Citation: Xue LI, Hong-Yun XU, Yi-Shu WANG, Yan-Hua SONG, Yan-Juan CUI. Preparation and Photocatalytic Performance of Thiophene-Ring Doped Carbon Nitride Nanosheets[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(4): 654-664. doi: 10.11862/CJIC.2022.077 shu

Preparation and Photocatalytic Performance of Thiophene-Ring Doped Carbon Nitride Nanosheets

School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212100, China

Corresponding author: Yan-Juan CUI, yjcui@just.edu.cn
Received Date: 5 November 2021
Revised Date: 6 February 2022

Figures(13)

Secondary thermal exfoliation is an effective method to synthesize 2D carbon nitride nanosheets (CNN). Further broadening the visible light response and optimizing the photoelectric conversion efficiency are effective strategies to improve the photocatalytic performance of CNN materials. In this work, we report thiophene-ring doped carbon nitride nanosheet photocatalysts (CNN-Th_x) prepared from in situ polymerization doping and secondary thermal exfoliation using 2-aminothiophene-3 -carbonitride as the molecular doping source. Thiophene-ring with excellent chemical properties was stably doped into conjugated CNN nanosheets. After secondary thermal exfoliation, the products maintained 2D hybrid conjugated polymer structures, and the thiophene-ring was still stably doped in the CNN conjugated heterocyclic skeleton. Thiophene-ring doping causes the further expansion of the π-conjugated system, reduces the bandgap, broadens the visible light absorption range, and accelerates the photoelectric conversion efficiency of the catalysts. At the same time, thermal exfoliation cooperated with thiophene doping leads to a more significant n-π^* transition, which greatly improves the photocatalytic activity of the catalysts. The results showed that CNN-Th_x had significantly enhanced photocatalytic reduction performance, in which the H₂ evolution activity of CNN-Th₁₀ reached 322.8 μmol·h^-1, and the generated H₂O₂ concentration reached 223.1 μmol·L^-1 after 4 h, which were 3.6 and 22.3 times that of CNN, respectively.
- carbon nitride nanosheets,
- doping,
- photocatalysis,
- H₂ evolution,
- H₂O₂ production
1. [1]
  Wang X C, Maeda K, Thomas A, Takanabe K, Xin G, Carlsson J M, Domen K, Antonietti M. A Metal-Free Polymeric Photocatalyst for Hydrogen Production from Water under Visible Light[J]. Nat. Mater., 2009,8(1):76-80. doi: 10.1038/nmat2317
2. [2]
  Naseri A, Samadi M, Pourjavadi A, Moshfegh A Z, Ramakrishna S. Graphitic Carbon Nitride (g-C₃N₄)-based Photocatalysts for Solar Hydrogen Generation: Recent Advances and Future Development Directions[J]. J. Mater. Chem. A, 2017,5(45):23406-23433. doi: 10.1039/C7TA05131J
3. [3]
  Reddy S S, Aryal U K, Jin H J, Gokulnath T, Rajalapati D G, Kranthiraja K, Shin S T, Jin S H. A New Benzodithiophene Based Donor-Acceptor π-Conjugated Polymer for Organic Solar Cells[J]. Macromol. Res., 2020,28(2):179-183. doi: 10.1007/s13233-020-8079-z
4. [4]
  Zhang G G, Lan Z A, Wang X C. Conjugated Polymers: Catalysts for Photocatalytic Hydrogen Evolution[J]. Angew. Chem. Int. Ed., 2016,55(51):15712-15727. doi: 10.1002/anie.201607375
5. [5]
  Yanagida S, Kabumoto A, Mizumoto K, Pac C, Yoshino K. Poly(p-phenylene)-Catalyzed Photoreduction of Water to Hydrogen[J]. J. Chem. Soc.-Chem. Commun., 1985,8:474-475.
6. [6]
  Slater A G, Cooper A I. Function-led Design of New Porous Materials[J]. Science, 2015,348(6238)aaa8075. doi: 10.1126/science.aaa8075
7. [7]
  Shen Q H, Li N X, Bibi R, Richard N, Liu M C, Zhou J C, Jing D W. Incorporating Nitrogen Defects into Novel Few-Layer Carbon Nitride Nanosheets for Enhanced Photocatalytic H₂ Production[J]. Appl. Surf. Sci., 2020,529147104. doi: 10.1016/j.apsusc.2020.147104
8. [8]
  Zhang G G, Savateev A, Zhao Y B, Li L N, Antonietti M. Advancing the n→π^* Electron Transition of Carbon Nitride Nanotubes for H₂ Photosynthesis[J]. J. Mater. Chem. A, 2017,5(25):12723-12728. doi: 10.1039/C7TA03777E
9. [9]
  Liu X L, Guo Y H, Wang P, Zhang Q Q, Wang Z Y, Liu Y Y, Zheng Z K, Cheng H F, Dai Y, Huang B B. The Synergy of Thermal Exfoliation and Phosphorus Doping in g-C₃N₄ for Improved Photocatalytic H₂ Generation[J]. Int. J. Hydrogen Energy, 2021,46(5):3595-3604. doi: 10.1016/j.ijhydene.2020.10.233
10. [10]
  Chen Y S, Yang B, Xie W Y, Zhao X Y, Wang Z, Su X T, Yang C. Combined Soft Templating with Thermal Exfoliation toward Synthesis of Porous g-C₃N₄ Nanosheets for Improved Photocatalytic Hydrogen Evolution[J]. J. Mater. Res. Technol., 2021,13:301-310. doi: 10.1016/j.jmrt.2021.04.056
11. [11]
  Bellamkonda S, Shanmugam R, Gangavarapu R R. Extending the π-electron Conjugation in 2D Planar Graphitic Carbon Nitride: Efficient Charge Separation for Overall Water Splitting[J]. J. Mater. Chem. A, 2019,7(8):3757-3771. doi: 10.1039/C8TA10580D
12. [12]
  Liu J, Yu Y, Qi R L, Cao C Y, Liu X Y, Zheng Y J, Song W G. Enhanced Electron Separation on In-Plane Benzene-Ring Doped g-C₃N₄ Nanosheets for Visible Light Photocatalytic Hydrogen Evolution[J]. Appl. Catal. B, 2019,244:459-464. doi: 10.1016/j.apcatb.2018.11.070
13. [13]
  Zhang J S, Chen X F, Takanabe K, Maeda K, Domen K, Epping J D, Fu X Z, Antonietti M, Wang X C. Synthesis of a Carbon Nitride Structure for Visible-Light Catalysis by Copolymerization[J]. Angew. Chem. Int. Ed., 2010,49(2):441-444. doi: 10.1002/anie.200903886
14. [14]
  Li M, Zhang S B, Liu X, Han J Y, Zhu X L, Ge Q F, Wang H. Polydo-pamine and Barbituric Acid Comodified Carbon Nitride Nanospheres for Highly Active and Selective Photocatalytic CO₂ Reduction[J]. Eur. J. Inorg. Chem., 2019,15(13):2058-2064.
15. [15]
  Zhang J S, Zhang G G, Chen X F, Lin S, Mohlmann L, Dolega G, Lipner G, Antonietti M, Blechert S, Wang X C. Co-monomer Control of Carbon Nitride Semiconductors to Optimize Hydrogen Evolution with Visible Light[J]. Angew. Chem. Int. Ed., 2012,51:3183-3187. doi: 10.1002/anie.201106656
16. [16]
  Goker S, Hizalan G, Aktas E, Kutkan S, Cirpan A, Toppare L. 2, 1, 3-Benzooxadiazole, Thiophene and Benzodithiophene based Random Copolymers for Organic Photovoltaics: Thiophene versus Thieno[3, 2-b]Thiophene as π-Conjugated Linkers[J]. New J. Chem., 2016,40(12):10455-10464. doi: 10.1039/C6NJ02469F
17. [17]
  Zhang K, Tieke B, Forgie J C, Vilela F, Skabara P J. Donor -Acceptor Conjugated Polymers Based on p-and o-Benzodifuranone and Thiophene Derivatives: Electrochemical Preparation and Optical and Electronic Properties[J]. Macromolecules, 2012,45(2):743-750. doi: 10.1021/ma202387t
18. [18]
  Zhang M W, Wang X C. Two Dimensional Conjugated Polymers with Enhanced Optical Absorption and Charge Separation for Photocatalytic Hydrogen Evolution[J]. Energy Environ. Sci., 2014,7(6):1902-1906. doi: 10.1039/c3ee44189j
19. [19]
  Ge F Y, Huang S Q, Yan J, Jing L Q, Chen F, Xie M, Xu Y G, Xu H, Li H M. Sulfur Promoted n-π^* Electron Transitions in Thiophene-Doped g-C₃N₄ for Enhanced Photocatalytic Activity[J]. Chin. J. Catal., 2021,42(3):450-459. doi: 10.1016/S1872-2067(20)63674-9
20. [20]
  Wang L C, Cao S, Guo K, Wu Z J, Ma Z, Piao L Y. Simultaneous Hydrogen and Peroxide Production by Photocatalytic Water Splitting[J]. Chin. J. Catal., 2019,40(3):470-475. doi: 10.1016/S1872-2067(19)63274-2
21. [21]
  Cui Y J, Wang Y X, Wang H, Cao F, Chen F Y. Polycondensation of Ammonium Thiocyanate into Novel Porous g-C₃N₄ Nanosheets as Photocatalysts for Enhanced Hydrogen Evolution under Visible Light Irradiation[J]. Chin. J. Catal., 2016,37(11):1899-1906. doi: 10.1016/S1872-2067(16)62509-3
22. [22]
  Chen Y L, Qu Y, Xu P, Zhou X, Sun J M. Insight into the Influence of Donor-Acceptor System on Graphitic Carbon Nitride Nanosheets for Transport of Photoinduced Charge Carriers and Photocatalytic H₂ Generation[J]. J. Colloid Interface Sci., 2021,601:326-337. doi: 10.1016/j.jcis.2021.05.145
23. [23]
  Fu Y S, Zhu J W, Hu C, Wu X D, Wang X. Covalently Coupled Hybrid of Graphitic Carbon Nitride with Reduced Graphene Oxide as a Superior Performance Lithiumion Battery Anode[J]. Nanoscale, 2014,6(21):12555-12564. doi: 10.1039/C4NR03145H
24. [24]
  Oh J, Yoo R J, Kim S Y, Lee Y J, Kim D W, Park S. Oxidized Carbon Nitrides: Water-Dispersible, Atomically Thin Carbon Nitride-Based Nanodots and Their Performances as Bioimaging Probes[J]. Chem. Eur. J., 2015,21(16):6241-6246. doi: 10.1002/chem.201406151
25. [25]
  Liu X, Zong H, Tan X L, Wang X Y, Qiu J, Kong F Y, Zhang J G, Fang S. Facile Synthesis of Modified Carbon Nitride with Enhanced Activity for Photocatalytic Degradation of Atrazine[J]. J. Environ. Chem. Eng., 2021,9(5)105807. doi: 10.1016/j.jece.2021.105807
26. [26]
  Sathyapalan A, Ng S C, Lohani A, Ong T T, Chen H, Zhang S, Lam Y M, Mhaisalkar S G. Novel Self Assembled Monolayers of Allyl Phenyl Thiophene Ether as Potential Dielectric Material for Organic Thin Film Transistors[J]. Thin Solid Films, 2008,516(16):5645-5648. doi: 10.1016/j.tsf.2007.07.120
27. [27]
  Nelson A J, Glenis S, Frank A J. XPS and UPS Investigation of PF₆ Doped and Undoped Poly 3-Methyl Thiophene[J]. J. Chem. Phys., 1987,87:5002-5006. doi: 10.1063/1.452815
28. [28]
  Liu G, Niu P, Sun C H, Smith S C, Chen Z G, Lu G Q, Cheng H M. Unique Electronic Structure Induced High Photoreactivity of Sulfur-Doped Graphitic C₃N₄[J]. J. Am. Chem. Soc., 2010,132(33):11642-11648. doi: 10.1021/ja103798k
29. [29]
  Zhang M W, Zhang J S, Chen Y, Wang X C. Molecular Pore-Wall Engineering of Mesozeolitic Conjugated Polymers for Photoredox Hydrogen Production with Visible Light[J]. J. Energy Chem., 2017,26(1):87-92. doi: 10.1016/j.jechem.2016.07.004
30. [30]
  Yang Q, Yang W B, He F F, Liu K W, Cao H M, Yan H J. One-Step Synthesis of Nitrogen-Defective Graphitic Carbon Nitride for Improving Photocatalytic Hydrogen Evolution[J]. J. Hazard. Mater., 2021,410124594. doi: 10.1016/j.jhazmat.2020.124594
31. [31]
  Li C M, Wu H H, Zhu D Q, Zhou T X, Yan M, Chen G, Sun J X, Dai G, Ge F, Dong H J. High-Efficient Charge Separation Driven Directionally by Pyridine Rings Grafted on Carbon Nitride Edge for Boosting Photocatalytic Hydrogen Evolution[J]. Appl. Catal. B, 2021,297120433. doi: 10.1016/j.apcatb.2021.120433
32. [32]
  Zhang J S, Zhang M W, Lin S, Fu X Z, Wang X C. Molecular Doping of Carbon Nitride Photocatalysts with Tunable Bandgap and Enhanced Activity[J]. J. Catal., 2014,310:24-30. doi: 10.1016/j.jcat.2013.01.008
33. [33]
  Jiang Z, Isaacs M A, Huang Z W, Shangguan W F, Deng Y F, Lee A F. Active Site Elucidation and Optimization in Pt Co-catalysts for Photocatalytic Hydrogen Production over Titania[J]. ChemCatChem, 2017,9(22):4268-4274. doi: 10.1002/cctc.201700901
34. [34]
  Yang J H, Wang D G, Han H X, Li C. Roles of Cocatalysts in Photo-catalysis and Photoelectrocatalysis[J]. Acc. Chem. Res., 2013,46(8):1900-1909. doi: 10.1021/ar300227e
35. [35]
  Yang L P, Dong G H, Jacobs D L, Wang Y H, Zang L, Wang C Y. Two-Channel Photocatalytic Production of H₂O₂ over g-C₃N₄ Nanosheets Modified with Perylene Imides[J]. J. Catal., 2017,352:274-281. doi: 10.1016/j.jcat.2017.05.010
1. [1]
  Guoqiang Chen , Zixuan Zheng , Wei Zhong , Guohong Wang , Xinhe Wu . Molten Intermediate Transportation-Oriented Synthesis of Amino-Rich g-C₃N₄ Nanosheets for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2406021-0. doi: 10.3866/PKU.WHXB202406021
2. [2]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Construction of Electron Bridge and Activation of MoS₂ Inert Basal Planes by Ni Doping for Enhancing Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-0. doi: 10.3866/PKU.WHXB202406024
3. [3]
  Jianqiao ZHANG , Yang LIU , Yan HE , Yaling ZHOU , Fan YANG , Shihui CHENG , Bin XIA , Zhong WANG , Shijian CHEN . Ni-doped WP₂ nanowire self-standingelectrode: Preparation and alkaline electrocatalytic hydrogen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(8): 1610-1616. doi: 10.11862/CJIC.20240444
4. [4]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
5. [5]
  Peng ZHOU , Xiao CAI , Qingxiang MA , Xu LIU . Effects of Cu doping on the structure and optical properties of Au₁₁(dppf)₄Cl₂ nanocluster. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1254-1260. doi: 10.11862/CJIC.20240047
6. [6]
  Fan JIA , Wenbao XU , Fangbin LIU , Haihua ZHANG , Hongbing FU . Synthesis and electroluminescence properties of Mn²⁺ doped quasi-two-dimensional perovskites (PEA)₂Pb_yMn_1-yBr₄. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1114-1122. doi: 10.11862/CJIC.20230473
7. [7]
  Ximeng CHI , Jianwei WEI , Yunyun WANG , Wenxin DENG , Jiayi DAI , Xu ZHOU . First-principles study of the electronic structure and optical properties of Au and I doped-inorganic lead-free double perovskite Cs₂NaBiCl₆. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1371-1379. doi: 10.11862/CJIC.20240401
8. [8]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . Remarkable Photocatalytic H₂O₂ Production Efficiency over Ultrathin g-C₃N₄ Nanosheet with Large Surface Area and Enhanced Crystallinity by Two-Step Calcination. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-0. doi: 10.3866/PKU.WHXB202406019
9. [9]
  Ronghui LI . Photocatalysis performance of nitrogen-doped CeO₂ thin films via ion beam-assisted deposition. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1123-1130. doi: 10.11862/CJIC.20240440
10. [10]
  Qin Li , Huihui Zhang , Huajun Gu , Yuanyuan Cui , Ruihua Gao , Wei-Lin Dai . In situ Growth of Cd_0.5Zn_0.5S Nanorods on Ti₃C₂ MXene Nanosheet for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2025, 41(4): 2402016-0. doi: 10.3866/PKU.WHXB202402016
11. [11]
  Chenye An , Sikandaier Abiduweili , Xue Guo , Yukun Zhu , Hua Tang , Dongjiang Yang . Hierarchical S-scheme Heterojunction of Red Phosphorus Nanoparticles Embedded Flower-like CeO₂ Triggering Efficient Photocatalytic Hydrogen Production. Acta Physico-Chimica Sinica, 2024, 40(11): 2405019-0. doi: 10.3866/PKU.WHXB202405019
12. [12]
  Tong Zhou , Xue Liu , Liang Zhao , Mingtao Qiao , Wanying Lei . Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction. Acta Physico-Chimica Sinica, 2024, 40(10): 2309020-0. doi: 10.3866/PKU.WHXB202309020
13. [13]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-0. doi: 10.3866/PKU.WHXB202312007
14. [14]
  Yu Wang , Haiyang Shi , Zihan Chen , Feng Chen , Ping Wang , Xuefei Wang . 具有富电子Pt^δ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H₂O₂生成选择性与活性. Acta Physico-Chimica Sinica, 2025, 41(7): 100081-0. doi: 10.1016/j.actphy.2025.100081
15. [15]
  Yang Xia , Kangyan Zhang , Heng Yang , Lijuan Shi , Qun Yi . Improving Photocatalytic H₂O₂ Production over iCOF/Bi₂O₃ S-Scheme Heterojunction in Pure Water via Dual Channel Pathways. Acta Physico-Chimica Sinica, 2024, 40(11): 2407012-0. doi: 10.3866/PKU.WHXB202407012
16. [16]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
17. [17]
  Yifan ZHAO , Qiyun MAO , Meijing GUO , Guoying ZHANG , Tongliang HU . Z-scheme bismuth-based multi-site heterojunction: Synthesis and hydrogen production from photocatalytic hydrogen production. Chinese Journal of Inorganic Chemistry, 2025, 41(7): 1318-1330. doi: 10.11862/CJIC.20250001
18. [18]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
19. [19]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-0. doi: 10.3866/PKU.WHXB202408005
20. [20]
  Jianyin He , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Construction of ZnCoP/CdLa₂S₄ Schottky Heterojunctions for Enhancing Photocatalytic Hydrogen Evolution. Acta Physico-Chimica Sinica, 2024, 40(11): 2404030-0. doi: 10.3866/PKU.WHXB202404030

Get Citation

PDF

XML

Metrics

PDF Downloads(6)
Abstract views(974)
HTML views(169)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142