Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions
Abstract
Single-atom catalysts (SACs) have attracted widespread interest for many catalytic applications because of their distinguishing properties. However, general and scalable synthesis of efficient SACs remains significantly challenging, which limits their applications. Here we report an efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks (M-N-Grs; M represents Fe, Co, Ni, Cu, etc.) at gram-scale. The highly compatible doped ZnO templates, acting as the dispersants of targeted metal heteroatoms, can react with the incoming gaseous organic ligands to form doped metal-organic framework thin shells, whose composition determines the heteroatom species and contents in M-N-Grs. We achieved over 1.2 atom % (5.85 wt %) metal loading content, superior oxygen reduction activity over commercial Pt/C catalyst, and a very high diffusion-limiting current (6.82 mA cm-2). Both experimental analyses and theoretical calculations reveal the oxygen reduction activity sequence of M-N-Grs. Additionally, the superior performance in Fe-N-Gr is mainly attributed to its unique electron structure, rich exposed active sites, and robust hollow framework: This synthesis strategy will stimulate the rapid development of SACs for diverse energy-related fields.
- Authors:
-
[2];
[6];
[7];
[1]
- Wuhan Univ. of Technology (China)
- Harvard Univ., Cambridge, MA (United States)
- Wuhan Univ. of Science and Technology (China)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- A*STAR (Singapore)
- Univ. of Surrey (United Kingdom)
- Univ. of Melbourne (Australia)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); National Key Research and Development Program of China; Natural Science Foundation of Hubei Province
- OSTI Identifier:
- 1798728
- Grant/Contract Number:
- AC02-06CH11357; 51832004; 51521001; 2016YFA0202603; 2019CFA001; B17034
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 8; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; redox reactions; oxides; metals; catalysts; metal oxide nanoparticles; single-atom catalyst; doped ZnO solid solution; hollow graphene framework; oxygen reduction reaction; universal approach
Citation Formats
Meng, Jiashen, Li, Jiantao, Liu, Jinshuai, Zhang, Xingcai, Jiang, Gengping, Ma, Lu, Hu, Zhi-Yi, Xi, Shibo, Zhao, Yunlong, Yan, Mengyu, Wang, Peiyao, Liu, Xiong, Li, Qidong, Liu, Jefferson Zhe, Wu, Tianpin, and Mai, Liqiang. Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions. United States: N. p., 2020.
Web. doi:10.1021/acscentsci.0c00458.
Meng, Jiashen, Li, Jiantao, Liu, Jinshuai, Zhang, Xingcai, Jiang, Gengping, Ma, Lu, Hu, Zhi-Yi, Xi, Shibo, Zhao, Yunlong, Yan, Mengyu, Wang, Peiyao, Liu, Xiong, Li, Qidong, Liu, Jefferson Zhe, Wu, Tianpin, & Mai, Liqiang. Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions. United States. https://doi.org/10.1021/acscentsci.0c00458
Meng, Jiashen, Li, Jiantao, Liu, Jinshuai, Zhang, Xingcai, Jiang, Gengping, Ma, Lu, Hu, Zhi-Yi, Xi, Shibo, Zhao, Yunlong, Yan, Mengyu, Wang, Peiyao, Liu, Xiong, Li, Qidong, Liu, Jefferson Zhe, Wu, Tianpin, and Mai, Liqiang. Tue .
"Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions". United States. https://doi.org/10.1021/acscentsci.0c00458. https://www.osti.gov/servlets/purl/1798728.
@article{osti_1798728,
title = {Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions},
author = {Meng, Jiashen and Li, Jiantao and Liu, Jinshuai and Zhang, Xingcai and Jiang, Gengping and Ma, Lu and Hu, Zhi-Yi and Xi, Shibo and Zhao, Yunlong and Yan, Mengyu and Wang, Peiyao and Liu, Xiong and Li, Qidong and Liu, Jefferson Zhe and Wu, Tianpin and Mai, Liqiang},
abstractNote = {Single-atom catalysts (SACs) have attracted widespread interest for many catalytic applications because of their distinguishing properties. However, general and scalable synthesis of efficient SACs remains significantly challenging, which limits their applications. Here we report an efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks (M-N-Grs; M represents Fe, Co, Ni, Cu, etc.) at gram-scale. The highly compatible doped ZnO templates, acting as the dispersants of targeted metal heteroatoms, can react with the incoming gaseous organic ligands to form doped metal-organic framework thin shells, whose composition determines the heteroatom species and contents in M-N-Grs. We achieved over 1.2 atom % (5.85 wt %) metal loading content, superior oxygen reduction activity over commercial Pt/C catalyst, and a very high diffusion-limiting current (6.82 mA cm-2). Both experimental analyses and theoretical calculations reveal the oxygen reduction activity sequence of M-N-Grs. Additionally, the superior performance in Fe-N-Gr is mainly attributed to its unique electron structure, rich exposed active sites, and robust hollow framework: This synthesis strategy will stimulate the rapid development of SACs for diverse energy-related fields.},
doi = {10.1021/acscentsci.0c00458},
journal = {ACS Central Science},
number = 8,
volume = 6,
place = {United States},
year = {Tue Jul 07 00:00:00 EDT 2020},
month = {Tue Jul 07 00:00:00 EDT 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Low-Temperature, Solution-Processed and Alkali Metal Doped ZnO for High-Performance Thin-Film Transistors
journal, January 2012
- Park, Si Yun; Kim, Beom Joon; Kim, Kyongjun
- Advanced Materials, Vol. 24, Issue 6
Coordination Tunes Selectivity: Two‐Electron Oxygen Reduction on High‐Loading Molybdenum Single‐Atom Catalysts
journal, April 2020
- Tang, Cheng; Jiao, Yan; Shi, Bingyang
- Angewandte Chemie International Edition, Vol. 59, Issue 23
Atomic cobalt on nitrogen-doped graphene for hydrogen generation
journal, October 2015
- Fei, Huilong; Dong, Juncai; Arellano-Jiménez, M. Josefina
- Nature Communications, Vol. 6, Issue 1
Catalysis by Supported Single Metal Atoms
journal, November 2016
- Liu, Jingyue
- ACS Catalysis, Vol. 7, Issue 1
Non-metal Single-Iodine-Atom Electrocatalysts for the Hydrogen Evolution Reaction
journal, July 2019
- Zhao, Yongqiang; Ling, Tao; Chen, Shuangming
- Angewandte Chemie International Edition, Vol. 58, Issue 35
Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth
journal, November 2017
- Wei, Hehe; Huang, Kai; Wang, Da
- Nature Communications, Vol. 8, Issue 1
The effect of process parameters on the size of ZnO nanoparticles synthesized via the sol–gel technique
journal, February 2013
- Ba-Abbad, Muneer M.; Kadhum, Abdul Amir H.; Bakar Mohamad, Abu
- Journal of Alloys and Compounds, Vol. 550
Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction
journal, April 2017
- Chen, Yuanjun; Ji, Shufang; Wang, Yanggang
- Angewandte Chemie International Edition, Vol. 56, Issue 24
Heterogeneous single-atom catalysis
journal, May 2018
- Wang, Aiqin; Li, Jun; Zhang, Tao
- Nature Reviews Chemistry, Vol. 2, Issue 6
Self-Supported Earth-Abundant Nanoarrays as Efficient and Robust Electrocatalysts for Energy-Related Reactions
journal, May 2018
- Liu, Jinlong; Zhu, Dongdong; Zheng, Yao
- ACS Catalysis, Vol. 8, Issue 7
Direct transformation of bulk copper into copper single sites via emitting and trapping of atoms
journal, October 2018
- Qu, Yunteng; Li, Zhijun; Chen, Wenxing
- Nature Catalysis, Vol. 1, Issue 10
Boosting oxygen reduction catalysis with abundant copper single atom active sites
journal, January 2018
- Li, Feng; Han, Gao-Feng; Noh, Hyuk-Jun
- Energy & Environmental Science, Vol. 11, Issue 8
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013
- Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
- Accounts of Chemical Research, Vol. 46, Issue 8
General Oriented Synthesis of Precise Carbon-Confined Nanostructures by Low-Pressure Vapor Superassembly and Controlled Pyrolysis
journal, November 2017
- Meng, Jiashen; Liu, Xiong; Li, Jiantao
- Nano Letters, Vol. 17, Issue 12
Ultrafine jagged platinum nanowires enable ultrahigh mass activity for the oxygen reduction reaction
journal, November 2016
- Li, Mufan; Zhao, Zipeng; Cheng, Tao
- Science, Vol. 354, Issue 6318
Photochemical route for synthesizing atomically dispersed palladium catalysts
journal, May 2016
- Liu, P.; Zhao, Y.; Qin, R.
- Science, Vol. 352, Issue 6287
Platinum single-atom and cluster catalysis of the hydrogen evolution reaction
journal, November 2016
- Cheng, Niancai; Stambula, Samantha; Wang, Da
- Nature Communications, Vol. 7, Issue 1
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011
- Suntivich, J.; May, K. J.; Gasteiger, H. A.
- Science, Vol. 334, Issue 6061
Metal-Free Catalysts for Oxygen Reduction Reaction
journal, May 2015
- Dai, Liming; Xue, Yuhua; Qu, Liangti
- Chemical Reviews, Vol. 115, Issue 11
Atomic Mechanism of Electrocatalytically Active Co–N Complexes in Graphene Basal Plane for Oxygen Reduction Reaction
journal, November 2015
- Li, Feng; Shu, Haibo; Hu, Chenli
- ACS Applied Materials & Interfaces, Vol. 7, Issue 49
Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation
journal, January 2020
- Zhao, Di; Zhuang, Zewen; Cao, Xing
- Chemical Society Reviews, Vol. 49, Issue 7
Hierarchically Porous M-N-C (M = Co and Fe) Single-Atom Electrocatalysts with Robust MN x Active Moieties Enable Enhanced ORR Performance
journal, August 2018
- Zhu, Chengzhou; Shi, Qiurong; Xu, Bo Z.
- Advanced Energy Materials, Vol. 8, Issue 29
A universal principle for a rational design of single-atom electrocatalysts
journal, April 2018
- Xu, Haoxiang; Cheng, Daojian; Cao, Dapeng
- Nature Catalysis, Vol. 1, Issue 5
Highly doped and exposed Cu( i )–N active sites within graphene towards efficient oxygen reduction for zinc–air batteries
journal, January 2016
- Wu, Haihua; Li, Haobo; Zhao, Xinfei
- Energy & Environmental Science, Vol. 9, Issue 12
Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction
journal, November 2017
- Chen, Wenxing; Pei, Jiajing; He, Chun-Ting
- Angewandte Chemie International Edition, Vol. 56, Issue 50
Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials
journal, August 2015
- Zitolo, Andrea; Goellner, Vincent; Armel, Vanessa
- Nature Materials, Vol. 14, Issue 9
Graphene Defects Trap Atomic Ni Species for Hydrogen and Oxygen Evolution Reactions
journal, February 2018
- Zhang, Longzhou; Jia, Yi; Gao, Guoping
- Chem, Vol. 4, Issue 2
Direct observation of noble metal nanoparticles transforming to thermally stable single atoms
journal, July 2018
- Wei, Shengjie; Li, Ang; Liu, Jin-Cheng
- Nature Nanotechnology, Vol. 13, Issue 9
Simple-Cubic Carbon Frameworks with Atomically Dispersed Iron Dopants toward High-Efficiency Oxygen Reduction
journal, February 2017
- Wang, Biwei; Wang, Xinxia; Zou, Jinxiang
- Nano Letters, Vol. 17, Issue 3
Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions
journal, January 2015
- Jiao, Yan; Zheng, Yao; Jaroniec, Mietek
- Chemical Society Reviews, Vol. 44, Issue 8
Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation
journal, September 2017
- Zhang, Hanguang; Hwang, Sooyeon; Wang, Maoyu
- Journal of the American Chemical Society, Vol. 139, Issue 40
Microwave-Assisted Rapid Synthesis of Graphene-Supported Single Atomic Metals
journal, July 2018
- Fei, Huilong; Dong, Juncai; Wan, Chengzhang
- Advanced Materials, Vol. 30, Issue 35
Single-Atom Electrocatalysts
journal, October 2017
- Zhu, Chengzhou; Fu, Shaofang; Shi, Qiurong
- Angewandte Chemie International Edition, Vol. 56, Issue 45
Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene
journal, November 2017
- Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira
- ACS Central Science, Vol. 3, Issue 12
A single iron site confined in a graphene matrix for the catalytic oxidation of benzene at room temperature
journal, December 2015
- Deng, Dehui; Chen, Xiaoqi; Yu, Liang
- Science Advances, Vol. 1, Issue 11
Harnessing the Wisdom in Colloidal Chemistry to Make Stable Single-Atom Catalysts
journal, July 2018
- Hülsey, Max J.; Zhang, Jiaguang; Yan, Ning
- Advanced Materials, Vol. 30, Issue 47
Advances in metal–organic framework coatings: versatile synthesis and broad applications
journal, January 2020
- Meng, Jiashen; Liu, Xiong; Niu, Chaojiang
- Chemical Society Reviews, Vol. 49, Issue 10
Heteroatom-Doped Transition Metal Electrocatalysts for Hydrogen Evolution Reaction
journal, February 2019
- Jin, Huanyu; Liu, Xin; Chen, Shuangming
- ACS Energy Letters, Vol. 4, Issue 4
Single-Atom Pd 1 /Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene
journal, August 2015
- Yan, Huan; Cheng, Hao; Yi, Hong
- Journal of the American Chemical Society, Vol. 137, Issue 33
Strategies for Stabilizing Atomically Dispersed Metal Catalysts
journal, December 2017
- Qin, Ruixuan; Liu, Pengxin; Fu, Gang
- Small Methods, Vol. 2, Issue 1
Ferromagnetism and possible application in spintronics of transition-metal-doped ZnO films
journal, June 2008
- Pan, F.; Song, C.; Liu, X. J.
- Materials Science and Engineering: R: Reports, Vol. 62, Issue 1
Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction
journal, February 2018
- Yang, Hong Bin; Hung, Sung-Fu; Liu, Song
- Nature Energy, Vol. 3, Issue 2
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018
- Liu, Lichen; Corma, Avelino
- Chemical Reviews, Vol. 118, Issue 10
Gelatin-derived sustainable carbon-based functional materials for energy conversion and storage with controllability of structure and component
journal, February 2015
- Wang, Zhong-Li; Xu, Dan; Zhong, Hai-Xia
- Science Advances, Vol. 1, Issue 1
Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst
journal, August 2017
- Chung, Hoon T.; Cullen, David A.; Higgins, Drew
- Science, Vol. 357, Issue 6350
Metal (Hydr)oxides@Polymer Core–Shell Strategy to Metal Single-Atom Materials
journal, August 2017
- Zhang, Maolin; Wang, Yang-Gang; Chen, Wenxing
- Journal of the American Chemical Society, Vol. 139, Issue 32
Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017
- Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
- Science, Vol. 355, Issue 6321
A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions
journal, April 2015
- Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai
- Nature Nanotechnology, Vol. 10, Issue 5
General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities
journal, January 2018
- Fei, Huilong; Dong, Juncai; Feng, Yexin
- Nature Catalysis, Vol. 1, Issue 1
Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts
journal, August 2016
- Yin, Peiqun; Yao, Tao; Wu, Yuen
- Angewandte Chemie International Edition, Vol. 55, Issue 36