華南理工大學(xué)和南京工業(yè)大學(xué)王強課題組—通過調(diào)節(jié)金屬與碳的電子相互作用來修飾碳納米管負載的鈀納米顆粒用于苯酚加氫

石墨烯研究 2021-09-24

展開全文

合成了雜原子摻雜碳材料，并將其作為鈀納米顆粒(NPs)的催化劑載體。許多Pd-C催化劑可以通過單摻雜、雙摻雜和多摻雜的雜原子到碳載體中產(chǎn)生。因此，尋求一種通用的描述符，無論摻雜類型如何，都將指導(dǎo)高效催化劑的設(shè)計。碳載體對鈀電子態(tài)的影響在催化過程中起著至關(guān)重要的作用，利用x射線光子光譜的結(jié)合能(BE)可以準(zhǔn)確而方便地描述其電子態(tài)。在這項工作中，通過熱裂解含雜原子前體合成了摻雜度可調(diào)的單(雙)摻雜碳納米管(CNTs)，并伴有氟化碳納米管的脫氟。密度泛函理論結(jié)果表明，摻雜碳納米管的電荷分布由摻雜構(gòu)型決定。負載Pd NPs后，載體的電荷被重新分布。同時，Pd⁰ 3d5/2的BEs也因金屬-碳電子相互作用(EMCI)而發(fā)生相應(yīng)的變化。最終，不同電子態(tài)的Pd NPs表現(xiàn)出對苯酚加氫周轉(zhuǎn)頻率的差異。因此，Pd NPs的電子狀態(tài)可以作為評價其催化性能和開發(fā)高效催化劑的指標(biāo)。

圖1合成摻雜碳納米管的流程圖和本工作中使用的兩種加熱模型。(b)雜原子摻雜和Pd NPs在摻雜CNTs上的負載示意圖。

圖2 (a) FCNTs在N₂流動下的熱重(TG)和微分TG (DTG)曲線。(b)以噻吩為S源，注入速率為1.5 mL h^-1的NH模式下，沉積3小時的熱解溫度和800℃下噻吩沉積時間對S摻雜劑含量的影響。(c)加熱方式對S摻雜劑含量12的影響，800℃，以噻吩為s源沉積2小時，注入速率為1.5 mL h^-1。(d)樣品的拉曼光譜。(e) 采用FH模式，以S粉為摻雜源，研究了溫度對S含量的影響(f) 通過FH模式改變前驅(qū)體中噻吩和吡啶的混合比例，在3ml h^-1注入速率下，可調(diào)節(jié)800℃下S和N的摻雜量。

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

圖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納米顆粒在不同載體上的Pd XPS 能譜。

圖5 優(yōu)化的雜原子摻雜石墨烯和Pd₄團簇的結(jié)構(gòu)和巴德爾電荷的示意圖。

圖6 (a)苯酚轉(zhuǎn)化率和環(huán)己酮選擇性對反應(yīng)時間的影響。(b) Pd催化劑上苯酚加氫過程中TOF對Pd結(jié)合能的影響。(c)苯酚轉(zhuǎn)化率和環(huán)己酮選擇性與循環(huán)次數(shù)有關(guān)。

華南理工大學(xué)Guangxing Yang, Hao Yu，和南京工業(yè)大學(xué)Qiang Wang等人于2021年發(fā)表在Chemical Engineering Journal（ https:///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 國家自然科學(xué)基金－青年基金，納米Cu電極表面及近表面物質(zhì)傳遞對CO2電還原C2產(chǎn)物選擇性作用機制研究，22008076, 24萬元，在研，國家級，主持

2021.06-2021.10 中國博士后科學(xué)基金第14批特別資助（站中）,CO2電還原動力學(xué)與近表面物質(zhì)傳遞耦合機制的原位譜學(xué)研究，2021T140217, 18萬元，在研，國家級，主持

2020.01-2022.12 廣東省基礎(chǔ)與應(yīng)用基礎(chǔ)研究基金項目－區(qū)域聯(lián)合基金-青年基金項目，Cu電極表面物質(zhì)傳遞對CO2電還原產(chǎn)物分布的影響機制，2019A1515110035，10萬元，在研，省部級，主持

2020.1-2021.12 華南理工大學(xué)制漿造紙工程國家重點實驗室開放基金項目，貴金屬單原子催化劑電轉(zhuǎn)化生物質(zhì)平臺分子的基礎(chǔ)研究，202013，5萬元，在研，省部級，主持

2019.06-2021.06 中國博士后科學(xué)基金第65批面上資助-二等資助項目， Cu電極上物質(zhì)傳遞對CO2電還原產(chǎn)物分布的作用機制研究，2019M652903，8萬元，在研，省部級，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

王強博士

副教授，碩士生導(dǎo)師, 2012年獲得新加坡南洋理工大學(xué)博士學(xué)位。2011年9月至2012年8月在新加坡科學(xué)技術(shù)研究局高性能計算研究所從事博士后工作。2012年9月加入南京工業(yè)大學(xué)工作。主要從事理論計算化學(xué)/材料模擬計算的相關(guān)研究。主持國家自然科學(xué)基金面上項目、青年項目、中國博士后基金及橫向項目10余項。入選江蘇省“六大人才高峰”高層次人才、“雙創(chuàng)計劃”科技副總、揚州市“綠揚金鳳計劃”優(yōu)秀博士等人才項目。

Email：wangqiang@njtech.edu.cn

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

教學(xué)工作：

主講本科生《物理化學(xué)》、《物理化學(xué)實驗》和研究生《高等物理化學(xué)II》、《量子化學(xué)計算》等課程。主持省級教學(xué)教改課題1項、校級4項，指導(dǎo)大學(xué)生創(chuàng)新創(chuàng)業(yè)訓(xùn)練計劃省級2項、校級6項，主編（排名第二）《Physical Chemistry》江蘇省高校重點教材一部，參編《物理化學(xué)》和《物理化學(xué)實驗》教材兩部。

科研工作：

主要從事碳納米材料（碳納米管、石墨烯、碳團簇和異質(zhì)結(jié)）的沉積、成核和生長機理及其調(diào)控機制和新型催化劑（單原子金屬、納米團簇、納米棒等）的設(shè)計及其催化反應(yīng)機理的相關(guān)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等期刊發(fā)表SCI論文65篇，被引1500余次，H-Index 18。其中高被引用論文4篇，被作為亮點再次報道3篇。現(xiàn)為Theoretical and Computational Chemistry (specialty section of Frontiers in Chemistry) 編委會評論編輯，《當(dāng)代化工研究》編輯委員會委員，Carbon、Nano Scale、J Phys Chem、Inorg Chem Front、Theor Chem Acc等期刊審稿人。

主持科研項目

(1)國家自然科學(xué)面上基金《可控生長石墨烯的理論研究》（No. 21373112， 2014/01--2017/12）在研，主持；

(2)國家自然科學(xué)青年基金《手性控制生長單壁碳納米管的理論研究》（No. 21203094， 2013/01--2015/12）已結(jié)題，主持；

(3)中國博士后科學(xué)基金第59批面上基金，2016M591834，在研，主持；

(4)南京工業(yè)大學(xué)人才啟動基金和南京工業(yè)大學(xué)人才團隊計劃培育項目。

主要研究方向：

(1) 新碳材料（碳納米管、石墨烯、碳團簇和碳納米帶）的沉積、成核和生長機理及其調(diào)控機制的理論計算研究；

(2) 新穎碳功能材料的設(shè)計及其電子結(jié)構(gòu)、光學(xué)、電學(xué)和磁學(xué)性質(zhì)的理論計算研究；

(3) 新穎重要分子簇、自由基的結(jié)構(gòu)、成鍵性質(zhì)、穩(wěn)定性、勢能面和反應(yīng)機理的量子化學(xué)計算研究。

(4) 新型催化劑（單原子、core-shell納米團簇、納米棒等）的設(shè)計及其結(jié)構(gòu)穩(wěn)定性、催化活性、選擇性和反應(yīng)機理的理論計算研究。

代表性論文：

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.
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.
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.
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.
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.
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. （高被引論文）
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.
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.
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.
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.
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.
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.
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.
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
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.
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.（高被引論文）
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.
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.
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.
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.
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.
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.
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–C_n Complexes, J. Phys. Chem. A, 116, 11709–11717, 2012.
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.
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./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./research/6181。