrocatalysts, advancing the fields of metal–air batteries.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2473653

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 32 Vol. 34; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Dual‐Phasic Carbon with Co Single Atoms and Nanoparticles as a Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Batteries Li, Jin‐Cheng; Meng, Yu; Zhang, Lili Advanced Functional Materials, Vol. 31, Issue 42 https://doi.org/10.1002/adfm.202103360	journal	July 2021
Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells Wang, Xiao Xia; Cullen, David A.; Pan, Yung-Tin Advanced Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adma.201706758	journal	January 2018
Promoting Oxygen Reduction Reaction by Inducing Out‐of‐Plane Polarization in a Metal Phthalocyanine Catalyst Li, Xiyu; Wu, Xingshun; Zhao, Yuan Advanced Materials, Vol. 35, Issue 30 https://doi.org/10.1002/adma.202302467	journal	June 2023
Coordination Engineering of Single‐Atom Catalysts for the Oxygen Reduction Reaction: A Review Zhang, Jincheng; Yang, Hongbin; Liu, Bin Advanced Energy Materials, Vol. 11, Issue 3 https://doi.org/10.1002/aenm.202002473	journal	November 2020
Carbon‐Nanotube‐Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High‐Efficiency and Long‐Life Rechargeable Zinc–Air Batteries Ding, Shichao; He, Lin; Fang, Lingzhe Advanced Energy Materials, Vol. 12, Issue 48 https://doi.org/10.1002/aenm.202202984	journal	November 2022
Promoting Oxygen Reduction Reaction on Atomically Dispersed Fe Sites via Establishing Hydrogen Bonding with the Neighboring P Atoms Zong, Lingbo; Fan, Kaicai; Li, Ping Advanced Energy Materials, Vol. 13, Issue 5 https://doi.org/10.1002/aenm.202203611	journal	December 2022
Highly Active and Durable Metal‐Free Carbon Catalysts for Anion‐Exchange Membrane Fuel Cells Yang, Liu; Liu, Huibing; Qiao, Zelong Advanced Energy Materials, Vol. 13, Issue 20 https://doi.org/10.1002/aenm.202204390	journal	April 2023
Carbon‐Based Electrocatalysts for Acidic Oxygen Reduction Reaction Cui, Pengbo; Zhao, Linjie; Long, Yongde Angewandte Chemie International Edition, Vol. 62, Issue 14 https://doi.org/10.1002/anie.202218269	journal	February 2023
Longitudinally Grafting of Graphene with Iron Phthalocyanine‐based Porous Organic Polymer to Boost Oxygen Electroreduction Li, Longbin; Tang, Xiannong; Huang, Senhe Angewandte Chemie International Edition, Vol. 62, Issue 22 https://doi.org/10.1002/anie.202301642	journal	April 2023
Well‐defined N₃C₁‐anchored Single‐Metal‐Sites for Oxygen Reduction Reaction Huang, Senhe; Tranca, Diana; Rodríguez‐Hernández, Fermin Angewandte Chemie International Edition, Vol. 63, Issue 1 https://doi.org/10.1002/anie.202314833	journal	November 2023
Hierarchical Porous Carbon Anchored Atomic/Clustered Cobalt for Boosting Oxygen Reduction Electrocatalysis Lyu, Xiao; Gu, Xiang; Li, Gen ChemCatChem, Vol. 14, Issue 24 https://doi.org/10.1002/cctc.202201192	journal	November 2022
Bulk preparation of free‐standing single‐iron‐atom catalysts directly as the air electrodes for high‐performance zinc‐air batteries Zhang, Hong‐Bo; Meng, Yu; Zhong, Hong Carbon Energy, Vol. 5, Issue 5 https://doi.org/10.1002/cey2.289	journal	December 2022
Single‐Atomic Site Catalyst with Heme Enzymes‐Like Active Sites for Electrochemical Sensing of Hydrogen Peroxide Ding, Shichao; Lyu, Zhaoyuan; Fang, Lingzhe Small, Vol. 17, Issue 25 https://doi.org/10.1002/smll.202100664	journal	May 2021
2D Single‐Atom Catalyst with Optimized Iron Sites Produced by Thermal Melting of Metal–Organic Frameworks for Oxygen Reduction Reaction Liu, Dong; Li, Jin‐Cheng; Ding, Shichao Small Methods, Vol. 4, Issue 6 https://doi.org/10.1002/smtd.201900827	journal	February 2020
A peroxidase-like single-atom Fe-N5 active site for effective killing human lung adenocarcinoma cells Zhu, Liye; Zhong, Hong; Du, Dan Nano Research, Vol. 16, Issue 4 https://doi.org/10.1007/s12274-022-5127-3	journal	November 2022
Boosting the activity of Fe-Nx moieties in Fe-N-C electrocatalysts via phosphorus doping for oxygen reduction reaction Li, Jin-Cheng; Zhong, Hong; Xu, Mingjie Science China Materials, Vol. 63, Issue 6 https://doi.org/10.1007/s40843-019-1207-y	journal	November 2019
An active and robust Si-Fe/N/C catalyst derived from waste reed for oxygen reduction Wei, Qiliang; Yang, Xiaohua; Zhang, Gaixia Applied Catalysis B: Environmental, Vol. 237 https://doi.org/10.1016/j.apcatb.2018.05.046	journal	December 2018
Coupling of iron phthalocyanine at carbon defect site via π-π stacking for enhanced oxygen reduction reaction Yu, Xuezheng; Lai, Shoujuan; Xin, Shishan Applied Catalysis B: Environmental, Vol. 280 https://doi.org/10.1016/j.apcatb.2020.119437	journal	January 2021
A comparative study of iron phthalocyanine electrocatalysts supported on different nanocarbons for oxygen reduction reaction Yang, Jun; Tao, Jie; Isomura, Takenori Carbon, Vol. 145 https://doi.org/10.1016/j.carbon.2019.01.022	journal	April 2019
Enhanced electronic interaction between iron phthalocyanine and cobalt single atoms promoting oxygen reduction in alkaline and neutral aluminum-air batteries Wang, Yibo; Li, Kaiqi; Cheng, Ruiqi Chemical Engineering Journal, Vol. 450 https://doi.org/10.1016/j.cej.2022.138213	journal	December 2022
Single-atom catalysts for next-generation rechargeable batteries and fuel cells Shah, Syed Shoaib Ahmad; Najam, Tayyaba; Bashir, Muhammad Sohail Energy Storage Materials, Vol. 45 https://doi.org/10.1016/j.ensm.2021.11.049	journal	March 2022
Bifunctional oxygen electrocatalysts enriched with single Fe atoms and NiFe2O4 nanoparticles for rechargeable zinc–air batteries Hu, Hao; Meng, Yu; Mei, Yi Energy Storage Materials, Vol. 54 https://doi.org/10.1016/j.ensm.2022.11.001	journal	January 2023
Theoretical Understandings of Graphene-based Metal Single-Atom Catalysts: Stability and Catalytic Performance Zhuo, Hong-Ying; Zhang, Xin; Liang, Jin-Xia Chemical Reviews, Vol. 120, Issue 21 https://doi.org/10.1021/acs.chemrev.0c00818	journal	October 2020
Two-Dimensional Atomically Dispersed Co–N/C Oxygen Reaction Electrocatalysts via Molten-Salt-Assisted Pyrolysis of Metal–Organic Frameworks Zhang, Xiao-Qian; Lyu, Zhaoyuan; Ding, Shichao The Journal of Physical Chemistry C, Vol. 127, Issue 25 https://doi.org/10.1021/acs.jpcc.3c02841	journal	June 2023
Highly Dispersive Cerium Atoms on Carbon Nanowires as Oxygen Reduction Reaction Electrocatalysts for Zn–Air Batteries Li, Jin-Cheng; Qin, Xueping; Xiao, Fei Nano Letters, Vol. 21, Issue 10 https://doi.org/10.1021/acs.nanolett.1c01493	journal	May 2021
Theoretically Revealed and Experimentally Demonstrated Synergistic Electronic Interaction of CoFe Dual-Metal Sites on N-doped Carbon for Boosting Both Oxygen Reduction and Evolution Reactions Zhou, Xuyan; Gao, Jiaojiao; Hu, Yixuan Nano Letters, Vol. 22, Issue 8 https://doi.org/10.1021/acs.nanolett.2c00658	journal	April 2022
Directional Manipulation of Electron Transfer by Energy Level Engineering for Efficient Cathodic Oxygen Reduction Wang, Yang; Zhou, Tianpei; Ruan, Shanshan Nano Letters, Vol. 22, Issue 16 https://doi.org/10.1021/acs.nanolett.2c01933	journal	August 2022
Regulating the FeN₄ Moiety by Constructing Fe–Mo Dual-Metal Atom Sites for Efficient Electrochemical Oxygen Reduction Zhu, Peng; Xiong, Xiang; Wang, Xiaolu Nano Letters, Vol. 22, Issue 23 https://doi.org/10.1021/acs.nanolett.2c03623	journal	November 2022
Bifunctional Oxygen Electrocatalysts Derived from Metal–Organic Framework-Hydrolyzed Nanosheets for Rechargeable Zn-Air Batteries He, Lin; Hu, Hao; Zhang, Hong-Bo ACS Applied Energy Materials, Vol. 5, Issue 12 https://doi.org/10.1021/acsaem.2c02168	journal	November 2022
Catalytic Activity of Co–X (X = S, P, O) and Its Dependency on Nanostructure/Chemical Composition in Lithium–Sulfur Batteries Feng, Shuo; Zhong, Hong; Song, Junhua ACS Applied Energy Materials, Vol. 1, Issue 12 https://doi.org/10.1021/acsaem.8b01434	journal	November 2018
Atomically Isolated Iron Atom Anchored on Carbon Nanotubes for Oxygen Reduction Reaction Liu, Dong; Li, Jin-Cheng; Shi, Qiurong ACS Applied Materials & Interfaces, Vol. 11, Issue 43 https://doi.org/10.1021/acsami.9b12054	journal	September 2019
Secondary-Atom-Assisted Synthesis of Single Iron Atoms Anchored on N-Doped Carbon Nanowires for Oxygen Reduction Reaction Li, Jin-Cheng; Xiao, Fei; Zhong, Hong ACS Catalysis, Vol. 9, Issue 7 https://doi.org/10.1021/acscatal.9b00869	journal	May 2019
Stabilizing Single-Atom Iron Electrocatalysts for Oxygen Reduction via Ceria Confining and Trapping Li, Jin-Cheng; Maurya, Sandip; Kim, Yu Seung ACS Catalysis, Vol. 10, Issue 4 https://doi.org/10.1021/acscatal.9b04621	journal	January 2020
Synergetic Contribution of Boron and Fe–N _x Species in Porous Carbons toward Efficient Electrocatalysts for Oxygen Reduction Reaction Yuan, Kai; Sfaelou, Stavroula; Qiu, Ming ACS Energy Letters, Vol. 3, Issue 1 https://doi.org/10.1021/acsenergylett.7b01188	journal	November 2017
N-Doped Carbon Nanosheet Networks with Favorable Active Sites Triggered by Metal Nanoparticles as Bifunctional Oxygen Electrocatalysts Huang, Xiaoxiao; Zhang, Yelong; Shen, Haoming ACS Energy Letters, Vol. 3, Issue 12 https://doi.org/10.1021/acsenergylett.8b01717	journal	November 2018
Bifunctional Single Atom Electrocatalysts: Coordination–Performance Correlations and Reaction Pathways Wan, Wenchao; Triana, Carlos A.; Lan, Jinggang ACS Nano, Vol. 14, Issue 10 https://doi.org/10.1021/acsnano.0c05088	journal	October 2020
Engineering Atomic Single Metal–FeN₄Cl Sites with Enhanced Oxygen-Reduction Activity for High-Performance Proton Exchange Membrane Fuel Cells Ding, Shichao; Barr, Jordan Alysia; Shi, Qiurong ACS Nano, Vol. 16, Issue 9 https://doi.org/10.1021/acsnano.2c06459	journal	September 2022
Rational Design of Flexible Zn-Based Batteries for Wearable Electronic Devices Xiao, Xiao; Zheng, Zhiyang; Zhong, Xiongwei ACS Nano, Vol. 17, Issue 3 https://doi.org/10.1021/acsnano.2c09509	journal	January 2023
Enhanced Catalytic Performance of Pt-Free Iron Phthalocyanine by Graphene Support for Efficient Oxygen Reduction Reaction Jiang, Yuanyuan; Lu, Yizhong; Lv, Xiangyu ACS Catalysis, Vol. 3, Issue 6 https://doi.org/10.1021/cs4001927	journal	April 2013
Tailoring Acidic Oxygen Reduction Selectivity on Single-Atom Catalysts via Modification of First and Second Coordination Spheres Tang, Cheng; Chen, Ling; Li, Haijing Journal of the American Chemical Society, Vol. 143, Issue 20 https://doi.org/10.1021/jacs.1c03135	journal	May 2021
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b06514	journal	September 2017
Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination Yuan, Kai; Lützenkirchen-Hecht, Dirk; Li, Longbin Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b11852	journal	January 2020
Promotion of oxygen reduction by a bio-inspired tethered iron phthalocyanine carbon nanotube-based catalyst Cao, Ruiguo; Thapa, Ranjit; Kim, Hyejung Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3076	journal	June 2013
Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity Shang, Huishan; Zhou, Xiangyi; Dong, Juncai Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16848-8	journal	June 2020
Iron phthalocyanine with coordination induced electronic localization to boost oxygen reduction reaction Chen, Kejun; Liu, Kang; An, Pengda Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18062-y	journal	August 2020
Fe–N–C electrocatalyst with dense active sites and efficient mass transport for high-performance proton exchange membrane fuel cells Wan, Xin; Liu, Xiaofang; Li, Yongcheng Nature Catalysis, Vol. 2, Issue 3 https://doi.org/10.1038/s41929-019-0237-3	journal	March 2019
A 3D bi-functional porous N-doped carbon microtube sponge electrocatalyst for oxygen reduction and oxygen evolution reactions Li, Jin-Cheng; Hou, Peng-Xiang; Zhao, Shi-Yong Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/C6EE02169G	journal	January 2016
Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction Wang, Jing; Liu, Wei; Luo, Gan Energy & Environmental Science, Vol. 11, Issue 12 https://doi.org/10.1039/C8EE02656D	journal	January 2018
Atomically dispersed metal–nitrogen–carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement He, Yanghua; Liu, Shengwen; Priest, Cameron Chemical Society Reviews, Vol. 49, Issue 11 https://doi.org/10.1039/C9CS00903E	journal	January 2020
Recent advances of noble-metal-free bifunctional oxygen reduction and evolution electrocatalysts Zhao, Chang-Xin; Liu, Jia-Ning; Wang, Juan Chemical Society Reviews, Vol. 50, Issue 13 https://doi.org/10.1039/D1CS00135C	journal	January 2021
A MnO_x enhanced atomically dispersed iron–nitrogen–carbon catalyst for the oxygen reduction reaction Ding, Shichao; Lyu, Zhaoyuan; Sarnello, Erik Journal of Materials Chemistry A, Vol. 10, Issue 11 https://doi.org/10.1039/D1TA07219F	journal	January 2022
Adjacent Fe Site boosts electrocatalytic oxygen evolution at Co site in single-atom-catalyst through a dual-metal-site design Chen, Changli; Sun, Mingzi; Zhang, Fang Energy & Environmental Science, Vol. 16, Issue 4 https://doi.org/10.1039/D2EE03930C	journal	January 2023
Decrypting the Influence of Axial Coordination on the Electronic Microenvironment of Co-N ₅ Site for Enhanced Electrocatalytic Reaction Huang, Bingyu; Huang, Senhe; Lu, Chenbao CCS Chemistry, Vol. 5, Issue 8 https://doi.org/10.31635/ccschem.022.202202241	journal	August 2023

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