Fabrication of Graphene Quantum Dots Modified BiOI/PAN Flexible Fiber with Enhanced Photocatalytic Activity

Citation: Rongan He, Rong Chen, Jinhua Luo, Shiying Zhang, Difa Xu. Fabrication of Graphene Quantum Dots Modified BiOI/PAN Flexible Fiber with Enhanced Photocatalytic Activity[J]. Acta Physico-Chimica Sinica, 2021, 37(6): 201102. doi: 10.3866/PKU.WHXB202011022 shu

石墨烯量子点修饰的BiOI/PAN柔性纤维的制备及其增强的光催化活性

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长沙学院环境光催化应用技术湖南省重点实验室, 长沙 410022

通讯作者: 许第发, xudifa@sina.com

基金项目:
国家自然科学基金 52073034

国家自然科学基金 21871030

湖南省自然科学基金 2018JJ2457

湖南省自然科学基金 2017JJ3340

湖南省教育厅科学研究项目 18A370

摘要: 在环境治理中，光催化氧化是去除有机污染物的一种很有前途的技术。与吸附、生物降解和化学氧化等方法相比，光催化氧化可以通过环境友好的方式，完全、方便、廉价地消除有机污染物。光催化氧化中，又以可见光光催化氧化更具优势，这是因为可见光在太阳光中的能量比例较高。碘氧化铋(BiOI)是一种很有前途的可见光光催化剂，不仅具有较窄的带隙，而且具有较低的价带(VB)，其产生的光生空穴能氧化分解多种有机污染物。然而，BiOI粉末回收困难、比表面积低、载流子复合快等缺点限制了其实际应用。同时，光催化剂的柔性和分级结构有利于这些材料的操作、回收和性能改进，也是非常可取的特性。为此，本文以静电纺丝制备的聚丙烯腈(PAN)纳米纤维为基底，通过原位反应的方法，制备了具有分级结构的柔性BiOI/PAN复合纤维。在BiOI/PAN纤维中，BiOI薄片围绕PAN纤维、垂直均匀地排列在其表面，形成独特的分级结构。在制备的过程中，PAN纤维中掺入的Bi(Ⅲ)会先形成的BiOI晶核，并成为BiOI纳米片生长的种子。这对分级结构的形成至关重要。紫外-可见漫反射光谱和光致发光发射分析显示，这种分级结构可以改善BiOI/PAN光纤的光吸收，促进光生载流子的形成。因此，BiOI/PAN纤维比BiOI粉末具有更高的光催化活性。进一步，用预先制备的石墨烯量子点(GQDs)对BiOI/PAN纤维进行修饰，可制备出GQDs修饰的BiOI/PAN纤维复合材料(GQD-BiOI/PAN)。所制备GQD-BiOI/PAN的形貌与BiOI/PAN纤维几乎是一样的。通过制备方法、光致发光发射、反应自由基测试和X射线光电子能谱(XPS)的综合分析，证实了GQDs与BiOI之间会形成梯型(S型)异质结。这种S型异质结不仅能有效地抑制光生空穴的复合，而且能保留GQDs的最低未占据分子轨道(LUMO)上还原能力更强的电子，以及BiOI的VB上氧化能力更强的空穴，用于光催化降解苯酚。在纤维分级结构和S型异质结的共同作用下，GQD-BiOI/PAN在可见光光催化氧化苯酚中，其性能明显优于BiOI粉末和BiOI/PAN纳米纤维。此外，由于粘结紧密，GQD-BIOI/PAN可以进行裁剪和徒手操作，回收利用非常方便。在循环性能测试中，没有明显的样品损失和光催化活性的降低的现象。本文的工作为制备柔性光催化剂提供了一条新的途径，并对光催化剂的增强提供了新的视野。

关键词:

English

Fabrication of Graphene Quantum Dots Modified BiOI/PAN Flexible Fiber with Enhanced Photocatalytic Activity

Hunan Province Key Laboratory of Applied Environmental Photocatalysis, Changsha University, Changsha 410022, China

Corresponding author: Difa Xu, xudifa@sina.com

Received Date: 06 November 2020
Accepted Date: 26 November 2020
Revised Date: 20 November 2020
Available Online: 15 June 2021
Fund Project:

Abstract: In environment remediation, photocatalytic oxidation is a promising technique for removing organic pollutants. Compared to adsorption, biodegradation, and chemical oxidation, photocatalytic oxidation can eliminate organic pollutants completely, conveniently, and cheaply in an environmentally friendly manner. Visible-light-driven photocatalytic oxidation is particularly advisable because of the high proportion of visible light energy in solar energy. Bismuth oxyiodide (BiOI) is a promising visible-light-driven photocatalyst for the oxidization of pollutants, not only because of its narrow band gap, but also for its relatively low valence band (VB), which is adequate for photogenerated holes to oxidize a variety of organic compounds. However, the shortcomings of BiOI powder, such the difficulty of recycling it, its low surface area, and fast carrier recombination, limit its practical applications. Meanwhile, the flexibility and hierarchical structure of photocatalysts are particularly advisable because these properties are beneficial for the convenient operation, recycling, and performance improvement of these materials. Herein, based on an electro-spun polyacrylonitrile (PAN) nanofiber substrate, a hierarchical BiOI/PAN fiber was prepared through an in situ reaction. In the as-prepared BiOI/PAN fibers, BiOI flakes were aligned vertically and uniformly around the PAN fibers. BiOI nuclei generated from pre-introduced Bi(Ⅲ) in the PAN fiber act as seeds for the growth of BiOI nanoplates, which is crucial for the formation of a hierarchical structure. Such a hierarchical structure can improve both the light absorption and carrier generation of the BiOI/PAN fibers, as demonstrated by UV-Vis diffuse reflectance spectra and photoluminescence emission. Therefore, the BiOI/PAN fibers exhibited higher photocatalytic activity than BiOI powder. When the BiOI/PAN fibers were decorated with pre-prepared graphene quantum dots (GQDs), a GQD-modified BiOI/PAN fibrous composite (GQD-BiOI/PAN) was fabricated. The morphology of the obtained GQD-BiOI/PAN fibers was nearly the same as that of the BiOI/PAN fibers. A step-scheme (S-scheme) heterojunction was formed between the GQDs and BiOI, which was confirmed by the fabrication method, photoluminescence emission, reactive radical tests, and XPS analysis. This kind of S-scheme heterojunction can not only effectively suppress the recombination of photogenerated holes, but can also reserve the more reductive electrons on the lowest unoccupied molecular orbital of GQDs and the more oxidative holes on the VB of BiOI, for the photocatalytic degradation of phenol. Because of the fibrous hierarchical structure and S-scheme heterojunction, GQD-BiOI/PAN outperformed BiOI nanoparticles and BiOI/PAN nanofibers in the photocatalytic oxidation of phenol under visible light. In addition, because of tight bonding, GQD-BiOI/PAN can be tailored and operated by hand, which is convenient for recycling. During recycling, no obvious loss of sample or decrease in photocatalytic activity was observed. This work provides a new pathway for the fabrication of flexible photocatalysts and a new insight into the enhancement of photocatalysts.

Key words:

1. [1]
  Khin, M. M.; Nair, A. S.; Babu, V. J.; Murugan, R.; Ramakrishna, S. Energ. Environ. Sci. 2012, 5, 8075. doi: 10.1039/c2ee21818f
2. [2]
  Brillas, E.; Martínez-Huitle, C. A. Appl. Catal. B 2015, 166–167, 603. doi: 10.1016/j.apcatb.2014.11.016
3. [3]
  Ibrahim, R. K.; Hayyan, M.; Alsaadi, M. A.; Hayyan, A.; Ibrahim, S. Environ. Sci. Pollut. Res. Int. 2016, 23, 13754. doi: 10.1007/s11356-016-6457-z
4. [4]
  Reddy, P. A. K.; Reddy, P. V. L.; Kwon, E.; Kim, K.; Akter, T.; Kalagara, S. Environ. Int. 2016, 91, 94. doi: 10.1016/j.envint.2016.02.012
5. [5]
  Wang, J.; Wang, S. J. Environ. Manage. 2016, 182, 620. doi: 10.1016/j.jenvman.2016.07.049
6. [6]
  王艺蒙, 张申平, 葛宇, 王臣辉, 胡军, 刘洪来.物理化学学报, 2020, 36, 1905083. doi: 10.3866/PKU.WHXB201905083Wang, Y.; Zhang, S.; Ge, Y.; Wang, C.; Hu, J.; Liu, H. Acta Phys. -Chim. Sin. 2020, 36, 1905083. doi: 10.3866/PKU.WHXB201905083
7. [7]
  Wang, S.; Yun, J.; Luo, B.; Butburee, T.; Peerakiatkhajohn, P.; Thaweesak, S.; Xiao, M.; Wang, L. J. Mater. Sci. Technol. 2017, 33, 1. doi: 10.1016/j.jmst.2016.11.017
8. [8]
  He, R.; Xu, D.; Cheng, B.; Yu, J.; Ho, W. Nanoscale Horiz. 2018, 3, 464. doi: 10.1039/c8nh00062j
9. [9]
  He, R.; Cao, S.; Zhou, P.; Yu, J. Chin. J. Catal. 2014, 35, 989. doi: 10.1016/S1872-2067(14)60075-9
10. [10]
  Xiang, X.; Zhu, B.; Cheng, B.; Yu, J.; Lv, H. Small 2020, 16, 2001024. doi: 10.1002/smll.202001024
11. [11]
  Liu, X.; Gu, S.; Zhao, Y.; Zhou, G.; Li, W. J. Mater. Sci. Technol. 2020, 56, 45. doi: 10.1016/j.jmst.2020.04.023
12. [12]
  Yang, Y.; Zhang, C.; Lai, C.; Zeng, G.; Huang, D.; Cheng, M.; Wang, J.; Chen, F.; Zhou, C.; Xiong, W. Adv. Colloid Interface Sci. 2018, 254, 76. doi: 10.1016/j.cis.2018.03.004
13. [13]
  He, R.; Zhang, J.; Yu, J.; Cao, S. J. Colloid Interface Sci. 2016, 478, 201. doi: 10.1016/j.jcis.2016.06.012
14. [14]
  Di, J.; Xia, J.; Li, H.; Guo, S.; Dai, S. Nano Energy 2017, 41, 172. doi: 10.1016/j.nanoen.2017.09.008
15. [15]
  Cheng, H.; Huang, B.; Dai, Y. Nanoscale 2014, 6, 2009. doi: 10.1039/c3nr05529a
16. [16]
  Anwer, H.; Mahmood, A.; Lee, J.; Kim, K.; Park, J.; Yip, A. C. K. Nano Res. 2019, 12, 955. doi: 10.1007/s12274-019-2287-0
17. [17]
  Sharma, K.; Dutta, V.; Sharma, S.; Raizada, P.; Hosseini-Bandegharaei, A.; Thakur, P.; Singh, P. J. Ind. Eng. Chem. 2019, 78, 1. doi: 10.1016/j.jiec.2019.06.022
18. [18]
  Xing, Z.; Zhang, J.; Cui, J.; Yin, J.; Zhao, T.; Kuang, J.; Xiu, Z.; Wan, N.; Zhou, W. Appl. Catal. B 2018, 225, 452. doi: 10.1016/j.apcatb.2017.12.005
19. [19]
  Komeily-Nia, Z.; Montazer, M.; Heidarian, P.; Nasri-Nasrabadi, B. Polym. Adv. Technol. 2019, 30, 235. doi: 10.1002/pat.4480
20. [20]
  Liao, C.; Ma, Z.; Dong, G.; Qiu, J. J. Am. Ceram. Soc. 2015, 98, 957. doi: 10.1111/jace.13388
21. [21]
  He, R.; Lou, Z.; Gui, J.; Tang, B.; Xu, D. Appl. Surf. Sci. 2020, 504, 144370. doi: 10.1016/j.apsusc.2019.144370
22. [22]
  Zhang, Q.; Bai, J.; Li, G.; Li, C. J. Solid State Chem. 2019, 270, 129. doi: 10.1016/j.jssc.2018.11.015
23. [23]
  Li, H.; Su, Z.; Hu, S.; Yan, Y. Appl. Catal. B 2017, 207, 134. doi: 10.1016/j.apcatb.2017.02.013
24. [24]
  Fu, J.; Zhu, B.; You, W.; Jaroniec, M.; Yu, J. Appl. Catal. B 2018, 220, 148. doi: 10.1016/j.apcatb.2017.08.034
25. [25]
  Karim, S. A.; Mohamed, A.; Abdel-Mottaleb, M. M.; Osman, T. A.; Khattab, A. J. Alloy. Compd. 2019, 772, 650. doi: 10.1016/j.jallcom.2018.09.155
26. [26]
  Mohamed, A.; Nasser, W. S.; Kamel, B. M.; Hashem, T. Eur. Polym. J. 2019, 113, 192. doi: 10.1016/j.eurpolymj.2019.01.062
27. [27]
  Prasanth, R.; Aravindan, V.; Srinivasan, M. J. Power Sources 2012, 202, 299. doi: 10.1016/j.jpowsour.2011.11.057
28. [28]
  Wang, K.; Shao, C.; Li, X.; Miao, F.; Lu, N.; Liu, Y. J. Sol-Gel Sci. Technol. 2016, 80, 783. doi: 10.1007/s10971-016-4161-6
29. [29]
  Xu, F.; Meng, K.; Cheng, B.; Wang, S.; Xu, J.; Yu, J. Nat. Commun. 2020, 11, 4613. doi: 10.1038/s41467-020-18350-7
30. [30]
  He, R.; Cheng, K.; Wei, Z.; Zhang, S.; Xu, D. Appl. Surf. Sci. 2019, 465, 964. doi: 10.1016/j.apsusc.2018.09.217
31. [31]
  Xu, Q.; Zhang, L.; Cheng, B.; Fan, J.; Yu, J. Chem 2020, 6, 1543. doi: 10.1016/j.chempr.2020.06.010
32. [32]
  Xie, Q.; He, W.; Liu, S.; Li, C.; Zhang, J.; Wong, P. K. Chin. J. Catal. 2020, 41, 140. doi: 10.1016/S1872-2067(19)63481-9
33. [33]
  He, F.; Meng, A.; Cheng, B.; Ho, W.; Yu, J. Chin. J. Catal. 2020, 41, 9. doi: 10.1016/S1872-2067(19)63382-6
34. [34]
  Li, X.; Xiong, J.; Gao, X.; Ma, J.; Chen, Z.; Kang, B.; Liu, J.; Li, H.; Feng, Z.; Huang, J. J. Hazard. Mater. 2020, 387, 121690. doi: 10.1016/j.jhazmat.2019.121690
35. [35]
  Wang, J.; Zhang, Q.; Deng, F.; Luo, X.; Dionysiou, D. D. Chem. Eng. J. 2020, 379, 122264. doi: 10.1016/j.cej.2019.122264
36. [36]
  He, R.; Liu, H.; Liu, H.; Xu, D.; Zhang, L. J. Mater. Sci. Technol. 2020, 52, 145. doi: 10.1016/j.jmst.2020.03.027
37. [37]
  Li, Z.; Wu, Z.; He, R.; Wan, L.; Zhang, S. J. Mater. Sci. Technol. 2020, 56, 151. doi: 10.1016/j.jmst.2020.02.061
38. [38]
  Xia, P.; Cao, S.; Zhu, B.; Liu, M.; Shi, M.; Yu, J.; Zhang, Y. Angew. Chem. Int. Ed. 2020, 59, 5218. doi: 10.1002/anie.201916012
39. [39]
  He, F.; Zhu, B.; Cheng, B.; Yu, J.; Ho, W.; Macyk, W. Appl. Catal. B 2020, 272, 119006. doi: 10.1016/j.apcatb.2020.119006
40. [40]
  Wang, Z.; Chen, Y.; Zhang, L.; Cheng, B.; Yu, J.; Fan, J. J. Mater. Sci. Technol. 2020, 56, 143. doi: 10.1016/j.jmst.2020.02.062
41. [41]
  Ge, H.; Xu, F.; Cheng, B.; Yu, J.; Ho, W. ChemCatChem 2019, 11, 6301. doi: 10.1002/cctc.201901486
42. [42]
  Yan, Y.; Gong, J.; Chen, J.; Zeng, Z.; Huang, W.; Pu, K.; Liu, J.; Chen, P. Adv. Mater. 2019, 31, 1808283. doi: 10.1002/adma.201808283
43. [43]
  Yeh, T.; Chen, S.; Teng, H. Nano Energy 2015, 12, 476. doi: 10.1016/j.nanoen.2015.01.021
44. [44]
  Roushani, M.; Mavaei, M.; Daneshfar, A.; Rajabi, H. R. J. Mater. Sci.: Mater. Electron. 2017, 28, 5135. doi: 10.1007/s10854-016-6169-7
45. [45]
  Ye, R.; Peng, Z.; Metzger, A.; Lin, J.; Mann, J. A.; Huang, K.; Xiang, C.; Fan, X.; Samuel, E. L. G.; Alemany, L. B.; et al. ACS Appl. Mater. Interface. 2015, 7, 7041. doi: 10.1021/acsami.5b01419
46. [46]
  Yan, M.; Hua, Y.; Zhu, F.; Gu, W.; Jiang, J.; Shen, H.; Shi, W. Appl. Catal. B 2017, 202, 518. doi: 10.1016/j.apcatb.2016.09.039
47. [47]
  Yuan, A.; Lei, H.; Xi, F.; Liu, J.; Qin, L.; Chen, Z.; Dong, X. J. Colloid Interface Sci. 2019, 548, 56. doi: 10.1016/j.jcis.2019.04.027
48. [48]
  Yan, Y.; Chen, J.; Li, N.; Tian, J.; Li, K.; Jiang, J.; Liu, J.; Tian, Q.; Chen, P. ACS Nano 2018, 12, 3523. doi: 10.1021/acsnano.8b00498
49. [49]
  胡超, 穆野, 李明宇, 邱介山.物理化学学报, 2019, 35, 572. doi: 10.3866/PKU.WHXB201806060Hu, C.; Mu, Y.; Li, M.; Qiu, J. Acta Phys. -Chim. Sin. 2019, 35, 572. doi: 10.3866/PKU.WHXB201806060
50. [50]
  Peng, J.; Gao, W.; Gupta, B. K.; Liu, Z.; Romero-Aburto, R.; Ge, L.; Song, L.; Alemany, L. B.; Zhan, X.; Gao, G.; et al. Nano Lett. 2012, 12, 844. doi: 10.1021/nl2038979
51. [51]
  Zhou, Q.; Song, Y.; Li, N.; Chen, D.; Xu, Q.; Li, H.; He, J.; Lu, J. ACS Sustain. Chem. Eng. 2020, 8, 7921. doi: 10.1021/acssuschemeng.0c01548
52. [52]
  Sun, X.; Li, H.; Ou, N.; Lyu, B.; Gui, B.; Tian, S.; Qian, D.; Wang, X.; Yang, J. Molecules 2019, 24, 344. doi: 10.3390/molecules24020344
53. [53]
  Zhu, S.; Zhao, X.; Song, Y.; Lu, S.; Yang, B. Nano Today 2016, 11, 128. doi: 10.1016/j.nantod.2015.09.002
54. [54]
  Sharma, S.; Dutta, V.; Singh, P.; Raizada, P.; Rahmani-Sani, A.; Hosseini-Bandegharaei, A.; Thakur, V. K. J. Clean. Prod. 2019, 228, 755. doi: 10.1016/j.jclepro.2019.04.292
55. [55]
  Dong, Y.; Shao, J.; Chen, C.; Li, H.; Wang, R.; Chi, Y.; Lin, X.; Chen, G. Carbon 2012, 50, 4738. doi: 10.1016/j.carbon.2012.06.002
56. [56]
  Babu, V. J.; Bhavatharini, R. S. R.; Ramakrishna, S. RSC Adv. 2014, 4, 19251. doi: 10.1039/C4RA00579A
57. [57]
  Zhou, X.; Shao, C.; Yang, S.; Li, X.; Guo, X.; Wang, X.; Li, X.; Liu, Y. ACS Sustain. Chem. Eng. 2018, 6, 2316. doi: 10.1021/acssuschemeng.7b03760
58. [58]
  Zhang, Y.; Park, M.; Kim, H. Y.; Ding, B.; Park, S. Appl. Surf. Sci. 2016, 384, 192. doi: 10.1016/j.apsusc.2016.05.039
59. [59]
  Li, S.; Zhou, S.; Xu, H.; Xiao, L.; Wang, Y.; Shen, H.; Wang, H.; Yuan, Q. J. Mater. Sci. 2016, 51, 6801. doi: 10.1007/s10853-016-9967-7

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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

石墨烯量子点修饰的BiOI/PAN柔性纤维的制备及其增强的光催化活性

通讯作者: 许第发, xudifa@sina.com

English

Fabrication of Graphene Quantum Dots Modified BiOI/PAN Flexible Fiber with Enhanced Photocatalytic Activity

Corresponding author: Difa Xu, xudifa@sina.com

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

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

石墨烯量子点修饰的BiOI/PAN柔性纤维的制备及其增强的光催化活性

通讯作者: 许第发, xudifa@sina.com

English

Fabrication of Graphene Quantum Dots Modified BiOI/PAN Flexible Fiber with Enhanced Photocatalytic Activity

Corresponding author: Difa Xu, xudifa@sina.com

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

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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