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清华大学成会明和周光敏课题组--石墨烯支持的单原子催化剂实现MoS2和Mo/Na2S之间的高效可逆转化

 石墨烯研究 2021-08-31

由于相对较高的容量和本质安全性,基于转换型金属硫化物 (MS) 钠离子电池 (SIBs) 负极引起了极大的关注。M/Na2S 在电荷中高度可逆地转化为原始MS,对电化学性能起着至关重要的作用。在这里,以传统的 MoS2 为例,在理论模拟的指导下,选择了氮掺杂石墨烯上的铁单原子催化剂(SAFe@NG),并首先将其用作基材,以促进 MoS2 在放电过程中的反应动力学。在接下来的充电过程中,结合光谱学和显微镜,证明了 SAFe@NG 催化剂能够实现 Mo/Na2S→NaMoS2→MoS2 的高效可逆转化反应。此外,理论模拟表明可逆转换机制显示出良好的形成能垒和反应动力学,其中具有 Fe-N4 配位中心的 SAFe@NG 促进了 Na2S/Mo 的均匀分散以及 Na2S NaMoS2 的分解。因此,SAFe@NG 催化剂可以实现高效的可逆转化反应 MoS2↔NaMoS2↔Mo/Na2S。这项工作为设计具有高效可逆机制的转换型材料提供了新的途径。

 Figure 1. MoS2在石墨烯、NGSAFe@NGSACo@NGSANi@NG SACu@NG 上的 a) 吸附能和 b) DOS(a) 中的插图是SAFe@NGMoS2吸附配置的侧视图。SAFe@NG的 c) TEM图像,d) HAADF图像和EDS映射图像,以及 e) AC-STEM-ADF图像,红色圆圈代表Fe单原子。f) SAFe@NGFe箔和FePcNEXAFS光谱的Fe L-edgeSAFe@NGFe箔、FePcFe3O4Fe K-edge g) XANES 光谱和 h) FT-EXAFS 光谱。

Figure 2. MoS2/SAFe@NGa) SEM图像和 b) TEM 图像。MoS2/SAFe@NG的 c) HAADF 图像,以及 d)相应EDS映射图像。e) MoS2/SACu@NGHRTEM图像。(e) 中的插图是 SAED 图案。f,g) MoS2/SAFe@NGAC-STEM-ADF图像,红色圆圈代表 Fe 单原子。h) SAFe@NGMoS2/SAFe@NGN 1s XPS 光谱。i) MoS2MoS2/GMoS2/NGMoS2/SAFe@NGMo 3dS 2p XPS 光谱。(e) 中的插图是MoS2/GMoS2/SAFe@NG的电荷密度差异。

Figure 3. MoS2/SAFe@NG 用于 SIBs 的电化学性能和反应动力学。

Figure 4. MoS2/SAFe@NG SIBs 的电化学反应机理。

Figure 5. 充电过程中可逆转换机制的理论模拟。

相关研究成果于2021年由清华大学Guangmin ZhouHui-Ming Cheng课题组,以及北航大学Qianfan Zhang课题组,发表在Adv. Mater.DOI: 10.1002/adma.202007090)上。原文:Efficient Reversible Conversion between MoS2 and Mo/Na2S Enabled by Graphene-Supported Single Atom Catalysts

Hui-Ming Cheng

Office:Nanshan Zhiyuan,C2-701
Email:chenghm@sz.tsinghua.edu.cn

Biography
Prof. Hui-Ming Cheng is a member of Chinese Academy of Sciences and a fellow of TWAS. He graduated from Hunan University, China in 1984 and received his Ph. D from Institute of Metal Research, Chinese Academy of Sciences (IMR CAS). He is a Professor andthe founding director of both the  Advanced Carbon Research Division of Shenyang National Laboratory for Materials Science,IMR CAS.His research activities focus on carbon nanotubes, graphene, other two-dimensional materials, energy storage materials, photocatalytic semiconducting materials, and bulk carbon materials.He has published over 580 paperswith close to 60,000 citations, an H-index of 106 and 84 ESI highly-cited papers(from 2008 to 2017), and is recognized as a Highly Cited Researcher in both materials science and chemistry fields by Clarivate Analytics (formerThomson Reuters). He has won both domestic and internationalawards including the State Natural Science Award of China in 2006 and 2017, Charles E. Pettinos Award from American Carbon Society in 2010, Felcht Award from SGL, Germany in 2015, and ACS Nano Lecture Award from American Chemical Society in 2017.He used to beanEditor of New Carbon Materialsfrom 1998 to 2015Energy Storage Materialssince 2015 and Associate Editor of Research Interests:
Synthesis, characterization and applications of carbon nanotubes, graphene and other low-dimensional materials;
Design and synthesis of nanostructured materials for clean energy applications;
Exploration of photochemically active materials for water-splitting and CO2 conversion;
Fabrication and applications of high-performance bulk carbon materials such as isotropic pyrolytic carbon and C/C composites.

Education
1992 Ph. D., Materials Science, IMR CAS, China
1987 M. S., Materials Science, IMR CAS, China
1984 B. S., Materials Science, Hunan University, Changsha, China

Professional Experience
Director and Professor, Low-Dimensional Material and Device Laboratory, Tsinghua-Berkeley Shenzhen Institute, Tsinghua University (9 months per year)  June 2016-now
Director and Professor, Advanced Carbon Division, Shenyang National Laboratory for Materials Science, IMR CAS (3 months per year)  June 2016-now
Director and Professor, Advanced Carbon Division, Shenyang National Laboratory for Materials Science, IMR CAS May 2001-May 2016
DeputyDirector (1st, 2nd and 3rd term), IMR CAS, China July 1998-July 2012
Professor, IMR CAS, China Nov. 1994-May 2001
Associate Professor, IMR CAS, China Sept. 1993-Oct. 1994
 
Research Associate, Faculty of Engineering, Nagasaki University, Japan April 1992-Aug. 1993
Working Experience at Foreign Institutions:
JSPS Fellow, Nagasaki University, Japan Feb. 2008-Feb. 2008 
TCT Fellow, Nanyang University of Technology, Singapore Feb. 2002-Feb. 2002 
Exchange Scientist, Australian Academy of Sciences, AU Apr. 2001-May 2001 
Invited Visiting Scientist, Japan Association for Promotion of Industrial Technology, Japan Feb. 2000-Mar. 2000
Senior Visiting Scientist, Dept. of Physics, MIT, USA. Nov. 1997-May 1998
Invited Researcher, Kyushu National Industrial Research Institute, AIST, Japan. Sept. 1996-Nov. 1996
April 1990-Mar. 1992

Publications
Representative Publications (*denotes corresponding author):
1.H. M. Cheng*, F. Li, G. Su, H. Y. Pan, L. L. He, X. Sun, M. S. Dresselhaus, Large-scale and low-cost synthesis of single-walled carbon nanotubes by the catalytic pyrolysis of hydrocarbons, Appl Phys Lett72 (25), 3282-3284, (1998).
2.H. M. Cheng*, F. Li, X. Sun, S. D. M. Brown, M. A. Pimenta, A. Marucci, G. Dresselhaus, M. S. Dresselhaus, Bulk morphology and diameter distribution of single-walled carbon nanotubes synthesized by catalytic decomposition of hydrocarbons, Chem Phys Lett 289, 602-610, (1998).
3.H. G. Yang, C. H. Sun, S. Z. Qiao*, J. Zou, G. Liu, S. C. Smith, H. M. Cheng, G. Q. Lu*, Anatase TiO2 single crystals with a large percentage of reactive facets, Nature 453 (7195), 638-642, (2008).
4.G. Liu, Y. N. Zhao, C. H. Sun, F. Li, G. Q. Lu*, H. M. Cheng*, Synergistic effects of B/N doping on the visible-light photocatalytic activity of mesoporous TiO2, Angewandte Chemie-Intern Edit47 (24), 4516-4520, (2008).
5.B. L. Liu, W. C. Ren*, L. B. Gao, S. S. Li, S. F. Pei, C. Liu, C. B. Jiang, H. M. Cheng*, Metal-catalyst-free growth of single-walled carbon nanotubes,JACS131 (6), 2082-2083, (2009).
6.Z. S. Wu, S. F. Pei, W. C. Ren*, D. M. Tang, L. B. Gao, B. L. Liu, F. Li, C. Liu, H. M. Cheng*, Field emission of single-layer graphene films prepared by electrophoretic deposition, Adv Mater21 (17), 1756-1760, (2009).
7.Z. P. Chen†, W. C. Ren†, L. B. Gao, B. L. Liu, S. F. Pei, H. M. Cheng*, Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition, Nature Mater 10 (6), 424-428(2011).
8.L. B. Gao†, W. C. Ren†, H. L. Xu, L. Jin, Z. X. Wang, T. Ma, L. P. Ma, Z. Y. Zhang, Q. Fu, L. M. Peng, X. H. Bao, H. M. Cheng*, Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum, Nature Commun 3, 699, (2012).
9.C. Xu†, L. B. Wang†, Z. B. Liu, L. Chen, J. K. Guo, N. Kang*, X. L. Ma, H. M. Cheng, W. C. Ren*, Large-area high-quality 2D ultrathin Mo2C superconducting crystals, Nature Mater 14 (11), 1135-1141, (2015).
10.Y. Gao, Z. B. Liu, D. M. Sun, L. Huang, L. P. Ma, L. C. Yin, T. Ma, Z. Y. Zhang, X. L. Ma, L. M. Peng, H. M. Cheng, W. C. Ren*, Large-area synthesis of high-quality and uniform monolayer WS2 on reusable Au foilsNature Commun 6, 8569, (2015).
11.F. Zhang†, P. X. Hou†, C. Liu*, B. W. Wang, H. Jiang, M. L. Chen, D. M. Sun,J.C. Li, H. T. Cong, E. I. Kauppinen, H. M. Cheng*, Growth of semiconducting single-wall carbon nanotubes with a narrow band-gap distribution, Nature Commun 7, 11160, (2016).
12.Y. Liu, Y. T. Shen, L. T. Sun*, J. C. Li, C. Liu, W. C. Ren, F. Li, L. B. Gao, J. Chen, F. C. Liu, Y. Y. Sun, N. J. Tang*, H. M. Cheng*, Y. W. Du, Elemental superdoping of graphene and carbon nanotubes, Nature Commun 7, 10921, (2016).
13.T. Ma, Z. B. Liu, J. X. Wen, Y. Gao, X. B. Ren, H. J. Chen, C. H. Jin, X. L. Ma, N. S. Xu, H. M. Cheng*, W. C. Ren*, Tailoring the thermal and electrical transport properties of graphene films by grain size engineering, Nature Commun 8, 14486, (2017).
14.Z. K. Zhang, J. H. Du, D. D. Zhang, H. D. Sun, L. C. Yin, L. P. Ma, J. S. Chen, D. G. Ma, H. M. Cheng, W. C. Ren*, Rosin-enabled ultraclean and damage-free transfer of graphene for large-area flexible organic light-emitting diodes, Nature Commun 8, 14560, (2017).
15.Z. H. Sun, J. Q. Zhang, L. C. Yin, G. J. Hu, R. P. Fang, H. M. Cheng, F. Li*, Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries, Nature Commun 8, 14627, (2017).
16.J. Zhao†, G. M. Zhou†, K. Yan, J. Xie, Y. Z. Li, L. Liao, Y. Jin, K. Liu, P. C. Hsu, J. Y. Wang, H. M. Cheng, Y. Cui*, Air-stable and freestanding lithium alloy/graphene foil as an alternative to lithium metal anodes, Nature Nano 12 (10), 993-999, (2017).
17.S. F. Pei, Q. W. Wei, K. Huang, H. M. Cheng, W. C. Ren*, Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation, Nature Commun 9, 145 (2018)
18.K. H. Thebo, X. T. Qian, Q. Zhang, L. Chen, H. M. Cheng, W. C. Ren*, Highly stable graphene-oxide-based membranes with superior permeability, Nature Commun 9, 1486, (2018).
19.S. Jiang†, P. X. Hou†, M. L. Chen, B. W. Wang, D. M. Sun, D. M. Tang, Q. Jin, Q. X. Guo, D. D. Zhang, J. H. Du, K. P. Tai, J. Tan, E. I. Kauppinen, C. Liu*, H. M. Cheng*, Ultrahigh-performance transparent conductive films of carbon-welded isolated single-wall carbon nanotubes, Science Advances 4 (5), 9264, (2018).
20.M. Wang, C. L. Jiang, S. Q. Zhang, X. H. Song, Y. B. Tang*, H. M. Cheng*, Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage, Nature Chem 10 (6), 667-672, (2018).

Awards
2017: The 2nd class National Natural Science Award (Basic Research on Synthesis and Application of High-Quality Graphene Materials), China
2017: The 1st class Natural Science Award of Liaoning Province (Design and Fabrication of Photocatalytic Materials for Solar Energy ), China
2017:The ACS Nano Lecture Award, American Chemical Society
2015: The 1st class Natural Science Award of Liaoning Province (Synthesis and Application Explorations of Graphene Materials), China
2015: The Utz-Hellmuth Felcht Award, SGL Group, Germany
2012: Distinguished Award for Novel Materials and Their Synthesis (NMS), IUPAC and Organization Committee of NMS
2012: Award for Scientific and Technological Progress (2nd class) of Ministry of Industry and Information Technology, China
2010: Prize for Scientific and Technological Progress of Ho Leung Ho Lee Foundation, China
2010: The Charles E. Pettinos Award, American Carbon Society, USA
2007: The Khwarizmi International Award, Iran
2006: The 2nd class National Natural Science Award (Synthesis and Study of Single-Walled and Double-Walled Carbon Nanotubes), China
2003: The 1st class Natural Science Award of Liaoning Province (Synthesis, Structures and Properties of Carbon Nanotubes), China
2001: China Youth Science & Technology Award, Ministry of Human Resources and China Association of Science and Technology, China
1999: Excellent Young Scientist Award, First Class, Chinese Academy of Sciences, China
1999: The Ryukiti Hasiguchi Foundation Award.

Guangmin Zhou 周光敏

副教授

Biography
Guangmin Zhou is an Associate Professor at Tsinghua-Berkeley Shenzhen Institute (TBSI), Tsinghua University, China. He received his Ph.D degree from Institute of Metal Research, Chinese Academy of Sciences in 2014 under the supervision of Prof. Hui-Ming Cheng & Prof. Feng Li, and then worked as a postdoc in UT Austin with Prof. Arumugam Manthiram from 2014-2015. After that, he was a postdoc fellow in the Department of Materials Science and Engineering at Stanford University with Prof. Yi Cui from 2015-2019. His research mainly focuses on energy-storage materials and devices. He has published over 90 papers, and first-authored 33 papers published inNature Nanotechnology (2), Chemical Reviews (1), Nature Communications (3), PNAS(2), Advanced Materials (4), etc.His publications have been cited more than 18000times with an H-index of 54 (Google Scholar).
Research
Design of high energy rechargeable batteries
Design and assembly of all solid state lithium batteries
3D printing techniques for electrode materials and devices
Development of flexible energy-storage materials and devices
In situcharacterization techniques for electrode reaction and failure mechanism
Education
Ph. D. in Material Science, Institute of Metal Research, Chinese Academy of Sciences, 2008-2014, Thesis advisor: Prof. Hui-Ming Cheng & Prof. Feng Li
B.S. in Material Forming and Control Engineering, Nanjing University of Science and Technology, 2004-2008
Professional Experience
2015-2019, Postdoctoral Fellow, Stanford University, USA, Advisor: Prof. Yi Cui
2014-2015, Postdoctoral Fellow, The University of Texas at Austin, USA, Advisor: Prof. Arumugam Manthiram
Publications
Google scholar link:
https://scholar.google.com/citations?user=smzbtMcAAAAJ&hl=en
Selected publications
1.    Zhou, G. M.;Paek, E.; Hwang, G. S.; Manthiram, A.*, Long-life Li/polysulphidebatteries with high sulphur loading enabled by lightweight three-dimensional nitrogen/sulphur codoped graphene sponge.Nature Communications,2015, 6, 7760.
2.    Zhou, G. M.#;Xu, L.#; Hu, G; Mai, L.*; Cui, Y.*, Nanowires for ElectrochemicalEnergy Storage,Chemical Reviews,2019,119, 11042-11109.
3.     Zhao, J.#;Zhou, G. M.#;(#Equally Contributed), Yan, K.; Xie, J.; Li, Y.; Liao, L.; Jin, Y.; Liu, K.; Hsu, P.; Wang, J.; Cheng, H.-M.;Cui, Y.*; Air-stable and freestanding lithium alloy/graphene foil as an alternative to lithium metal anodes,NatureNanotechnology,2017, 12, 993-999.
4.    Zhou, G. M.#;Yang, A.#; Wang, Y.; Gao, G.; Pei, A.; Yu, X.; Zhu, Y.; Zong, L.; Liu,B.; Xu, J.; Liu, N.; Zhang, J.; Li, Y.; Wang, L.; Hwang, H.; Brongersma, M.;Chu, S.;Cui, Y.*; Electrotunable liquid sulphur microdroplets,Nature Communications,2020, in press.
5.     Yang, A.#;Zhou, G. M.#;Kong, X.; Vilá, R.; Pei, A.; Wu, Y.; Yu, X.; Zheng, X.; Wu, C.; Liu, B.; Chen, H.; Xu, Y.; Chen, D.; Li, Y.; Fakra, S.; Hwang, H.; Qin, J.;Chu,S.;Cui, Y.*; Electrochemical generation of liquid and solid sulfur on two-dimensional layered materials with distinct areal capacities,Nature Nanotechnology,2020, in press.
6.    Zhou, G. M.#;Pei, S. F.#; Li, L.; Wang, D. W; Wang, S. G; Huang, K.; Yin, L. C.;Li, F.*; Cheng, H.-M.*, A Graphene-Pure Sulphur Sandwich Structure for Ultrafast, Long-Life Lithium–Sulphur Batteries,Advanced Materials,2014, 26, 625–631.
7.   Zhou, G. M.;Li, L; Wang, D. W; Shan, X. Y.; Pei, S. F.; Li, F.*; Cheng, H.-M.*,A Flexible Sulfur-Graphene-Polypropylene Separator Integrated Electrode for Advanced Li–S Batteries.Advanced Materials,2015, 27, 641-647.
8.    Zhou, G. M.#;Sun, J.#; Jin, Y.; Chen, W.; Zu, C. X.; Zhang, R.; Qiu, Y.; Zhao, J.;Zhuo, D.; Liu, Y. Y.; Tao, X.; Liu, W.; Yan, K.; Lee, H. Y.; Cui, Y.*, Sulfiphilic nickel phosphosulfide enabled Li2S impregnation in 3D graphene cages for Li-S batteries,Advanced Materials,2017, 29, 1603366.
9.    Jin, Y.#;Zhou, G. M.;#Shi, F.; Zhuo. D.; Zhao, J.; Liu, K.; Liu, Y.; Zu, C.; Chen, W.; Zhang, R.; Cui, Y.*, Reactivation of dead sulphide species in lithium polysulphide flow battery for grid scale energy storage,Nature Communications,2017, 8, 462.
10. Zhou, G. M.;Li, F.; Cheng, H.-M.*, Progress in flexible lithium batteries andfuture prospects,Energy Environ. Sci.,2014, 7(4), 1307–1338.
11. Zhou, G. M.#;Tian, H.#; Jin, Y.#; Tao, X.; Liu, B.; Zhang, R.; Seh, Z.; Zhuo, D.;Liu, Y. Y.; Sun, J.; Zhao, J.; Zu, C. X.; Wu, S. D.; Zhang, Q. F.; Cui, Y.*, Catalytic oxidation of Li2S on the surface of metal sulphides for Li-S batteries,PNAS,2017, 114, 840-845.
12. Zhou, G. M.;Zhao, Y; Manthiram, A.*, Dual-confined Flexible Sulfur CathodesEncapsulated in Nitrogen-doped Double-shelled Hollow Carbon Spheres and Wrapped with Graphene for Li-S Batteries.Adv. Energy Mater.,2015, 5, 1402263.
13. Zhou, G. M.;Paek, E.; Hwang, G. S.; Manthiram, A.*, High-Performance Lithium-Sulfur Batteries with a Self-Supported, 3D Li2S-Doped Graphene Aerogel Cathode.Adv. Energy Mater.,2016, 6, 1501355.
14. Zhou, G. M.;Wang, D. W; Yin, L. C.; Li, N.; Li, F.*; Cheng, H.-M., Oxygenbridges between NiO nanosheets and graphene for improvement of lithium storage,ACS Nano, 2012, 6, 3214–3223.
15.Zhou, G. M.;Yin, L. C.; Wang, D. W; Li, L; Pei, S.F.; Gentle, I; Li, F.*, and Cheng, H.-M.*, Fibrous Hybrid of Graphene and Sulfur Nanocrystals for High Performance Lithium-Sulfur Batteries.ACS Nano,2013, 7, 5367–5375.
16.Zhou, G. M.#;Wang, D. W#; Li, F.*; Hou, P. X.; Yin, L. C.; Liu, C; Lu, G. Q.; Gentle, I; Cheng, H.-M.*, A flexible nanostructured sulphur-carbon nanotube cathode with high rate performance for Li-S batteries,Energy Environ. Sci.,2012, 5, 8901–8906.
17. Zhou, G. M.;Wang, D. W; Li, F.*; Zhang, L. L.; Li, N.; Wu, Z. S.; Wen, L.; Lu, G.Q.; Cheng, H.-M.*, Graphene-wrapped Fe3O4 anode material with improved reversible capacity and cyclic stability for lithium ion batteries,Chem. Mater., 2010,22, 5306– 5313.
18. Zhou, G. M.#;Li, L#; Ma, C. Q; Wang, S. G; Shi, Y; Koratkar, N; Ren, W. C; Li,F.*; Cheng, H.-M.*, A graphene foam electrode with high sulfur loading for flexible and high energy Li-S batteries.Nano Energy,2015, 11, 356-365.
19. Zhou, G. M.;Zhao, Y; Zu, C; Manthiram, A.*, Free-standing TiO2nanowire-embedded graphene hybrid membrane for advanced Li/dissolved polysulfide batteries.Nano Energy,2015, 12, 240-249.
20.  Chen, L.;#Zhou, G. M.;#Liu, Z.; Ma, X.; Chen, J.; Zhang, Z. Y.; Ma, X. L.; Li, F.; Cheng, H.-M. Ren, W. C*, Scalable Clean Exfoliation of High-Quality Few-Layer Black Phosphorus for a Flexible Lithium Ion Battery,Advanced Materials,2016, 28, 510–517.
21.  Liu, N.#;Zhou, G. M.#;(#Equally Contributed), Yang, A.; Yu, X.; Shi, F.; Sun, J.; Zhang, J.; Liu, B.; Wu, C.; Tao, X.; Sun, Y.; Cui, Y.*; Chu, S.*, Direct electrochemical generation of super-cooled sulfur microdroplets well below their melting temperature,PNAS,2019, 116 (3) 765-770.
Awards
“Highly Cited Researcher” in Materials Science by Clarivate Analytics, 2018, 2019 Excellent reviewer award for Energy Storage Materials, 2016, 2017, 2018 Energy Storage Materials Young Scientist Award, 2018
Excellent Doctorate Theses Award of Chinese Academy of Sciences, 2015 Carbon Journal Prize (Only one person all over the world every year), 2015 Excellence in Review Award for Carbon, 2015
The Special Prize of President Scholarship for Postgraduate Students of CAS, 2014 SHI CHANGXU Award (First Scholarship) by IMR CAS, 2011, 2014
The National Scholarship for Postgraduate Students, 2012, 2013
Teaching
To be determined
Opening
We are seeking highly motivated Research Assistant, Graduate Students and Postdoctoral Fellows to work in the Low Dimensional Materials and Devices Laboratory, Shenzhen Geim Graphene Center (SGC) at Tsinghua Berkeley Shenzhen Institute (TBSI), Tsinghua University. Applicants should send the application to guangminzhou@sz.tsinghua.edu.cn.

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