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; Shuai, Ling; Li, Yizhe; Cao, Rui; Qiu, Ming; Zhuang, Xiaodong; Leung, Michael K.  H.; Chen, Yiwang; Scherf, Ullrich

doi:10.1021/jacs.9b11852

Title: Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination

Journal Article · Mon Jan 06 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11852· OSTI ID:1604565

^[1]; Lützenkirchen-Hecht, Dirk ^[2]; Li, Longbin ^[3]; Shuai, Ling ^[4]; Li, Yizhe ^[3]; Cao, Rui ^[5]; Qiu, Ming ^[4];

^[6]; Leung, Michael K. H. ^[7];

^[3]; Scherf, Ullrich ^[2]

Nanchang Univ., (China). College of Chemistry/Inst. of Polymers and Energy Chemistry; Bergische Univ. (Germany). Macromolecular Chemistry Group and Inst. for Polymer Technology
Bergische Univ. (Germany). Macromolecular Chemistry Group and Inst. for Polymer Technology
Nanchang Univ., (China). College of Chemistry/Inst. of Polymers and Energy Chemistry
Central China Normal Univ., Wuhan (China). Inst. of Nanoscience and Nanotechnology, College of Physical Science and Technology
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Shanghai Jiao Tong Univ. (China). Meso-Entropy Matter Lab, Shanghai Key Lab. of Electrical Insulation and Thermal Ageing, State Key Lab. of Metal Matrix Composites, School of Chemistry and Chemical Engineering
City Univ. of Hong Kong (Hong Kong). Inst. Ability R&D Energy Research Centre, School of Energy and Environment

Atomically dispersed transition metal active sites have emerged as one of the most important fields of study because they display promising performance in catalysis and have the potential to serve as ideal models for fundamental understanding. However, both the preparation and determination of such active sites remain a challenge. The structural engineering of carbon- and nitrogen-coordinated metal sites (M–N–C, M = Fe, Co, Ni, Mn, Cu, etc.) via employing new heteroatoms, e.g., P and S, remains challenging. In this study, carbon nanosheets embedded with nitrogen and phosphorus dual-coordinated iron active sites (denoted as Fe-N/P-C) were developed and determined using cutting edge techniques. Both experimental and theoretical results suggested that the N and P dual-coordinated iron sites were favorable for oxygen intermediate adsorption/desorption, resulting in accelerated reaction kinetics and promising catalytic oxygen reduction activity. This work not only provides efficient way to prepare well-defined single-atom active sites to boost catalytic performance but also paves the way to identify the dual-coordinated single metal atom sites.

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Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-76SF00515; 2018M632599; 18PJ1406100; 19JC412600; CCNU18TS045; BX201700112; 2018CFB531; 21704038; 21720102002; 5171101862; 51722304; 51761135114; 51811530013; 51973114; 20171ACB21009; 2018ACB21021; 20192BCB23001; 2017YFE9134000

OSTI ID:: 1604565

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 5; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 391 works

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References (55)

Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks Chong, Lina; Wen, Jianguo; Kubal, Joseph Science, Vol. 362, Issue 6420 https://doi.org/10.1126/science.aau0630	journal	November 2018
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
Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells Li, Jiazhan; Chen, Mengjie; Cullen, David A. Nature Catalysis, Vol. 1, Issue 12 https://doi.org/10.1038/s41929-018-0164-8	journal	October 2018
Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems Gewirth, Andrew A.; Varnell, Jason A.; DiAscro, Angela M. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00335	journal	December 2017
Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst Chung, Hoon T.; Cullen, David A.; Higgins, Drew Science, Vol. 357, Issue 6350 https://doi.org/10.1126/science.aan2255	journal	August 2017
Tunable intrinsic strain in two-dimensional transition metal electrocatalysts Wang, Lei; Zeng, Zhenhua; Gao, Wenpei Science, Vol. 363, Issue 6429 https://doi.org/10.1126/science.aat8051	journal	February 2019
In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces Dong, Jin-Chao; Zhang, Xia-Guang; Briega-Martos, Valentín Nature Energy, Vol. 4, Issue 1 https://doi.org/10.1038/s41560-018-0292-z	journal	December 2018
Identification of active sites for acidic oxygen reduction on carbon catalysts with and without nitrogen doping Jia, Yi; Zhang, Longzhou; Zhuang, Linzhou Nature Catalysis, Vol. 2, Issue 8 https://doi.org/10.1038/s41929-019-0297-4	journal	June 2019
Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms Qu, Yunteng; Li, Zhijun; Chen, Wenxing Nature Catalysis, Vol. 1, Issue 10 https://doi.org/10.1038/s41929-018-0146-x	journal	October 2018
Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction Wang, Jing; Huang, Zhengqing; Liu, Wei Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10385	journal	November 2017
Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction Chen, Yuanjun; Ji, Shufang; Wang, Yanggang Angewandte Chemie International Edition, Vol. 56, Issue 24 https://doi.org/10.1002/anie.201702473	journal	April 2017
Coordination of Atomic Co–Pt Coupling Species at Carbon Defects as Active Sites for Oxygen Reduction Reaction Zhang, Longzhou; Fischer, Julia Melisande Theresa Agatha; Jia, Yi Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b04647	journal	July 2018
Multiscale Principles To Boost Reactivity in Gas-Involving Energy Electrocatalysis Tang, Cheng; Wang, Hao-Fan; Zhang, Qiang Accounts of Chemical Research, Vol. 51, Issue 4 https://doi.org/10.1021/acs.accounts.7b00616	journal	January 2018
Carbon-based metal-free catalysts Liu, Xien; Dai, Liming Nature Reviews Materials, Vol. 1, Issue 11 https://doi.org/10.1038/natrevmats.2016.64	journal	September 2016
Few-layer graphdiyne doped with sp-hybridized nitrogen atoms at acetylenic sites for oxygen reduction electrocatalysis Zhao, Yasong; Wan, Jiawei; Yao, Huiying Nature Chemistry, Vol. 10, Issue 9 https://doi.org/10.1038/s41557-018-0100-1	journal	August 2018
Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction Gong, K.; Du, F.; Xia, Z. Science, Vol. 323, Issue 5915, p. 760-764 https://doi.org/10.1126/science.1168049	journal	February 2009
Carbon‐Based Metal‐Free ORR Electrocatalysts for Fuel Cells: Past, Present, and Future Yang, Lijun; Shui, Jianglan; Du, Lei Advanced Materials, Vol. 31, Issue 13 https://doi.org/10.1002/adma.201804799	journal	January 2019
Chemical Approaches to Carbon‐Based Metal‐Free Catalysts Liu, Dong; Dai, Liming; Lin, Xuanni Advanced Materials, Vol. 31, Issue 13 https://doi.org/10.1002/adma.201804863	journal	January 2019
Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts Guo, D.; Shibuya, R.; Akiba, C. Science, Vol. 351, Issue 6271 https://doi.org/10.1126/science.aad0832	journal	January 2016
A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai Nature Nanotechnology, Vol. 10, Issue 5 https://doi.org/10.1038/nnano.2015.48	journal	April 2015
In situ nanoarchitecturing and active-site engineering toward highly efficient carbonaceous electrocatalysts Yuan, Kai; Lu, Chenbao; Sfaelou, Stavroula Nano Energy, Vol. 59 https://doi.org/10.1016/j.nanoen.2019.02.043	journal	May 2019
Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications Chen, Yuanjun; Ji, Shufang; Chen, Chen Joule, Vol. 2, Issue 7 https://doi.org/10.1016/j.joule.2018.06.019	journal	July 2018
Hollow N-Doped Carbon Spheres with Isolated Cobalt Single Atomic Sites: Superior Electrocatalysts for Oxygen Reduction Han, Yunhu; Wang, Yang-Gang; Chen, Wenxing Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10194	journal	November 2017
Atomic Fe Dispersed on N-Doped Carbon Hollow Nanospheres for High-Efficiency Electrocatalytic Oxygen Reduction Chen, Yifan; Li, Zhijuan; Zhu, Yanbo Advanced Materials, Vol. 31, Issue 8 https://doi.org/10.1002/adma.201806312	journal	December 2018
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa Nature Materials, Vol. 14, Issue 9 https://doi.org/10.1038/nmat4367	journal	August 2015
−60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance Huang, Kai; Zhang, Le; Xu, Ting Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08484-8	journal	February 2019
Cascade anchoring strategy for general mass production of high-loading single-atomic metal-nitrogen catalysts Zhao, Lu; Zhang, Yun; Huang, Lin-Bo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09290-y	journal	March 2019
Ultrahigh‐Loading Zinc Single‐Atom Catalyst for Highly Efficient Oxygen Reduction in Both Acidic and Alkaline Media Li, Jia; Chen, Siguo; Yang, Na Angewandte Chemie International Edition, Vol. 58, Issue 21 https://doi.org/10.1002/anie.201902109	journal	May 2019
A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen-Doped Carbon-Nanosphere-Supported Metal Isolated-Single-Atomic-Site Catalysts Han, Aijuan; Chen, Wenxing; Zhang, Shaolong Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201706508	journal	March 2018
Edge-Site Engineering of Atomically Dispersed Fe–N ₄ by Selective C–N Bond Cleavage for Enhanced Oxygen Reduction Reaction Activities Jiang, Rui; Li, Li; Sheng, Tian Journal of the American Chemical Society, Vol. 140, Issue 37 https://doi.org/10.1021/jacs.8b07294	journal	August 2018
An Isolated Zinc-Cobalt Atomic Pair for Highly Active and Durable Oxygen Reduction Lu, Ziyang; Wang, Bo; Hu, Yongfeng Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201810175	journal	February 2019
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
A Tannic Acid-Derived N-, P-Codoped Carbon-Supported Iron-Based Nanocomposite as an Advanced Trifunctional Electrocatalyst for the Overall Water Splitting Cells and Zinc-Air Batteries Qin, Qing; Jang, Haeseong; Li, Ping Advanced Energy Materials, Vol. 9, Issue 5 https://doi.org/10.1002/aenm.201803312	journal	December 2018
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
Versatile Strategy for Tuning ORR Activity of a Single Fe-N ₄ Site by Controlling Electron-Withdrawing/Donating Properties of a Carbon Plane Mun, Yeongdong; Lee, Seonggyu; Kim, Kyeounghak Journal of the American Chemical Society, Vol. 141, Issue 15 https://doi.org/10.1021/jacs.8b13543	journal	March 2019
Atomically dispersed nickel–nitrogen–sulfur species anchored on porous carbon nanosheets for efficient water oxidation Hou, Yang; Qiu, Ming; Kim, Min Gyu Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09394-5	journal	March 2019
Carbon Nanosheets Containing Discrete Co-N _x -B _y -C Active Sites for Efficient Oxygen Electrocatalysis and Rechargeable Zn–Air Batteries Guo, Yingying; Yuan, Pengfei; Zhang, Jianan ACS Nano, Vol. 12, Issue 2 https://doi.org/10.1021/acsnano.7b08721	journal	January 2018
Atomically Dispersed Iron-Nitrogen Species as Electrocatalysts for Bifunctional Oxygen Evolution and Reduction Reactions Chen, Pengzuo; Zhou, Tianpei; Xing, Lili Angewandte Chemie International Edition, Vol. 56, Issue 2 https://doi.org/10.1002/anie.201610119	journal	December 2016
A Bifunctional Hybrid Electrocatalyst for Oxygen Reduction and Evolution: Cobalt Oxide Nanoparticles Strongly Coupled to B,N-Decorated Graphene Tong, Yun; Chen, Pengzuo; Zhou, Tianpei Angewandte Chemie International Edition, Vol. 56, Issue 25 https://doi.org/10.1002/anie.201702430	journal	May 2017
Ultrathin Nitrogen-Doped Holey Carbon@Graphene Bifunctional Electrocatalyst for Oxygen Reduction and Evolution Reactions in Alkaline and Acidic Media Sun, Jiqing; Lowe, Sean E.; Zhang, Lijuan Angewandte Chemie International Edition, Vol. 57, Issue 50 https://doi.org/10.1002/anie.201811573	journal	November 2018
Two-Dimensional Core-Shelled Porous Hybrids as Highly Efficient Catalysts for the Oxygen Reduction Reaction Yuan, Kai; Zhuang, Xiaodong; Fu, Haiyan Angewandte Chemie International Edition, Vol. 55, Issue 24 https://doi.org/10.1002/anie.201600850	journal	April 2016
N,P Co‐Coordinated Manganese Atoms in Mesoporous Carbon for Electrochemical Oxygen Reduction Zhu, Xiaofeng; Amal, Rose; Lu, Xunyu Small, Vol. 15, Issue 29 https://doi.org/10.1002/smll.201804524	journal	January 2019
Efficient Electrochemical and Photoelectrochemical Water Splitting by a 3D Nanostructured Carbon Supported on Flexible Exfoliated Graphene Foil Hou, Yang; Qiu, Ming; Zhang, Tao Advanced Materials, Vol. 29, Issue 3 https://doi.org/10.1002/adma.201604480	journal	November 2016
MOF-Derived Bifunctional Cu ₃ P Nanoparticles Coated by a N,P-Codoped Carbon Shell for Hydrogen Evolution and Oxygen Reduction Wang, Rui; Dong, Xi-Yan; Du, Jiao Advanced Materials, Vol. 30, Issue 6 https://doi.org/10.1002/adma.201703711	journal	December 2017
N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions Zhang, Jintao; Qu, Liangti; Shi, Gaoquan Angewandte Chemie International Edition, Vol. 55, Issue 6 https://doi.org/10.1002/anie.201510495	journal	December 2015
In Situ Self-Template Synthesis of Fe–N-Doped Double-Shelled Hollow Carbon Microspheres for Oxygen Reduction Reaction Huang, Zheng; Pan, Hongyu; Yang, Wenji ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b05832	journal	January 2018
Novel Iron/Cobalt-Containing Polypyrrole Hydrogel-Derived Trifunctional Electrocatalyst for Self-Powered Overall Water Splitting Yang, Jia; Wang, Xu; Li, Bo Advanced Functional Materials, Vol. 27, Issue 17 https://doi.org/10.1002/adfm.201606497	journal	March 2017
Atomically Dispersed Transition Metals on Carbon Nanotubes with Ultrahigh Loading for Selective Electrochemical Carbon Dioxide Reduction Cheng, Yi; Zhao, Shiyong; Johannessen, Bernt Advanced Materials, Vol. 30, Issue 13 https://doi.org/10.1002/adma.201706287	journal	February 2018
A Bimetallic Zn/Fe Polyphthalocyanine-Derived Single-Atom Fe-N ₄ Catalytic Site:A Superior Trifunctional Catalyst for Overall Water Splitting and Zn-Air Batteries Pan, Yuan; Liu, Shoujie; Sun, Kaian Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201804349	journal	May 2018
A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature Deng, Dehui; Chen, Xiaoqi; Yu, Liang Science Advances, Vol. 1, Issue 11 https://doi.org/10.1126/sciadv.1500462	journal	December 2015
Magnetic and hyperfine properties of Fe2P nanoparticles dispersed in a porous carbon matrix Viali, G. L.; Gonçalves, G. R.; Passamani, E. C. Journal of Magnetism and Magnetic Materials, Vol. 401 https://doi.org/10.1016/j.jmmm.2015.10.028	journal	March 2016
Gelatin-derived sustainable carbon-based functional materials for energy conversion and storage with controllability of structure and component Wang, Zhong-Li; Xu, Dan; Zhong, Hai-Xia Science Advances, Vol. 1, Issue 1 https://doi.org/10.1126/sciadv.1400035	journal	February 2015
Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction Yang, Liu; Cheng, Daojian; Xu, Haoxiang Proceedings of the National Academy of Sciences, Vol. 115, Issue 26 https://doi.org/10.1073/pnas.1800771115	journal	June 2018
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
Reactive Multifunctional Template-Induced Preparation of Fe-N-Doped Mesoporous Carbon Microspheres Towards Highly Efficient Electrocatalysts for Oxygen Reduction Meng, Fan-Lu; Wang, Zhong-Li; Zhong, Hai-Xia Advanced Materials, Vol. 28, Issue 36 https://doi.org/10.1002/adma.201602490	journal	July 2016

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Title: Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination

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