华南理工大学和南京工业大学王强课题组—通过调节金属与碳的电子相互作用来修饰碳纳米管负载的钯纳米颗粒用于苯酚加氢

合成了杂原子掺杂碳材料，并将其作为钯纳米颗粒(NPs)的催化剂载体。许多Pd-C催化剂可以通过单掺杂、双掺杂和多掺杂的杂原子到碳载体中产生。因此，寻求一种通用的描述符，无论掺杂类型如何，都将指导高效催化剂的设计。碳载体对钯电子态的影响在催化过程中起着至关重要的作用，利用x射线光子光谱的结合能(BE)可以准确而方便地描述其电子态。在这项工作中，通过热裂解含杂原子前体合成了掺杂度可调的单(双)掺杂碳纳米管(CNTs)，并伴有氟化碳纳米管的脱氟。密度泛函理论结果表明，掺杂碳纳米管的电荷分布由掺杂构型决定。负载Pd NPs后，载体的电荷被重新分布。同时，Pd0 3d5/2的BEs也因金属-碳电子相互作用(EMCI)而发生相应的变化。最终，不同电子态的Pd NPs表现出对苯酚加氢周转频率的差异。因此，Pd NPs的电子状态可以作为评价其催化性能和开发高效催化剂的指标。

图1合成掺杂碳纳米管的流程图和本工作中使用的两种加热模型。(b)杂原子掺杂和Pd NPs在掺杂CNTs上的负载示意图。

图2 (a) FCNTs在N2流动下的热重(TG)和微分TG (DTG)曲线。(b)以噻吩为S源，注入速率为1.5 mL h-1的NH模式下，沉积3小时的热解温度和800℃下噻吩沉积时间对S掺杂剂含量的影响。(c)加热方式对S掺杂剂含量12的影响，800℃，以噻吩为s源沉积2小时，注入速率为1.5 mL h-1。(d)样品的拉曼光谱。(e) 采用FH模式，以S粉为掺杂源，研究了温度对S含量的影响(f) 通过FH模式改变前驱体中噻吩和吡啶的混合比例，在3ml h-1注入速率下，可调节800℃下S和N的掺杂量。

图3 (a) S@CNTs的TEM图，(b) C和S的STEM-EDS线扫描，(C) S@CNT的HRTEM图，(d)-(h) EDS元素映射S@CNTs。

图4. Pd/p-CNTs， (b) Pd/S@CNTs， (c) Pd/N@CNTs， (d) Pd/P@CNTs， (e) Pd/N&S@CNTs， (f) Pd/N&P@CNTs， (g) Pd纳米颗粒在不同载体上的Pd XPS 能谱。

图5 优化的杂原子掺杂石墨烯和Pd4团簇的结构和巴德尔电荷的示意图。

图6 (a)苯酚转化率和环己酮选择性对反应时间的影响。(b) Pd催化剂上苯酚加氢过程中TOF对Pd结合能的影响。(c)苯酚转化率和环己酮选择性与循环次数有关。

华南理工大学Guangxing Yang, Hao Yu，和南京工业大学Qiang Wang等人于2021年发表在Chemical Engineering Journal（ https://doi.org/10.1016/j.cej.2021.131758）上。原文：Modifying carbon nanotubes supported palladium nanoparticles via regulating the electronic metal-carbon interaction for phenol hydrogenation。

Guangxing YangPh.D.

E-mail: yanggx@scut.edu.cn

Education

2013.08-2018.05   University of New Hampshire, PhD in Chemical Engineering

2008.09-2011.06  South China University of Technology, China M.S. in Industrial Catalysis

2004.09-2008.06 South China University of Technology, B.S. in Chemical Engineering and Technology

Working Experience

2018.9-present

2018.05-2018.08   Postdoc, School of Chemistry and Chemical Engineering, South China University of TechnologyPhD researcher, Department of Chemical Engineering at University of

New Hampshire

2013.08-2015.05  Teaching Assistant, Department of Chemical Engineering at University of New Hampshire

2011.07-2013.06 Assistant Engineer, Sinopec Limited-Guangzhou

Research Interests

1. Electrooxidation of ethanol, methanol and CO molecules to CO2 on noble metal catalysts for fuel cells.

2. Electrochemical conversion of CO2 to valuable molecules in aqueous electrolyte and thermal conversion of CO2 to valuable molecules in the gas phase.

Projects

2021.01-2023.12 国家自然科学基金－青年基金，纳米Cu电极表面及近表面物质传递对CO2电还原C2产物选择性作用机制研究，22008076,   24万元，在研，国家级，主持

2021.06-2021.10 中国博士后科学基金第14批特别资助（站中）,CO2电还原动力学与近表面物质传递耦合机制的原位谱学研究，2021T140217, 18万元，在研，国家级，主持

2020.01-2022.12 广东省基础与应用基础研究基金项目－区域联合基金-青年基金项目，Cu电极表面物质传递对CO2电还原产物分布的影响机制，2019A1515110035，10万元，在研，省部级，主持

2020.1-2021.12 华南理工大学制浆造纸工程国家重点实验室开放基金项目，贵金属单原子催化剂电转化生物质平台分子的基础研究，202013，5万元，在研，省部级，主持

2019.06-2021.06 中国博士后科学基金第65批面上资助-二等资助项目， Cu电极上物质传递对CO2电还原产物分布的作用机制研究，2019M652903，8万元，在研，省部级，主持

Publications

1. Guangxing Yang,Lida Farsi, Yuhan Mei, Xing Xu, Anyin   Li, N Aaron Deskins, Xiaowei Teng*. Conversion of ethanol via C-C   splitting on noble metal surfaces in room-temperature liquid-phase, Journal of the American Chemical Society,2019, 141(24), 9444–9447

2. Dongyan Shen#, Yong Liu#, Guangxing Yang*,   Hao Yu, Peng-Fei Liu, Feng Peng*. Surface-structure sensitive chemical diffusivity   and reactivity of CO adsorbates on noble metal electrocatalysts, Applied Catalysis B: Environmental, 2021, 281, 119522

Ph.D.Hao Yu

Tel:  86-20-8711 4916

Fax: 86-20-8711 4916

Email: yuhao@scut.edu.cn

Education

2005      Tsinghua University, Beijing, China, Ph.D.in Chemical Engineering                    Supervisor: Prof. Fei Wei

1999      Tsinghua University, Beijing, China, B. S. in Chemical Engineering

Work  Experience

2013-present    Professor, School of Chemistry and Chemical Engineering, South China University of                                     Technology, P.R. China

2012-2013         Visiting Scholar, Department of Chemical and Biomolecular Engineering, University of                                 California, Los Angeles

2008-2013         Associate Professor, School of Chemistry and Chemical Engineering, South China                                          University of Technology, P.R. China

2005-2008         Assistant Professor, School of Chemistry and Chemical Engineering, South China                                           University of Technology, P.R. China

Research Interests

(1) Novel catalysts based on carbon nanomaterials

(2) Sustainable catalytic oxidation technology

(3) Catalytic reaction engineering

The research has been supported by the National Natural Science Foundation of China, the Guangdong Natural Science Funds for Distinguished Young Scholar, and Program for New Century Excellent Talents in University etc.

Honors and Awards

2013    New Century Excellent Talents in University, Ministry of Education of the People's Republic of                     China

2012    Distinguished Young Scholar, Guangdong Provincial National Science Foundation

2011    The Pearl River New-Star of Science & Technology supported by Guangzhou City

2010    Liao Shijun,Peng Feng, Liu Junmin, Wang Rongfang, Wang Hhongjuan,Yu Hao, Wu                                    Yanni, Liang Zhenxing, Xu Leiming, Second-grade Natural Science Award of Chinese Minster                      Education

2005    Wei Fei, Qian Weizhong, Luo Gguohua, Wang Yao, Wang Zhanwen, Jin Yongn, Yu Hao, Li                          Zhifei,Zhang Qunfeng,Liu Tang, Ni

王 强   博士

副教授，硕士生导师, 2012年获得新加坡南洋理工大学博士学位。2011年9月至2012年8月在新加坡科学技术研究局高性能计算研究所从事博士后工作。2012年9月加入南京工业大学工作。主要从事理论计算化学/材料模拟计算的相关研究。主持国家自然科学基金面上项目、青年项目、中国博士后基金及横向项目10余项。入选江苏省“六大人才高峰”高层次人才、“双创计划”科技副总、扬州市“绿扬金凤计划”优秀博士等人才项目。

Email：wangqiang@njtech.edu.cn

URL: http://www.researcherid.com/rid/D-3480-2011

教学工作：

主讲本科生《物理化学》、《物理化学实验》和研究生《高等物理化学II》、《量子化学计算》等课程。主持省级教学教改课题1项、校级4项，指导大学生创新创业训练计划省级2项、校级6项，主编（排名第二）《Physical Chemistry》江苏省高校重点教材一部，参编《物理化学》和《物理化学实验》教材两部。

科研工作：  

主要从事碳纳米材料（碳纳米管、石墨烯、碳团簇和异质结）的沉积、成核和生长机理及其调控机制和新型催化剂（单原子金属、纳米团簇、纳米棒等）的设计及其催化反应机理的相关研究。迄今在如Nature Commun、Angew Chem Int Edit、ACS Catal、ACS Nano、J Phys Chem Lett、Carbon、Energy Environ Sci、Small、Chem Commun、Phys Chem Chem Phys、J Comput Chem、 J Phys Chem A、J Chem Phys和Theor Chem Acc等期刊发表SCI论文65篇，被引1500余次，H-Index 18。其中高被引用论文4篇，被作为亮点再次报道3篇。现为Theoretical and Computational Chemistry (specialty section of Frontiers in Chemistry) 编委会评论编辑，《当代化工研究》编辑委员会委员，Carbon、Nano Scale、J Phys Chem、Inorg Chem Front、Theor Chem Acc等期刊审稿人。

主持科研项目

(1)国家自然科学面上基金《可控生长石墨烯的理论研究》 （No. 21373112， 2014/01--2017/12）在研，主持；

(2)国家自然科学青年基金《手性控制生长单壁碳纳米管的理论研究》 （No. 21203094， 2013/01--2015/12） 已结题，主持；

(3)中国博士后科学基金第59批面上基金，2016M591834，在研，主持；

(4)南京工业大学人才启动基金和南京工业大学人才团队计划培育项目。

主要研究方向：

(1) 新碳材料（碳纳米管、石墨烯、碳团簇和碳纳米带）的沉积、成核和生长机理及其调控机制的理论计算研究；

(2) 新颖碳功能材料的设计及其电子结构、光学、电学和磁学性质的理论计算研究；

(3) 新颖重要分子簇、自由基的结构、成键性质、稳定性、势能面和反应机理的量子化学计算研究。

(4) 新型催化剂（单原子、core-shell纳米团簇、纳米棒等）的设计及其结构稳定性、催化活性、选择性和反应机理的理论计算研究。

代表性论文：

  1. Pengfei Liu, Yanhui Yang, Qiang Wang,* Mechanism insights into direct conversion of syngas into C2 oxygenates via key intermediate C2O2 over Ni-Supported graphene, Carbon, 175, 322-333, 2021.

  2. Wenjuan Liu,* Xiao Chen, Xiaoyong Ding, Qiang Long, Xiaolong Lu,* Qiang Wang,* and Zhongwei Guab, Visible-light-driven cuprous oxide nanomotors with surface-heterojunction-induced propulsion, Nanoscale Horizons, DOI: 10.1039/d0nh00663g, 2021.

  3. Jianmei Huang, Qiang Wang,* Pengfei Liu, Guang-hui Chen and Yanhui Yang,* Tuning adlayer-substrate interactions of graphene/h-BN heterostructures on Cu(111)–Ni and Ni(111)–Cu surface alloys, RSC Adv., 11, 1916–1927, 2021.

  4. Hengyue Xu, Pengfei Liu, Wenjie Zhang, Qiang Wang,* Yanhui Yang,* Structure, stability, electronic and magnetic properties of monometallic Pd, Pt, and bimetallic Pd-Pt core–shell nanoparticles, Chem. Phys., 539, 110953, 2020.

  5. Haoyun Lu, Mengqi Qian, Qiang Wang,* Yanhui Yang, Direct ring-open mechanism of pyridine formation by replacement of one carbon in benzene with one nitrogen atom, J. Phys. Org. Chem., e4061, 2020.

  6. Xueqing Gao, Yingdong Chen, Tong Sun, Jianmei Huang, Wei Zhang,* Qiang Wang,* and Rui Cao,* Karst landform-featured monolithic electrode for water electrolysis in neutral media, Energy Environ. Sci, 13(1), 174-182, 2020. （高被引论文）

  7. Qiang Wang,* Pengfei Liu, Xin Bian, Jianmei Huang, Wei-qi Li, Guang-hui Chen, Yanhui Yang,* Adlayer-substrate interactions in controlled growth of graphene/h-BN heterostructure on Ni(111) and Cu(111) surfaces, Appl. Surf. Sci., 480, 154-161, 2019.

  8. Zhiyan He, Baoqiang Dong, Wenli Wang, Guangxing Yang, Yonghai Cao, Hongjuan Wang, Yanhui Yang, Qiang Wang,* Feng Peng, and Hao Yu,* Elucidating Interaction between Palladium and N‑Doped Carbon Nanotubes: Effect of Electronic Property on Activity for Nitrobenzene Hydrogenation, ACS Catal, 9(4), 2893-2901, 2019.

  9. Xiaoshan Wang, Zhiwei Wang, Jindong Zhang, Xiang Wang, Zhipeng Zhang, Jialiang Wang, Zhaohua Zhu, Zhuoyao Li, Yao Liu, Xuefeng Hu, Junwen Qiu, Guohua Hu, Bo Chen, Ning Wang, Qiyuan He, Junze Chen, Jiaxu Yan, Wei Zhang, Tawfique Hasan, Shaozhou Li, Hai Li, Hua Zhang, Qiang Wang*, Xiao Huang* & Wei Huang *, Realization of vertical metal semiconductor heterostructures via solution phase epitaxy, Nature Commun., 9(1), 3611, 2018.

  10. Qiang Wang,⁎ Xianfei Lu, Yanzhong Zhen, Wei-qi Li, Guang-hui Chen, and Yanhui Yang, Structure, stability, electronic, magnetic, and catalytic properties of monometallic Pd, Au, and bimetallic Pd-Au core-shell nanoparticles, J. CHEM. PHYS.,149, 244307, 2018.

  11. Xueqing Gao, Jing Qi, Shanhong Wan, Wei Zhang,* Qiang Wang,* and Rui Cao*, Conductive Molybdenum Sulfide for Efficient Electrocatalytic Hydrogen Evolution, Small, 14, 1803361, 2018.

  12. Qiang Wang,* Xinyan Wang, Jianlan Liu, and Yanhui Yang*，Cu-Ni core-shell nanoparticles: structure, stability, electronic, and magnetic properties: a spin-polarized density functional study，J. Nanopart. Res.，2017，19(2)，13570-13578.

  13. Lu Wang, Qiang Wang,* Jianmei Huang, Wei-qi Li, Guang-hui Chen and Yanhui Yang*，Interface and interaction of graphene layers on SiC(000-1) covered with TiC(111) intercalation，Phys. Chem. Chem. Phys.， 2017，19(39)，26765-26775.

  14. Teng Wang, Yajun Zheng, Xiaoting Wang, Qiang Wang,* Congyu Ke,Daniel E. Austin,* Xiaoxiao Han and Zhiping Zhang*，Abnormal adsorption and desorption behavior of pharmaceutical drugs on polystyrene microspheres，Rsc Adv.，2017，7(32)，19639-19644

  15. Xin Bian, Qiang Wang*, Xinyan Wang, Lu Wang, Wei-qi Li, Guang-hui Chen, and Hongjun Zhu*. Graphene layers on bimetallic Ni/Cu(111) surface and near surface alloys in controlled growth of graphene. RSC Adv., 6, 74973-74981,2016.

  16. Li Tao#, Qiang Wang#, (共同一作)Shuo Dou, Zhaoling Ma, Jia Huo, Shuangyin Wang and Liming Dai, Edge-rich and dopant-free graphene as a highly efficient metal-free electrocatalyst for the oxygen reduction reaction. Chem. Commun., 52, 2764-2767, 2016.（高被引论文）

  17. Qiuhong Liu, Xia Weijun, Zhenjun Wu, Jia Huo, Dongdong Liu, Qiang Wang* and Shuangyin Wang, The origin of the enhanced performance of nitrogen-doped MoS2 in lithium ion batteries. Nanotechnology, 27(17), 175402, 2016.

  18. Xiaoye Shan, Qiang Wang*, Xin Bian, Wei-qi Li, Guang-hui Chen and Hongjun Zhu*. Graphene layers on Si-face and C-face surfaces and interaction with Si and C atoms in layer controlled graphene growth on SiC substrates. RSC Adv., 5, 78625-78633,2015.

  19. Zhimin Yang, Qiang Wang*, Xiaoye Shan, Wei-qi Li, Guang-hui Chen and Hongjun Zhu*. DFT study of Fe-Ni Core-shell Nanoparticles: Stability, Catalytic Activity and Interaction with Carbon Atom for Single-walled Carbon Nanotube Growth [J]. J. Chem. Phys. 142(7): 074306, 2015.

  20. Zhimin Yang, Qiang Wang*, Xiaoye Shan, Shuo-Wang Yang and Hongjun Zhu*. Theoretical Investigation on Carbon Nucleation on Nickel Carbides at Initial Stages of Single-walled Carbon Nanotube Formation [J]. Phys. Chem. Chem. Phys.16(36): 19654-19660, 2014.

  21. Anli Shen；Yuqin；Qiang Wang；Robert A. W. Dryfe；Xiaobing Huang；Liming Dai；Shuangyin Wang，Oxygen Reduction Reaction in a Droplet on Graphite: Direct Evidence that the Edge Is More Active than the Basal Plane，Angew. Chem. Int. Edit., 53(40), 10804–10808, 2014.

  22. Wang, Qiang; Wei, Li; Sullivan, M.; Yang, Shuo-Wang.; Chen, Yuan*, Graphene layers on Cu and Ni (111) surfaces in layer controlled graphene growth. RSC Adv., 3, 3046-3053, 2013.

  23. Wang Qiang; Wang Hong; Wei Li; Yang Shuo-Wang; Yuan Chen*, Reactive Sites for Chiral Selective Growth of Single Walled Carbon Nanotubes: A DFT Study of Ni55–Cn Complexes, J. Phys. Chem. A, 116, 11709–11717, 2012.

  24. Qiang Wang; Kok Hwa Lim; Shuo-Wang Yang; Yanhui Yang; Yuan Chen*; Atomic Carbon Adsorption on Ni Nanoclusters: A DFT Study, Theor. Chem. Acc., 128, 17-24, 2011.

  25. Wang, Qiang; Yang, Shuo-Wang; Yang, Yanhui; Chan-Park, Mary; Chen, Yuan*; Charge Transfer between Metal Clusters and Growing Carbon Structures in Chirality-Controlled Single Walled Carbon Nanotube Growth, J. Phys. Chem. Lett., 2, 1009–1014, 2011. Highlighted on NPG (Nature Publishing Group) Asia material: http://www.natureasia.com/asia-materials/highlight.php?id=936。

    Wang, Qiang; Ng, Man-Fai; Yang, Shuo-Wang; Yang, Yanhui; Chen, Yuan;* The Mechanism of Single-Walled Carbon Nanotube Growth and Chirality Selection Induced by Carbon Atom and Dimer Addition, ACS Nano, 4(2) 939–946, 2010. Highlighted on Agency for Science, Technology and Research of Singapore (A*STAR): http://www.research.a-star.edu.sg/research/6181。

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