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

doi:10.3866/PKU.WHXB202009045

摘要/Abstract

摘要：

金属有机骨架(MOFs)在可见光光催化方面具有重要的应用价值，但其通常受制于稳定性不佳和光生电荷复合率高的缺点。与无机半导体复合是提高MOFs活性的有效途径之一。本文以水热法制备NH₂-UiO-66，在其表面包裹非晶态的TiO₂层，制备出一种核壳结构的MOF@TiO₂催化剂(NH₂-UiO-66@TiO₂)，并考察了其在可见光下对甲苯的降解性能。实验结果表明其性能优于NH₂-UiO-66及直接固混法制备的样品。在可见光照射下，其3 h内的甲苯降解效率可达76.7%，是NH₂-UiO-66的1.48倍。四次重复使用实验证明其光催化性能稳定，仅有轻微失活，且经乙醇洗涤后可恢复活性。采用X射线衍射(XRD)等表征手段考察了其物理化学特性，并根据表征结果和光催化活性数据探究了NH₂-UiO-66@TiO₂光催化性能的提升机理。结果表明，NH₂-UiO-66@TiO₂一方面得益于NH₂-UiO-66的可见光激发特性和超大的比表面积(914.9 m²·g^-1)，可以拓宽光吸收范围，有效吸附和活化污染物; 另一方面在于包覆的TiO₂与NH₂-UiO-66形成了异质结，可以有效拓宽光吸收范围，提高光生电子空穴对的利用率。电子和空穴对一经形成即可通过界面转移。空穴会在NH₂-UiO-66的HOMO与H₂O结合形成羟基自由基(·OH)。同时，电子在TiO₂的导电与氧分子结合生成超氧自由基(·O₂^-)。两种自由基数量的增加致使甲苯有效氧化。本研究可为核壳结构的MOF@光催化剂设计和室内空气的光催化净化提供参考。

关键词: 核壳结构, 可见光, 光催化剂, NH₂-UiO-66, TiO₂

Abstract:

Metal-organic frameworks (MOFs) are of significant interest for photocatalysis using visible light, but they are typically limited by the instability and high recombination ratio of photoexcited pairs. Integrating MOFs into an inorganic semiconductor is one of the most widespread methods to promote their activity. In this study, a core-shell structured MOF@TiO₂ (NH₂-UiO-66@TiO₂) was synthesized as an efficient photocatalyst for the degradation of toluene. Pristine NH₂-UiO-66 was synthesized by a hydrothermal method as the core, which was then coated with an amorphous TiO₂ shell. Compared with pristine NH₂-UiO-66 and other samples prepared by the direct mixing of NH₂-UiO-66 and TiO₂, NH₂-UiO-66@TiO₂ exhibited a higher degradation rate of toluene. Using NH₂-UiO-66@TiO₂ as a catalyst, the degradation efficiency of toluene reached 76.7% within 3 h, which is 1.48 times higher than that of NH₂-UiO-66. The degradation performance was also stable in four repeated reuse experiments, and the slight deactivation was reactivated after washing with ethanol. A series of characterization methods were used to determine the physicochemical properties of NH₂-UiO-66@TiO₂, including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Using the measured physicochemical properties, the photocatalytic mechanism of NH₂-UiO-66@TiO₂ was explored. NH₂-UiO-66 is an ideal photocatalyst, with visible-light response and a huge specific surface area (914.9 m²·g^-1), which is favorable for the utilization of sunlight as well as the absorption of pollutants in indoor air. In addition, a new interface formed between the two components (NH₂-UiO-66 and TiO₂), which efficiently broaden the light absorption area and enhanced the utilization of photogenerated species. The photogenerated holes and electrons could transfer through the interlayer as soon as they were formed. It is speculated that holes would transfer to the HOMO of NH₂-UiO-66, and then combine with H₂O molecules to form hydroxyl radicals (·OH). At the same time, more electrons tended to combine with oxygen molecules in the conduction band of TiO₂ rather than recombine with holes. Consequently, the recombination rate of electrons and holes decreased, while the quantity of oxygen radicals and hydroxyl radicals increased. Toluene was efficiently oxidized by these two types of radicals. Owing to the outstanding properties mentioned above, the strategy of constructing NH₂-UiO-66@TiO₂ is considered to be an effective approach. This work may provide new insights into the design of core-shell structured MOF@photocatalysts for the photocatalytic degradation of indoor air pollutants.

Key words: Core-shell structure, Visible light responsed, Photocatalyst, NH₂-UiO-66, TiO₂

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.

Yi Zhou, Weilong Ouyang, Yuejun Wang, Haiqiang Wang, Zhongbiao Wu. Core-Shell Structured NH₂-UiO-66@TiO₂ Photocatalyst for the Degradation of Toluene under Visible Light Irradiation[J]. Acta Phys. -Chim. Sin., 2021, 37(8): 2009045.

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202009045

https://www.whxb.pku.edu.cn/CN/Y2021/V37/I8/2009045

图/表 11

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

参考文献 31

1	Wang S. B. ; Ang H. M. ; Tade M. O. Environ. Int. 2007, 33, 694. doi: 10.1016/j.envint.2007.02.011
2	Guieysse B. ; Hort C. ; Platel V. ; Munoz R. ; Ondarts M. ; Revah S. Biotechnol. Adv. 2008, 26, 398. doi: 10.1016/j.biotechadv.2008.03.005
3	Fei X. Q. ; Cao S. ; Ouyang W. L. ; Wen Y. X. ; Wang H. Q. ; Wu Z. B. Chem. Eng. J. 2020, 387, 11. doi: 10.1016/j.cej.2019.123411
4	Mamaghani A. H. ; Haghighat F. ; Lee C. -S. Appl. Catal. B-Environ. 2017, 203, 247. doi: 10.1016/j.apcatb.2016.10.037
5	Dong F. ; Zhang Y. X. ; Zhang S. Front. Chem. 2019, 7, 3. doi: 10.3389/fchem.2019.00303
6	Tang Q. J. ; Sun Z. X. ; Wang P. L. ; Li Q. ; Wang H. Q. ; Wu Z. B. Appl. Surf. Sci. 2019, 463, 456. doi: 10.1016/j.apsusc.2018.08.245
7	Cui H. Q. ; Jing L. Q. ; Xie M. Z. ; Li Z, J. Acta Phys. -Chim. Sin. 2014, 30, 1903.
	崔海琴; 井立强; 谢明政; 李志君. 物理化学学报, 2014, 30, 1903. doi: 10.3866/PKU.WHXB201407173
8	Shayegan Z. ; Lee C. -S. ; Haghighat F. Chem. Eng. J. 2018, 334, 2408. doi: 10.1016/j.cej.2017.09.153
9	Chen R. F. ; Yao Z. X. ; Han N. ; Ma X. C. ; Li L. Q. ; Liu S. M. ; Sun H. Q. ; Wang S. B. ACS Omega 2020, 5, 15402. doi: 10.1021/acsomega.0c01504
10	Cui L. X. ; Zou X. H. ; Liu Y. N. ; Li X. ; Jiang L. C. ; Li C. Y. ; Yang L. Q. ; Yu M. J. ; Wang Y. G. J. Colloid Interface Sci. 2020, 577, 233. doi: 10.1016/j.jcis.2020.05.023
11	Wang X. J. ; Zhao X. L. ; Zhang D. Q. ; Li G. S. ; Li H. X. Appl. Catal. B-Environ. 2018, 228, 47. doi: 10.1016/j.apcatb.2018.01.066
12	Wan S. P. ; Ou M. ; Zhong Q. ; Wang X. M. Chem. Eng. J. 2019, 358, 1287. doi: 10.1016/j.cej.2018.10.120
13	Shen L. J. ; Liang S. J. ; Wu W. M. ; Liang R. W. ; Wu L. J. Mater. Chem. A 2013, 1, 11473. doi: 10.1039/c3ta12645e
14	Chen X. L. ; Cai Y. ; Liang R. ; Tao Y. ; Wang W. C. ; Zhao J. J. ; Chen X. F. ; Li H. X. ; Zhang D. Q. Appl. Catal. B-Environ. 2020, 267 doi: 10.1016/j.apcatb.2020.118687
15	Bai Y. R. ; Dong J. P. ; Hou Y. Q. ; Guo Y. P. ; Liu Y. J. ; Li Y. L. ; Han X. J. ; Huang Z. G. Chem. Eng. J. 2019, 361, 703. doi: 10.1016/j.cej.2018.12.109
16	Gao S. ; Cen W. L. ; Li Q. ; Li J. Y. ; Lu Y. F. ; Wang H. Q. ; Wu Z. B. Appl. Catal. B-Environ. 2018, 227, 190. doi: 10.1016/j.apcatb.2018.01.007
17	Wang H. M. ; Yu T. ; Tan X. ; Zhang H. B. ; Li P. ; Liu H. M. ; Shi L. ; Li X. L. ; Ye J. H. Ind. Eng. Chem. Res. 2016, 55, 8096. doi: 10.1021/acs.iecr.6b01400
18	Li X. Y. ; Pi Y. H. ; Hou Q. Q. ; Yu H. ; Li Z. ; Li Y. W. ; Xiao J. Chem. Commun. 2018, 54, 1917. doi: 10.1039/c7cc09072b
19	Zhang J. H. ; Hu Y. ; Qin J. X. ; Yang Z. X. ; Fu M. L. Chem. Eng. J. 2020, 385, 123814. doi: 10.1016/j.cej.2019.123814
20	Cao. S. The Research on Catalytic Combustion Performance of CH₂Cl₂ over Ceria-Titania-Based Complex Metal Oxides. Ph. D. Dissertation, Zhejiang University, Hangzhou, 2016.
	曹爽.铈钛基复合金属氧化物催化氧化二氯甲烷的研究[博士学位论文].杭州: 浙江大学, 2016.
21	Wang Y. ; Li L. J. ; Dai P. C. ; Yan L. T. ; Cao L. ; Gu X. ; Zhao X. B. J. Mater. Chem. A 2017, 5, 22372. doi: 10.1039/c7ta06060b
22	Li X. Y. ; Pi Y. H. ; Xia Q. B. ; Li Z. ; Xiao J. Appl. Catal. B-Environ. 2016, 191, 192. doi: 10.1016/j.apcatb.2016.03.034
23	Xie T. P. ; Liu Y. ; Wang H. Q. ; Wu Z. B. Appl. Surf. Sci. 2018, 444, 320. doi: 10.1016/j.apsusc.2018.03.072
24	Liu Y. Q. ; Zhou Y. ; Tang Q. J. ; Li Q. ; Chen S. ; Sun Z. X. ; Wang H. Q. RSC Adv. 2020, 10, 1757. doi: 10.1039/c9ra09270f
25	Zhao W. R. ; Shi Q. M. ; Liu Y. Acta Phys. -Chim. Sin. 2014, 30 (7), 1318.
	赵伟荣; 施巧梦; 刘莹. 物理化学学报, 2014, 30 (7), 1318. doi: 10.3866/PKU.WHXB201404222
26	Xie T. P. ; Zhang Y. Y. ; Yao W. Y. ; Liu Y. ; Wang H. Q. ; Wu Z. B. Catal. Sci. Technol. 2019, 9, 1178. doi: 10.1039/c8cy02344a
27	Huo W. C. ; Cao T. ; Xu W. N. ; Guo Z. Y. ; Liu X. Y. ; Yao H. C. ; Zhang Y. X. Chin. J. Catal. 2020, 41, 268. doi: 10.1016/s1872-2067(19)63460-1
28	Guan Z. J. ; Xu Z. Q. ; Li Q. Y. ; Wang P. ; Li G. Q. ; Yang J. J. Appl. Catal. B-Environ. 2018, 227, 512. doi: 10.1016/j.apcatb.2018.01.068
29	Huang H. W. ; He Y. ; Li X. W. ; Li M. ; Zeng C. ; Dong F. ; Du X. ; Zhang T. R. ; Zhang Y. H. J. Mater. Chem. A 2015, 3, 24547. doi: 10.1039/c5ta07655b
30	Zhao Q. ; Wang J. L. ; Li Z. P. ; Guo Y. ; Wang J. ; Tang B. ; Kansha Y. ; Yoshida A. ; Abudula A. ; Guan G. Q. J. Photochem. Photobiol. A: Chem. 2020, 399, 112625. doi: 10.1016/j.jphotochem.2020.112625
31	Zhao W. R. ; Xi H. P. ; Liao Q. W. Acta Phys. -Chim. Sin. 2013, 29 (10), 2232.
	赵伟荣; 奚海萍; 廖求文. 物理化学学报, 2013, 29 (10), 2232. doi: 10.3866/PKU.WHXB201308291

[1]	王吉超, 乔秀, 史维娜, 贺景, 陈军, 张万庆. 多面体状Cu₂O修饰片状BiOI的S型异质结构筑及光催化水蒸气中CO₂转化性能研究[J]. 物理化学学报, 2023, 39(6): 2210003 -0 .
[2]	吕娜, 荆雪东, 许瑶, 鲁巍, 刘奎朝, 张振翼. 多组分纳米纤维体系中载流子动力学的有效级联调制及其高效光催化产氢性能研究[J]. 物理化学学报, 2023, 39(4): 2207045 -0 .
[3]	杨越, 朱加伟, 王鹏彦, 刘海咪, 曾炜豪, 陈磊, 陈志祥, 木士春. 镶嵌于NH₂-MIL-125 (Ti)衍生氮掺多孔碳中的花状超细纳米TiO₂作为高活性和稳定性的锂离子电池负极材料[J]. 物理化学学报, 2022, 38(6): 2106002 - .
[4]	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 - .
[5]	王苹, 李海涛, 曹艳洁, 余火根. 羧基功能化石墨烯增强TiO₂光催化产氢性能[J]. 物理化学学报, 2021, 37(6): 2008047 - .
[6]	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 - .
[7]	李喜宝, 刘积有, 黄军同, 何朝政, 冯志军, 陈智, 万里鹰, 邓芳. 全有机S型异质结PDI-Ala/S-C₃N₄光催化剂增强光催化性能[J]. 物理化学学报, 2021, 37(6): 2010030 - .
[8]	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 - .
[9]	金飘, 官自超, 梁燕, 谭凯, 王霞, 宋光铃, 杜荣归. NiO/TiO₂异质结构纳米管阵列膜对不锈钢的光生阴极保护及其储能性能[J]. 物理化学学报, 2021, 37(3): 1906033 - .
[10]	刘柏侨, 许韵华, 夏冬冬, 肖承义, 杨兆凡, 李韦伟. 基于非富勒烯电子受体的半透明有机太阳能电池[J]. 物理化学学报, 2021, 37(3): 2009056 - .
[11]	杨晓庆, 杨华琳, 卢欢, 丁皓璇, 童妍心, 饶斐, 张鑫, 申茜, 高健智, 朱刚强. 高催化活性2D/2D Ti₃C₂/Bi₄O₅Br₂纳米片异质结的构建及其可见光催化去除NO[J]. 物理化学学报, 2021, 37(10): 2005008 - .
[12]	张超, 李思汉, 吴辰亮, 李小青, 严新焕. Pt@Au/Al₂O₃核壳纳米粒子的制备和表征及其在催化氧化甲苯中的应用[J]. 物理化学学报, 2020, 36(8): 1907057 - .
[13]	刘丹叶,陈东,刘卉,杨军. 贵金属在Ag₂S纳米颗粒中由内向外的迁移现象[J]. 物理化学学报, 2020, 36(7): 1906069 - .
[14]	郁桂云,胡丰献,程伟伟,韩字童,刘超,戴勇. ZnCuAl-LDH/Bi₂MoO₆纳米复合材料的构建及其可见光催化降解性能[J]. 物理化学学报, 2020, 36(7): 1911016 - .
[15]	李玉红,吴新平,刘聪,王萌,宋本腾,郁桂云,杨刚,侯文华,龚学庆,彭路明. 部分还原二氧化钛的NMR和EPR研究[J]. 物理化学学报, 2020, 36(4): 1905021 - .

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

Core-Shell Structured NH₂-UiO-66@TiO₂ Photocatalyst for the Degradation of Toluene under Visible Light Irradiation

RichHTML

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 31

相关文章 15

Metrics

推荐阅读 0