Citation: Lei Zhang, Zhe-Ji Wang, Bo Ma, Xiang-Yang Li, Yu-Chi Dai, Guowen Hu, Yong Peng, Qiang Wang, Hao-Li Zhang. Covalent carbene modification of 2D black phosphorus[J]. Chinese Chemical Letters, ;2022, 33(10): 4640-4644. doi: 10.1016/j.cclet.2021.12.046 shu

Covalent carbene modification of 2D black phosphorus

Lei Zhang ^{a, b} ,
Zhe-Ji Wang ^a ,
Bo Ma ^a ,
Xiang-Yang Li ^a ,
Yu-Chi Dai ^a ,
Guowen Hu ^a ,
Yong Peng ^c ,
Qiang Wang ^{a, b, *,} ,
Hao-Li Zhang ^{a, d, *,}

a.
State Key Laboratory of Applied Organic Chemistry (SKLAOC), Key Laboratory of Special Function Materials and Structure Design (MOE), College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
b.
Office of Laboratory and Equipment Management, Lanzhou University, Lanzhou 73000, China
c.
Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, School of Physical Science and Technology, Lanzhou University, Lanzhou 730000, China
d.
Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin 300072, China

qiangwang@lzu.edu.cn

haoli.zhang@lzu.edu.cn

Received Date: 30 September 2021
Revised Date: 30 October 2021
Accepted Date: 20 December 2021
Available Online: 24 December 2021

Figures(9)

Black phosphorus (BP) has attracted an ever-growing interest due to its unique anisotropic two-dimensional structure, impressive photoelectronic properties and attractive application potential. However, the tools for bandgap engineering and passivation via covalent modification of BP nanosheets remain limited to diazonium salt and nucleophilic addition methods, so that developing new modification strategies for BP nanosheets is crucial to explore its physical and chemical properties and enrich the toolbox for functionalization. Herein, we report the covalent modification of liquid-phase exfoliated BP nanosheets based on a rational analysis of BP structure. The modification of BP is achieved via carbene, a highly reactive organic mediate. The carbene modification improves the solubility and stability of BP nanosheets. Detailed microscopic and spectroscopic characterizations including infrared spectra, Raman spectra, X-ray photoelectron spectra, SEM and TEM were conducted to provide insights for the reaction. The proof of the existence of covalent bonds between BP nanosheets and organic moieties confirms the successful modification. Moreover, theoretical calculations were conducted to unveil the reaction mechanism of the two different types of bonds and the chemical property of two-dimensional BP.
- Two-dimensional materials,
- Black phosphorus,
- Covalent functionalization,
- Carbene,
- Solubility
1. [1]
  R. Roldan, L. Chirolli, E. Prada, et al., Chem. Soc. Rev. 46 (2017) 4387–4399. doi: 10.1039/C7CS00210F
2. [2]
  H. Zhang, ACS Nano 9 (2015) 9451–9469. doi: 10.1021/acsnano.5b05040
3. [3]
  H. Huang, J. Zha, S. Li, C. Tan, Chin. Chem. Lett. 33 (2022) 163–176. doi: 10.1016/j.cclet.2021.06.004
4. [4]
  J.N. Coleman, M. Lotya, A. O'Neill, et al., Science 331 (2011) 568–571. doi: 10.1126/science.1194975
5. [5]
  A.C. Ferrari, F. Bonaccorso, V. Fal'ko, et al., Nanoscale 7 (2015) 4598–4810.
6. [6]
  Z. Zhou, B. Li, C. Shen, et al., Small 16 (2020) 2004173. doi: 10.1002/smll.202004173
7. [7]
  L. Li, Y. Yu, G.J. Ye, et al., J. Am. Chem. Soc. 36 (1914) 1344–1363. doi: 10.1021/ja02184a002
8. [8]
  J.S. Miao, L. Zhang, C. Wang, 2D Mater. 6 (2019) 032003. doi: 10.1088/2053-1583/ab1ebd
9. [9]
  Z. Guo, H. Zhang, S. Lu, et al., Adv. Funct. Mater. 25 (2015) 6996–7002. doi: 10.1002/adfm.201502902
10. [10]
  C. Qian, R. Wang, M. Li, Colloid. Surf. A Physicochem. Engin. Asp. 608 (2021) 125616. doi: 10.1016/j.colsurfa.2020.125616
11. [11]
  R. Wang, X. Yan, B. Ge, et al., ACS Sustain. Chem. Engin. 8 (2020) 4521–4536. doi: 10.1021/acssuschemeng.9b07840
12. [12]
  M.B. Erande, M.S. Pawar, D.J. Late, ACS Appl. Mater. Interfaces 8 (2016) 11548–11556. doi: 10.1021/acsami.5b10247
13. [13]
  L. Zhang, L.F. Gao, L.X. Li, et al., Mater. Chem. Front. 2 (2018) 1700–1706. doi: 10.1039/C8QM00237A
14. [14]
  A. Ambrosi, Z. Sofer, M. Pumera, Angew. Chem. Int. Ed. 56 (2017) 10443–10445. doi: 10.1002/anie.201705071
15. [15]
  E.A. Lewis, J.R. Brent, B. Derby, S.J. Haigh, D.J. Lewis, Chem. Commun. 53 (2017) 1445–1458. doi: 10.1039/C6CC09658A
16. [16]
  A. Hirsch, J.M. Englert, F. Hauke, Acc. Chem. Res. 46 (2013) 87–96. doi: 10.1021/ar300116q
17. [17]
  C. Xing, L. Liu, D. Fan, Z. Peng, H. Zhang, FlatChem 13 (2019) 8–24. doi: 10.1016/j.flatc.2018.12.002
18. [18]
  G.L. Paulus, Q.H. Wang, M.S. Strano, Mater. Today 19 (2016) 140–145. doi: 10.1016/j.mattod.2015.08.019
19. [19]
  K.C. Knirsch, N.C. Berner, H.C. Nerl, et al., ACS Nano 9 (2015) 6018–6030. doi: 10.1021/acsnano.5b00965
20. [20]
  S. Thurakkal, X. Zhang, Adv. Sci. 7 (2020) 1902359. doi: 10.1002/advs.201902359
21. [21]
  Z. Liu, B. Zhang, N. Dong, J. Wang, Y. Chen, J. Mater. Chem. C 8 (2020) 10197–10203. doi: 10.1039/d0tc00685h
22. [22]
  Z. Sofer, J. Luxa, D. Bousa, Angew. Chem. Int. Ed. 56 (2017) 9891–9896. doi: 10.1002/anie.201705722
23. [23]
  C.R. Ryder, J.D. Wood, S.A. Wells, Nat. Chem. 8 (2016) 597–602. doi: 10.1038/nchem.2505
24. [24]
  A. Mitrovic, S. Wild, V. Lloret, Chem. Eur. J. 15 (2020) 3361–3366.
25. [25]
  J.R. Brent, N. Savjani, E.A. Lewis, et al., Chem. Commun. 50 (2014) 13338–13341. doi: 10.1039/C4CC05752J
26. [26]
  Y. Chen, R.C. Haddon, S. Fang, J. Mater. Res. 13 (2011) 2423–2431.
27. [27]
  C.K. Chua, A. Ambrosi, M. Pumera, Chem. Commun. 48 (2012) 5376–5378. doi: 10.1039/c2cc31936e
28. [28]
  J. Sturala, A. Ambrosi, Z. Sofer, M. Pumera, Angew. Chem. Int. Ed. 5 (2018) 14837–14840. doi: 10.1002/anie.201809341
29. [29]
  T. Mou, B. Wang, ACS Omega 3 (2018) 2445–2451. doi: 10.1021/acsomega.7b01992
30. [30]
  Y. Liu, P. Gao, T. Zhang, et al., Angew. Chem. Int. Ed. 58 (2019) 1479–1483. doi: 10.1002/anie.201813218
31. [31]
  K. Zhou, J. Liu, P. Wen, Y. Hu, Z. Gui, Appl. Surf. Sci. 316 (2014) 237–244. doi: 10.1016/j.apsusc.2014.07.136
32. [32]
  R.H. Goncalves, R. Fiel, M.R. Soares, et al., Chem. Eur. J. 21 (2015) 15583–15588. doi: 10.1002/chem.201502303
33. [33]
  S. Eigler, A. Hirsch, Angew. Chem. Int. Ed. 53 (2014) 7720–7738. doi: 10.1002/anie.201402780
34. [34]
  Y. Zhu, A.L. Higginbotham, J.M. Tour, Chem. Mater. 21 (2009) 5284–5291. doi: 10.1021/cm902939n
1. [1]
  Yu-Hui Zhang , Ye Tian , Xianliang Sheng , Chen-Shuang Liu , Lu-Qiang Wei , Jie Wang , Yong Chen . Construction of a black phosphorous-based noncovalent multiple nanosupramolecular assembly for synergistic targeted photothermal and chemodynamic therapy. Chinese Chemical Letters, 2025, 36(4): 110193-. doi: 10.1016/j.cclet.2024.110193
2. [2]
  Ying-Di Hao , Zhi-Qian Lin , Xiao-Yu Guo , Jiao Liang , Can-Kun Luo , Qian-Tao Wang , Li Guo , Yong Wu . Rhodium-catalyzed Doyle-Kirmse rearrangement reactions of sulfoxoniun ylides. Chinese Chemical Letters, 2024, 35(4): 108834-. doi: 10.1016/j.cclet.2023.108834
3. [3]
  Ziyang Yin , Lingbin Xie , Weinan Yin , Ting Zhi , Kang Chen , Junan Pan , Yingbo Zhang , Jingwen Li , Longlu Wang . Advanced development of grain boundaries in TMDs from fundamentals to hydrogen evolution application. Chinese Chemical Letters, 2024, 35(5): 108628-. doi: 10.1016/j.cclet.2023.108628
4. [4]
  Jiahao Li , Guinan Chen , Chunhong Chen , Yuanyuan Lou , Zhihao Xing , Tao Zhang , Chengtao Gong , Yongwu Peng . Modulated synthesis of stoichiometric and sub-stoichiometric two-dimensional covalent organic frameworks for enhanced ethylene purification. Chinese Chemical Letters, 2025, 36(1): 109760-. doi: 10.1016/j.cclet.2024.109760
5. [5]
  Xi Zhou , Shengyao Wang . Dynamic two-dimensional covalent organic frameworks via ‘wine rack' design. Chinese Journal of Structural Chemistry, 2025, 44(4): 100464-100464. doi: 10.1016/j.cjsc.2024.100464
6. [6]
  Yuting Wu , Haifeng Lv , Xiaojun Wu . Design of two-dimensional porous covalent organic framework semiconductors for visible-light-driven overall water splitting: A theoretical perspective. Chinese Journal of Structural Chemistry, 2024, 43(11): 100375-100375. doi: 10.1016/j.cjsc.2024.100375
7. [7]
  Jia Zhou , Huaying Zhong . Experimental Design of Computational Materials Science Combined with Machine Learning. University Chemistry, 2025, 40(3): 171-177. doi: 10.12461/PKU.DXHX202406004
8. [8]
  Jie Zhou , Chuanxiang Zhang , Changchun Hu , Shuo Li , Yuan Liu , Zhu Chen , Song Li , Hui Chen , Rokayya Sami , Yan Deng . Electrochemical aptasensor based on black phosphorus-porous graphene nanocomposites for high-performance detection of Hg²⁺. Chinese Chemical Letters, 2024, 35(11): 109561-. doi: 10.1016/j.cclet.2024.109561
9. [9]
  Yuhao Ma , Yufei Zhou , Mingchuan Yu , Cheng Fang , Shaoxia Yang , Junfeng Niu . Covalently bonded ternary photocatalyst comprising MoSe₂/black phosphorus nanosheet/graphitic carbon nitride for efficient moxifloxacin degradation. Chinese Chemical Letters, 2024, 35(9): 109453-. doi: 10.1016/j.cclet.2023.109453
10. [10]
  Kun Tang , Fen Su , Shijie Pan , Fengfei Lu , Zhongfu Luo , Fengrui Che , Xingxing Wu , Yonggui Robin Chi . Enones from aldehydes and alkenes by carbene-catalyzed dehydrogenative couplings. Chinese Chemical Letters, 2024, 35(9): 109495-. doi: 10.1016/j.cclet.2024.109495
11. [11]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
12. [12]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
13. [13]
  Tian Yang , Yi Liu , Lina Hua , Yaoyao Chen , Wuqian Guo , Haojie Xu , Xi Zeng , Changhao Gao , Wenjing Li , Junhua Luo , Zhihua Sun . Lead-free hybrid two-dimensional double perovskite with switchable dielectric phase transition. Chinese Chemical Letters, 2024, 35(6): 108707-. doi: 10.1016/j.cclet.2023.108707
14. [14]
  Zhuoer Cai , Yinan Zhang , Xiu-Ni Hua , Baiwang Sun . Phase transition arising from order-disorder motion in stable layered two-dimensional perovskite. Chinese Journal of Structural Chemistry, 2024, 43(11): 100426-100426. doi: 10.1016/j.cjsc.2024.100426
15. [15]
  Muhammad Riaz , Rakesh Kumar Gupta , Di Sun , Mohammad Azam , Ping Cui . Selective adsorption of organic dyes and iodine by a two-dimensional cobalt(II) metal-organic framework. Chinese Journal of Structural Chemistry, 2024, 43(12): 100427-100427. doi: 10.1016/j.cjsc.2024.100427
16. [16]
  Zhe Li , Ping-Zhao Liang , Li Xu , Fei-Yu Yang , Tian-Bing Ren , Lin Yuan , Xia Yin , Xiao-Bing Zhang . Three positive charge nonapoptotic-induced photosensitizer with excellent water solubility for tumor therapy. Chinese Chemical Letters, 2024, 35(8): 109190-. doi: 10.1016/j.cclet.2023.109190
17. [17]
  Zhihong LUO , Yan SHI , Jinyu AN , Deyi ZHENG , Long LI , Quansheng OUYANG , Bin SHI , Jiaojing SHAO . Two-dimensional silica-modified polyethylene oxide solid polymer electrolyte to enhance the performance of lithium-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 1005-1014. doi: 10.11862/CJIC.20230444
18. [18]
  Lu LIU , Huijie WANG , Haitong WANG , Ying LI . Crystal structure of a two-dimensional Cd(Ⅱ) complex and its fluorescence recognition of p-nitrophenol, tetracycline, 2, 6-dichloro-4-nitroaniline. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1180-1188. doi: 10.11862/CJIC.20230489
19. [19]
  Xuan Zhu , Lin Zhou , Xiao-Yun Huang , Yan-Ling Luo , Xin Deng , Xin Yan , Yan-Juan Wang , Yan Qin , Yuan-Yuan Tang . (Benzimidazolium)2GeI4: A layered two-dimensional perovskite with dielectric switching and broadband near-infrared photoluminescence. Chinese Journal of Structural Chemistry, 2024, 43(6): 100272-100272. doi: 10.1016/j.cjsc.2024.100272
20. [20]
  Xinghong Cai , Qiang Yang , Yao Tong , Lanyin Liu , Wutang Zhang , Sam Zhang , Min Wang . AlO₂: A novel two-dimensional material with a high negative Poisson's ratio for the adsorption of volatile organic compounds. Chinese Chemical Letters, 2025, 36(2): 109586-. doi: 10.1016/j.cclet.2024.109586

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1011)
HTML views(187)

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