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

doi:10.3866/PKU.WHXB202011022

摘要/Abstract

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: 分级, 光催化氧化, 苯酚, S型异质结, 可见光

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: Hierarchical, Photocatalytic oxidization, Phenol, S-scheme heterojunction, Visible light

点击下载补充材料PDF格式文件

赫荣安, 陈容, 罗金花, 张世英, 许第发. 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[J]. 物理化学学报, 2021, 37(6), 2011022. doi: 10.3866/PKU.WHXB202011022

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 Phys. -Chim. Sin. 2021, 37(6), 2011022. doi: 10.3866/PKU.WHXB202011022

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202011022

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I6/2011022

图/表 11

Fig 1

Fig 2

Fig 3

Fig 4

Fig 5

Fig 6

Fig 7

Fig 8

Fig 9

Fig 10

Fig 11

参考文献 59

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	Brillas E. ; Martínez-Huitle C. A. Appl. Catal. B 2015, 166–167, 603. doi: 10.1016/j.apcatb.2014.11.016
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	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	Wang J. ; Wang S. J. Environ. Manage. 2016, 182, 620. doi: 10.1016/j.jenvman.2016.07.049
6	Wang Y. ; Zhang S. ; Ge Y. ; Wang C. ; Hu J. ; Liu H. Acta Phys. -Chim. Sin. 2020, 36, 1905083.
	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.WHXB201905083
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	He R. ; Xu D. ; Cheng B. ; Yu J. ; Ho W. Nanoscale Horiz. 2018, 3, 464. doi: 10.1039/c8nh00062j
9	He R. ; Cao S. ; Zhou P. ; Yu J. Chin. J. Catal. 2014, 35, 989. doi: 10.1016/S1872-2067(14)60075-9
10	Xiang X. ; Zhu B. ; Cheng B. ; Yu J. ; Lv H. Small 2020, 16, 2001024. doi: 10.1002/smll.202001024
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	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	He R. ; Zhang J. ; Yu J. ; Cao S. J. Colloid Interface Sci. 2016, 478, 201. doi: 10.1016/j.jcis.2016.06.012
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	Cheng H. ; Huang B. ; Dai Y. Nanoscale 2014, 6, 2009. doi: 10.1039/c3nr05529a
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	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	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	Komeily-Nia Z. ; Montazer M. ; Heidarian P. ; Nasri-Nasrabadi B. Polym. Adv. Technol. 2019, 30, 235. doi: 10.1002/pat.4480
20	Liao C. ; Ma Z. ; Dong G. ; Qiu J. J. Am. Ceram. Soc. 2015, 98, 957. doi: 10.1111/jace.13388
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	Zhang Q. ; Bai J. ; Li G. ; Li C. J. Solid State Chem. 2019, 270, 129. doi: 10.1016/j.jssc.2018.11.015
23	Li H. ; Su Z. ; Hu S. ; Yan Y. Appl. Catal. B 2017, 207, 134. doi: 10.1016/j.apcatb.2017.02.013
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	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	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	Prasanth R. ; Aravindan V. ; Srinivasan M. J. Power Sources 2012, 202, 299. doi: 10.1016/j.jpowsour.2011.11.057
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	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	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	Xu Q. ; Zhang L. ; Cheng B. ; Fan J. ; Yu J. Chem 2020, 6, 1543. doi: 10.1016/j.chempr.2020.06.010
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	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	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	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	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	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	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	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	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	Ge H. ; Xu F. ; Cheng B. ; Yu J. ; Ho W. ChemCatChem 2019, 11, 6301. doi: 10.1002/cctc.201901486
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	Yeh T. ; Chen S. ; Teng H. Nano Energy 2015, 12, 476. doi: 10.1016/j.nanoen.2015.01.021
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	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	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	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	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	Hu C. ; Mu Y. ; Li M. ; Qiu J. Acta Phys. -Chim. Sin. 2019, 35, 572.
	胡超; 穆野; 李明宇; 邱介山; 物理化学学报, 2019, 35, 572. doi: 10.3866/PKU.WHXB201806060
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	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	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	Zhu S. ; Zhao X. ; Song Y. ; Lu S. ; Yang B. Nano Today 2016, 11, 128. doi: 10.1016/j.nantod.2015.09.002
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	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	Babu V. J. ; Bhavatharini R. S. R. ; Ramakrishna S. RSC Adv. 2014, 4, 19251. doi: 10.1039/C4RA00579A
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	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	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

[1]	昝忠奇, 李喜宝, 高晓明, 黄军同, 罗一丹, 韩露. 0D/2D碳氮量子点(CNQDs)/BiOBr复合的S型异质结高效光催化降解和产H₂O₂[J]. 物理化学学报, 2023, 39(6): 2209016 - .
[2]	张怡宁, 高明, 陈松涛, 王会琴, 霍鹏伟. Ag/CN/ZnIn₂S₄ S型异质结等离子体光催化剂的制备及其增强光还原CO₂研究[J]. 物理化学学报, 2023, 39(6): 2211051 - .
[3]	罗铖, 龙庆, 程蓓, 朱必成, 王临曦. Pt-C₃N₄/BiOCl S型异质结应用于光催化CO₂还原的理论计算研究[J]. 物理化学学报, 2023, 39(6): 2212026 - .
[4]	张珂瑜, 李云锋, 袁仕丹, 张洛红, 王倩. S型异质结H₂O₂光催化剂的研究进展[J]. 物理化学学报, 2023, 39(6): 2212010 - .
[5]	孔菁, 张金贵, 张素芬, 奚菊群, 沈明. 可见光激发的BiOI/ZnO纳米复合抗菌剂制备及其抗菌活性与机制[J]. 物理化学学报, 2023, 39(12): 2212039 - .
[6]	张利君, 吴有林, Tsubaki Noritatsu, 靳治良. CeO₂-Cu₂O 2D/3D S型异质结界面促进有序电荷转移以实现高效光催化析氢[J]. 物理化学学报, 2023, 39(12): 2302051 - .
[7]	刘珊池, 王凯, 杨梦雪, 靳治良. Mn_0.2Cd_0.8S@CoAl LDH S-型异质结构建及其光催化析氢性能研究[J]. 物理化学学报, 2022, 38(7): 2109023 - .
[8]	朱弼辰, 洪小洋, 唐丽永, 刘芹芹, 唐华. 二维/一维BiOBr_0.5Cl_0.5/WO₃ S型异质结助力光催化CO₂还原[J]. 物理化学学报, 2022, 38(7): 2111008 - .
[9]	韩高伟, 徐飞燕, 程蓓, 李佑稷, 余家国, 张留洋. 反蛋白石结构ZnO@PDA用于增强光催化产H₂O₂性能[J]. 物理化学学报, 2022, 38(7): 2112037 - .
[10]	王文亮, 张灏纯, 陈义钢, 史海峰. 具有光催化与光芬顿反应协同作用的2D/2D α-Fe₂O₃/g-C₃N₄ S型异质结用于高效降解四环素[J]. 物理化学学报, 2022, 38(7): 2201008 - .
[11]	李钱, 胡静, 周易, 王海强, 吴忠标. La掺杂BiOI微球可见光下光催化氧化NO性能研究[J]. 物理化学学报, 2021, 37(8): 2009100 - .
[12]	周易, 欧阳威龙, 王岳军, 王海强, 吴忠标. 核壳结构NH₂-UiO-66@TiO₂的制备及其可见光下的甲苯降解性能研究[J]. 物理化学学报, 2021, 37(8): 2009045 - .
[13]	郑倩, 曹玥晗, 黄南建, 张瑞阳, 周莹. BN诱导BiOI富氧{110}面的暴露并增强其可见光催化氧化性能[J]. 物理化学学报, 2021, 37(8): 2009063 - .
[14]	张鹏, 王继全, 李源, 姜丽莎, 王壮壮, 张高科. 非贵金属助剂Ni₂P修饰类石墨碳氮化物光催化剂增强可见光光催化产氢性能[J]. 物理化学学报, 2021, 37(8): 2009102 - .
[15]	梅子慧, 王国宏, 严素定, 王娟. 微波辅助快速制备2D/1D ZnIn₂S₄/TiO₂ S型异质结及其光催化制氢性能[J]. 物理化学学报, 2021, 37(6): 2009097 - .