溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

引用本文: 白金, 陈鑫, 奚兆毅, 王翔, 李强, 胡绍争. 溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响[J]. 物理化学学报, 2017, 33(3): 611-619. doi: 10.3866/PKU.WHXB201611102 shu

Citation: BAI Jin, CHEN Xin, XI Zhao-Yi, WANG Xiang, LI Qiang, HU Shao-Zheng. Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst[J]. Acta Physico-Chimica Sinica, 2017, 33(3): 611-619. doi: 10.3866/PKU.WHXB201611102 shu

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

辽宁石油化工大学化学化工与环境学部, 辽宁抚顺 113001
基金项目:
国家自然科学基金（41571464）；辽宁省教育厅项目（L2014145）及辽宁省自然科学基金（201602467）资助

摘要: 采用离子液体[Bmim]Br为溶剂，溶剂热后处理法制备了具有大比表面积和氮空穴的石墨相氮化碳催化剂。采用X射线衍射（XRD）光谱、扫描电镜（SEM）、氮气吸附、紫外-可见（UV-Vis）光谱、X射线光电子能谱（XPS）、荧光光谱（PL）、电子顺磁共振谱（EPR）、程序升温脱附（TPD）等分析手段对制备的催化剂进行了表征。结果表明经过溶剂热后处理的催化剂形貌由无规则的层状结构变为尺寸为30-40 nm的纳米颗粒，导致比表面积从8.6 m²·g^-1增加到37.9 m²·g^-1。从N₂-TPD、荧光光谱及密度泛函理论（DFT）模拟计算的结果得出，氮空穴不仅能捕获光生电子促进电子空穴的有效分离，还能吸附并活化反应物氮气分子。溶剂热处理后，增加的比表面积导致更多的氮空穴作为反应活性位暴露在催化剂表面，是固氮活性显著提高。本文还探讨了可能的反应机理。

关键词:

English

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst

College of Chemistry, Chemical Engineering, and Environmental Engineering, Liaoning Shihua University, Fushun 113001, Liaoning Province, P. R. China
Received Date: 23 September 2016
Revised Date: 10 November 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (41571464)

Abstract: In this work, graphitic carbon nitride (g-C₃N₄) with large surface area and many nitrogen vacancies was synthesized by introducing ionic liquid[Bmim]Br as a solvent into the solvothermal post-treatment. X-ray diffraction (XRD), N₂ adsorption, scanning electron microscopy (SEM), UV-Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), temperature-programmed desorption of N₂ (N₂-TPD), and photoluminescence (PL) spectroscopy were used to characterize the prepared catalysts. The morphology of the as-prepared g-C₃N₄ was markedly changed from an orderless layered structure to nanoparticles with a uniform size distribution of around 30-40 nm after the introduction of[Bmim]Br, leading an increase in surface area from 8.6 to 37.9 m²·g^-1. N₂-TPD, photoluminescence spectra, and density functional theory (DFT) simulations indicated that the nitrogen vacancies not only trapped the photogenerated electrons to enhance their separation rate, but also served as active sites for the adsorption and activation of N₂ molecules. The increased surface area of the as-prepared g-C₃N₄ meant that more nitrogen vacancies were exposed on the surface, leading to a markedly promoted nitrogen photofixation ability. The possible reaction mechanism is proposed.

Key words:

1. [1]
  Vol'pin, M. E.; Shur, V. B.; Berkovich, E. G. Inorg. Chim. Acta 1998, 280, 264. doi: 10.1016/S0020-1693(98)00206-0
2. [2]
  Leigh, G. J. Science 1998, 279, 506. doi: 10.1126/science.279.5350.506
3. [3]
  Tamelen, E. E.; Akermark, B. J. Am. Chem. Soc.1968, 90, 4492. doi: 10.1021/ja01018a074
4. [4]
  Dickson, C. R.; Nozik, A. J. J. Am. Chem. Soc.1978, 100, 8007. doi: 10.1021/ja00493a039
5. [5]
  Hu, S. Z.; Li, Y. M.; Li, F. Y.; Fan, Z. P.; Ma, H. F.; Li, W.; Kang, X. X. ACS. Sus. Chem. Eng. 2016, 4, 2269. doi: 10.1021/acssuschemeng.5b01742
6. [6]
  Ranjit, K. T.; Viswanathan, B. Indian J. Chem. Sect. A 1996, 35, 443.
7. [7]
  Schrauzer, G. N.; Guth, T. D. J. Am. Chem. Soc.1977, 99, 7189. doi: 10.1021/ja00464a015
8. [8]
  Ranjit, K. T.; Varadarajan, T. K.; Viswanathan, B. J. Photochem.Photobiol. A:Chem.1996, 96, 181. doi: 10.1016/1010-6030(95)04290-3
9. [9]
  Rusina, O.; Linnik, O.; Eremenko, A.; Kisch, H. Chem. Eur. J.2003, 9, 561. doi: 10.1002/chem.200390059
10. [10]
  Hoshino, K. Chem. Eur. J.2001, 7, 2727. doi: 10.1002/1521-3765(20010702)7:13<2727::AID-CHEM2727>3.0.CO;2-4
11. [11]
  Hoshino, K.; Inui, M.; Kitamura, T.; Kokado, H. Angew. Chem.Int. Ed.2000, 39, 2509. doi: 10.1002/1521-3773(20000717)39:14<2509::AID-ANIE2509>3.0.CO;2-I
12. [12]
  Zhao, W. R.; Zhang, J.; Zhu, X.; Zhang, M.; Tang, J.; Tan, M.; Wang, Y. Appl. Catal. B:Environ.2014, 144, 468. doi: 10.1016/j.apcatb.2013.07.047
13. [13]
  Liang, Y. T.; Vijayan, B. K.; Gray, K. A.; Hersam, M. C. Nano Lett.2011, 11, 2865. doi: 10.1021/nl2012906
14. [14]
  Walter, M. G.; Warren, E. L.; McKone, J. R.; Boettcher, S.W.; Mi, Q.; Santori, E. A.; Lewis, N. S. Chem. Rev.2010, 110, 6446. doi: 10.1021/cr1002326
15. [15]
  Britto, P. J.; Santhanam, K. S. V.; Rubio, A.; Alonso, J. A.; Ajayan, P. M. Adv. Mater.1999, 11, 154. doi: 10.1002/(SICI)1521-4095(199902)11:2<154::AID-ADMA154>3.0.CO;2-B
16. [16]
  Zhu, D.; Zhang, L.; Ruther, R. E.; Ruther, R. J. Nat. Mater.2013, 12, 836. doi: 10.1038/nmat3696
17. [17]
  Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M. Nat. Mater.2009, 8, 76. doi: 10.1038/nmat2317
18. [18]
  Zhao, Z.W.; Sun, Y. J.; Dong, F. Nanoscale 2015, 7, 15. doi: 10.1039/c4nr03008g
19. [19]
  Zheng, Y.; Liu, J.; Liang, J.; Jaroniec, M.; Qiao, S. Energy Environ. Sci. 2012, 5, 6717. doi: 10.1039/c2ee03479d
20. [20]
  Zheng, Y.; Jiao, Y.; Chen, J.; Liu, J.; Liang, J.; Du, A.; Zhang, W.; Zhu, Z.; Jaroniec, M.; Smith, S. C.; Lu, G.; Qiao, S. J. Am.Chem. Soc.2011, 133, 20116. doi: 10.1021/ja209206c
21. [21]
  Xu, J.; Wu, H. T.; Wang, X.; Xue, B.; Li, Y. X.; Cao, Y. Phys. Chem. Chem. Phys.2013, 15, 4510. doi: 10.1039/c3cp44402c
22. [22]
  Li, Q.; Yang, J.; Feng, D.; Wu, Z.; Wu, Q.; Park, S. S.; Ha, C. S.; Zhao, D. Nano Res.2010, 3, 632. doi: 10.1007/s12274-010-0023-7
23. [23]
  Park, S. S.; Chu, S.W.; Xue, C.; Zhao, D.; Ha, C. S. Mater. J.Chem.2011, 21, 10801. doi: 10.1039/c1jm10849b
24. [24]
  Welton, T. Chem. Rev. 1999, 99, 2071. doi: 10.1021/cr980032t
25. [25]
  Keim, W. Angew. Chem. Int. Ed.2000, 39, 3772. doi: 10.1002/1521-3773(20001103)39:21<3772::AID-ANIE3772>3.0.CO;2-5
26. [26]
  Kubisa, P. Prog. Polym. Sci. 2004, 29, 3. doi: 10.1016/j.progpolymsci.2003.10.002
27. [27]
  Paramasivam, I.; Macak, J. M.; Selvam, T.; Schmuki, P.Electrochim. Acta 2008, 54, 643. doi: 10.1016/j.electacta.2008.07.031
28. [28]
  Yoo, K. S.; Lee, T. G.; Kim, J. Microporous Mesoporous Mat.2005, 84, 211. doi: 10.1016/j.micromeso.2005.05.029
29. [29]
  Ding, K. L.; Miao, Z. J.; Liu, Z. M.; Zhang, Z. F.; Han, B. X.; An, G. M.; Miao, S. D.; Xie, Y. J. Am. Chem. Soc.2007, 129, 6362. doi: 10.1021/ja070809c
30. [30]
  Liu, Y.; Li, J.; Wang, M. J.; Li, Z. Y.; Liu, H. T.; He, P.; Yang, X.R.; Li, J. H. Cryst. Growth Des.2005, 5, 1643. doi: 10.1021/cg050017z
31. [31]
  Xu, L.; Xia, J. X.; Xu, H.; Yin, S.; Wang, K.; Huang, L. Y.; Wang, L. G.; Li, H. M. J. Power Sources 2014, 245, 866. doi: 10.1016/j.jpowsour.2013.07.014
32. [32]
  Di, J.; Xia, J. X.; Yin, S.; Xu, H.; Xu, L.; He, M. Q.; Li, H. M.; Xu, L.; Jiang, Y. P. RSC Adv. 2013, 3, 19624. doi: 10.1039/c3ra42269k
33. [33]
  Xiao, D. L.; Li, S. Q.; Liu, S. B.; He, H.; Lu, J. R. New J. Chem.2016, 40, 320. doi: 10.1039/c5nj01717c
34. [34]
  Di, J.; Xia, J. X.; Yin, S.; Xu, H.; Xu, L.; Xu, Y. G.; He, M. Q.; Li, H. M. J. Mater. Chem. A. 2014, 2, 5340. doi: 10.1039/c3ta14617k
35. [35]
  Dong, G. H.; Ho, W. K.; Wang, C. Y. J. Mater. Chem. A 2015, 3, 23435. doi: 10.1039/c5ta06540b
36. [36]
  Li, H.; Shang, J.; Ai, Z. H.; Zhang, L. Z. J. Am. Chem. Soc.2015, 137, 6393. doi: 10.1021/jacs.5b03105
37. [37]
  Hong, Z. H.; Shen, B.; Chen, Y. L.; Lin, B. Z.; Gao, B. F.J. Mater. Chem. A 2013, 1, 11754. doi: 10.1039/c3ta12332d
38. [38]
  Hu, S. Z.; Li, F. Y.; Fan, Z. P.; Gui, J. Z. J. Power Sources 2014, 250, 30. doi: 10.1016/j.jpowsour.2013.10.132
39. [39]
  Yang, R. C.; Lu, X. J.; Huang, X.; Chen, Z. M.; Zhang, X.; Xu, M. D.; Song, Q.W.; Zhu, L. T. Appl. Catal. B:Environ.2015, 170-171, 225. doi: 10.1016/j.apcatb.2015.01.046
40. [40]
  Wang, Z. H.; Ma, W. H.; Chen, C. C.; Ji, H.W.; Zhao, J. C.Chem. Eng. J.2011, 170, 353. doi: 10.1016/j.cej.2010.12.002
41. [41]
  Wang, X. C.; Chen, X. F.; Thomas, A.; Fu, X. Z.; Antonietti, M.Adv. Mater.2009, 21, 1609. doi: 10.1002/adma.200802627
42. [42]
  Oregan, B.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737ao
43. [43]
  Yan, S. C.; Li, Z. S.; Zou, Z. G. Langmuir 2009, 25, 10397. doi: 10.1021/la900923z
44. [44]
  Hu, S. Z.; Ma, L.; Xie, Y.; Li, F. Y.; Fan, Z. P.; Wang, F.; Wang, Q.; Wang, Y. J.; Kang, X. X.; Wu, G. Dalton Trans. 2015, 44, 20889. doi: 10.1039/c5dt04035c
45. [45]
  Lei, W.; Portehault, D.; Dimova, R.; Antoniettit, M. J. Am.Chem. Soc. 2011, 133, 7121. doi: 10.1021/ja200838c
46. [46]
  Zhang, Y.W.; Liu, J. H.; Wu, G.; Chen, W. Nanoscale 2012, 4, 5300. doi: 10.1039/c2nr30948c
47. [47]
  Hu, S. Z.; Ma, L.; Li, F. Y.; Fan, Z. P.; Wang, Q.; Bai, J.; Kang, X. X.; Wu, G. RSC Adv. 2015, 5, 90750. doi: 10.1039/c5ra15611d619

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沈阳化工大学材料科学与工程学院沈阳 110142

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

English

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C₃N₄ Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

溶剂热后处理对石墨相氮化碳光化学固氮产氨性能的影响

English

Influence of Solvothermal Post-Treatment on Photochemical Nitrogen Conversion to Ammonia with g-C3N4 Catalyst

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

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