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

引用本文: 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): 200909. doi: 10.3866/PKU.WHXB202009097 shu

Citation: Zihui Mei, Guohong Wang, Suding Yan, Juan Wang. Rapid Microwave-Assisted Synthesis of 2D/1D ZnIn₂S₄/TiO₂ S-Scheme Heterojunction for Catalyzing Photocatalytic Hydrogen Evolution[J]. Acta Physico-Chimica Sinica, 2021, 37(6): 200909. doi: 10.3866/PKU.WHXB202009097 shu

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

湖北师范大学污染物分析与资源化湖北省重点实验室，湖北黄石 435002

通讯作者: 王国宏, wanggh2003@163.com

基金项目:
国家自然科学基金 22075072

国家自然科学基金 52003079

湖北省自然科学基金 2019CFB568

摘要: 能源危机的威胁在过去二十年里引起了全球性广泛关注。由于地球上具有丰富的太阳能和水资源，光催化分解水制氢被认为是获取绿色能源的一种有效途径。迄今为止，许多光催化剂已经得到了深入研究。其中，TiO₂以其无毒、化学稳定性高、形态可控、光催化活性强等优点得到了广泛的关注。特别是1D结构的TiO₂纳米纤维具有独特的一维电子转移轨迹，较大的吸附能力和较高的光生电子-空穴对(e^--h⁺)传输速率等优点在光催化领域更是受到研究人员的青睐。尽管如此，TiO₂仍存在带隙大、光生电子-空穴对复合速率快等缺点，使其在制氢反应(HER)中效率不高。因此，构建高性能、经济、环保的光催化剂是实现太阳能高效转化的一大挑战。最近，各种提高TiO₂光催化活性的策略得到了广泛研究，包括与窄带隙半导体(如ZnIn₂S₄)的耦合等。另外，微波辅助合成技术以其成本低、设备简单、环境无污染、反应速度快等优点，已成为制备光催化半导体材料的一种重要手段。在本工作中，为解决TiO₂带隙宽(约3.2 eV)和电子-空穴对复合速率快等缺点，通过微波辅助合成技术快速地将2D结构的ZnIn₂S₄纳米片原位组装在TiO₂纳米纤维上，构筑2D/1D ZnIn₂S₄/TiO₂ S型异质结。通过调节ZnIn₂S₄前驱体与TiO₂ NFs的摩尔比，可以很容易地控制TiO₂纳米纤维上ZnIn₂S₄负载量。实验结果表明：相对于纯ZnIn₂S₄和TiO₂而言，ZnIn₂S₄/TiO₂异质结光催化剂在太阳光照射下的光吸收和制氢性能得到明显提高。在优化条件下，样品ZT-0.5 (ZnIn₂S₄与TiO₂的摩尔比为0.5)具有最佳制氢性能，达到8774 μmol·g^-1·h^-1，分别是纯TiO₂纳米纤维(3312 μmol·g^-1·h^-1)和ZnIn₂S₄ (3114 μmol·g^-1·h^-1)纳米片的2.7倍和2.8倍。基于实验结果，我们提出来一种在ZnIn₂S₄和TiO₂间形成的S型异质结机理，并很好地阐释了ZnIn₂S₄/TiO₂复合材料光催化制氢活性增强的原因。

关键词:

English

Rapid Microwave-Assisted Synthesis of 2D/1D ZnIn₂S₄/TiO₂ S-Scheme Heterojunction for Catalyzing Photocatalytic Hydrogen Evolution

Hubei Key Laboratory of Pollutant Analysis and Reuse Technology, Hubei Normal University, Huangshi 435002, Hubei Province, China

Corresponding author: Guohong Wang, E-mail: wanggh2003@163.com

Received Date: 29 September 2020
Accepted Date: 31 October 2020
Revised Date: 21 October 2020
Available Online: 15 June 2021
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

Hubei Provincial Natural Science Foundation of China

Abstract: The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.

Key words:

1. [1]
  Zhang, T. M.; Wan, Y. Y.; Xie, H. Y.; Mu, Y.; Du, P. W.; Wang, D.; Wu, X. J.; Ji, H. X.; Wan, L. J. J. Am. Chem. Soc. 2018, 140 (24), 7561. doi: 10.1021/jacs.8b02156
2. [2]
  Meng, A. Y.; Zhang, L. Y.; Cheng, B.; Yu, J. G. Adv. Mater. 2019, 31 (30), 1807660. doi: 10.1002/adma.201807660
3. [3]
  Di, T. M.; Xu, Q. L.; Ho, W. K.; Tang, H.; Xiang, Q. J.; Yu, J. G. ChemCatChem 2019, 11 (5), 1394. doi: 10.1002/cctc.201802024
4. [4]
  Xu, Q. L.; Ma, D. K.; Yang, S. B.; Tian, Z. F.; Cheng, B.; Fan, J. J. Appl. Surf. Sci. 2019, 495, 143555. doi: 10.1016/j.apsusc.2019.143555
5. [5]
  Sadowski, R.; Wach, A.; Buchalska, M.; Kuśtrowski, P.; Macyk, W. Appl. Surf. Sci. 2019, 475, 710. doi: 10.1016/j.apsusc.2018.12.286
6. [6]
  张驰, 吴志娇, 刘建军, 朴玲钰.物理化学学报, 2017, 33, 1492. doi: 10.3866/PKU.WHXB201704141Zhang, C.; Wu, Z. J.; Liu, J. J.; Piao, L. Y. Acta Phys. -Chim. Sin. 2017, 33, 1492. doi: 10.3866/PKU.WHXB201704141
7. [7]
  Ji, Y. C.; Yang, R. Q.; Wang, L. W.; Song, G. X.; Wang, A. Z.; Lv, Y. W.; Gao, M. M.; Zhang, J.; Yu, X. Chem. Eng. J. 2020, 40, 126226. doi: 10.1016/j.cej.2020.126226
8. [8]
  Xu, F. Y.; Zhu, B. C.; Cheng, B.; Yu, J. G.; Xu, J. S. Adv. Opt. Mater. 2018, 6 (23), 180911. doi: 10.1002/adom.201800911
9. [9]
  吴进, 刘京, 夏雾, 任颖异, 王锋.物理化学学报, 2021, 37, 2008043. doi: 10.3866/PKU.WHXB202008043Wu, J.; Liu, J.; Xia, W.; Ren, Y. Y.; Wang, F. Acta Phys. -Chim. Sin. 2021, 37, 2008043. doi: 10.3866/PKU.WHXB202008043
10. [10]
  Liu, G.; Wang, G. H.; Hu, Z. H.; Su, Y. R.; Zhao, L. Appl. Surf. Sci. 2019, 465, 902. doi: 10.1016/j.apsusc.2018.09.216
11. [11]
  Chu, Z. D.; Qiu, L. L.; Chen, Y.; Zhuang, Z. S.; Du, P. F.; Xiong, J. J. Phys. Chem. Solids. 2020, 136, 109138. doi: 10.1016/j.jpcs.2019.109138
12. [12]
  刘阳, 郝旭强, 胡海强, 靳治良.物理化学学报, 2021, 37, 2008030. doi: 10.3866/PKU.WHXB202008030Liu, Y.; Hao, X. Q.; Hu, H, Q.; Ging, Z. L. Acta Phys. -Chim. Sin. 2021, 37, 2008030. doi: 10.3866/PKU.WHXB202008030
13. [13]
  Li, X. Z.; Yan, X. Y.; Lu, X. W.; Zuo, S. X.; Li, Z. Y.; Yao, C.; Ni, C. Y. J. Catal. 2018, 357, 59. doi: 10.1016/j.jcat.2017.10.024
14. [14]
  Li, H. F.; Yu, H. T.; Quan, X.; Chen, S.; Zhang, Y. B. ACS Appl. Mater. Interface 2016, 8 (3), 2111. doi: 10.1021/acsami.5b10613
15. [15]
  Shen, J.; Wang, R.; Liu, Q. Q.; Yang, X. F.; Tang, H.; Yang, J. Chin. J. Catal. 2019, 40 (3), 380. doi: 10.1016/S1872-2067(18)63166-3
16. [16]
  潘金波, 申升, 周威, 唐杰, 丁洪志, 王进博, 陈浪, 区泽堂, 尹双凤.物理化学学报, 2020, 36, 1905068. doi: 10.3866/PKU.WHXB201905068Pan, J. B.; Shen, S.; Zhou, W.; Tang, J.; Ding, H. Z.; Wang, J. B.; Chen, L.; Au, C. T.; Yin, S. F. Acta Phys. -Chim. Sin. 2020, 36, 1905068. doi: 10.3866/PKU.WHXB201905068
17. [17]
  黄娟娟, 杜建梅, 杜海威, 徐更生, 袁玉鹏.物理化学学报, 2020, 36, 1905056. doi: 10.3866/PKU.WHXB201905056Huang, J. J.; Du, J. M.; Du, H. W.; Xu, G. S.; Yuan, Y. P. Acta Phys. -Chim. Sin. 2020, 36, 1905056. doi: 10.3866/PKU.WHXB201905056
18. [18]
  Xia, P. F.; Cao, S. W.; Zhu, B. C.; Liu, M. J.; Shi, M. S.; Yu, J. G.; Zhang, Y. F. Angew. Chem. Int. Ed. 2020, 59 (13), 5218. doi: 10.1002/ange.201916012
19. [19]
  Li, Z. J.; Wang, X. H.; Tian, W. L.; Meng, A. L.; Yang, L. N. ACS Sustain. Chem. Eng. 2019, 7 (24), 20190. doi: 10.1021/acssuschemeng.9b06430
20. [20]
  He, F.; Meng, A. Y.; Cheng, B.; Ho, W. K.; Yu, J. G. Chin. J. Catal. 2020, 41 (1), 9. doi: 10.1016/S1872-2067(19)63382-6
21. [21]
  Luo, J. H.; Lin, Z. X.; Zhao, Y.; Jiang, S. J.; Song, S. Q. Chin. J. Catal. 2020, 41 (1), 122. doi: 10.1016/S1872-2067(19)63490-X
22. [22]
  Wang, J.; Wang, G. H.; Cheng, B.; Yu, J. G.; Fan, J. J. Chin. J. Catal. 2021, 42 (1), 56. doi: 10.1016/S1872-2067(20)63634-8
23. [23]
  Wei, J. X.; Chen, Y. W.; Zhang, H. Y.; Zhuang, Z. Y.; Yu, Y. Chin. J. Catal. 2021, 42 (1), 78. doi: 10.1016/S1872-2067(20)63661-0
24. [24]
  Peng, J. J.; Shen, J.; Yu, X. H.; Tang, H.; Zulfiqar; Liu, Q. Q. Chin. J. Catal. 2021, 42 (1), 87. doi: 10.1016/S1872-2067(20)63595-1
25. [25]
  Wang, Z. L.; Chen, Y. F.; Zhang, L. Y.; Cheng, B.; Yu, J. G.; Fan, J. J. J. Mater. Sci. Technol. 2020, 56, 143. doi: 10.1016/j.jmst.2020.02.062
26. [26]
  Li, Z. F.; Wu, Z. H.; He, R. A.; Wan, L.; Zhang, S. Y. J. Mater. Sci. Technol. 2020, 56, 151. doi: 10.1016/j.jmst.2020.02.061
27. [27]
  Wang, Y. Y.; Wang, K.; Wang, J. L.; Wu, X. Y.; Zhang, G. K. J. Mater. Sci. Technol. 2020, 56, 236. doi: 10.1016/j.jmst.2020.03.039
28. [28]
  Liu, H.; Yu, D.Q.; Sun, T. B.; Du, H. Y.; Jiang, W. T.; Yaseen, M.; Huang, L. Appl. Surf. Sci. 2019, 473, 855. doi: 10.1016/j.apsusc.2018.12.162
29. [29]
  Nasr, M.; Eid, C.; Habchi, R.; Miele, P.; Bechelany, M. ChemSusChem 2018, 11 (18), 3023. doi: 10.1002/cssc.201800874
30. [30]
  Chen, W.; Liu, T. Y.; Huang, T.; Liu, X. H.; Yang, X. J. Nanoscale 2016, 8 (6), 3711. doi: 10.1039/c5nr07695a
31. [31]
  Xia, Y.; Li, Q.; Lv, K. L.; Li, M. Appl. Surf. Sci. 2017, 398, 81. doi: 10.1016/j.apsusc.2016.12.006
32. [32]
  Wei, N.; Wu, Y. H.; Wang, M. L.; Sun, W. X.; Li, Z. K.; Ding, L.; Cui, H. Z. Nanotechnology 2018, 30 (4), 045701. doi: 10.1088/1361-6528/aaecc6
33. [33]
  Zhu, Y. J.; Chen, F. Chem. Rev. 2014, 114 (12), 6462. doi: 10.1021/cr400366s
34. [34]
  Lin, B.; Li, H.; An, H.; Hao, W. B.; Wei, J. J.; Dai, Y. Z.; Ma, C. S.; Yang, G. D. Appl. Catal. B-Environ. 2018, 220, 542. doi: 10.1016/j.apcatb.2017.08.071
35. [35]
  Sing, K. S. Pure Appl. Chem. 1985, 57 (4), 603. doi: 10.1351/pac198254112201
36. [36]
  Wang, J.; Wang, G. H.; Wang, X.; Su, Y. R.; Tang, H. Carbon 2019, 149, 618. doi: 10.1016/j.carbon.2019.04.088
37. [37]
  Zhou, X. J.; Shao, C. L.; Li, X. H.; Wang, X. X.; Guo, X. H.; Liu, Y. C. J. Hazard. Mater. 2018, 344, 113. doi: 10.1016/j.jhazmat.2017.10.006
38. [38]
  Cao, S. W.; Shen, B. J.; Tong, T.; Fu, J. W.; Yu, J. G. Adv. Funct. Mater. 2018, 28 (21), 1800136. doi: 10.1002/adfm.201800136
39. [39]
  Liu, J. J. J. Phys. Chem. C 2015, 119 (51), 28417. doi: 10.1021/acs.jpcc.5b09092
40. [40]
  Gao, D. D.; Yuan, R. R.; Fan, J. J.; Hong, X. K.; Yu, H. G. J. Mater. Sci. Technol. 2020, 56, 122. doi: 10.1016/j.jmst.2020.02.031
41. [41]
  He, R. G.; Liu, H. J.; Liu, H. M.; Xu, D. F.; Zhang, L. Y. J. Mater. Sci. Technol. 2020, 52, 145. doi: 10.1016/j.jmst.2020.03.027
42. [42]
  Xu, F. Y.; Zhang, J. J.; Zhu, B. C.; Yu, J. G.; Xu, J. S. Appl. Catal. B-Environ. 2018, 230, 194. doi: 10.1016/j.apcatb.2018.02.042
43. [43]
  Xu, Q. L.; Zhang, L. Y.; Yu, J. G.; Wageh, S.; Al-Ghamdi, A. A.; Jaroniec, M. Mater. Today 2018, 21 (10), 1042. doi: 10.1016/j.mattod.2018.04.008
44. [44]
  Xia, Y.; Tian, Z. H.; Heil, T.; Meng, A. Y.; Cheng, B.; Cao, S. W.; Yu, J. G.; Antonietti, M. Joule 2019, 3 (11), 2792. doi: 10.1016/j.joule.2019.08.011
45. [45]
  Ge, H. N.; Xu, F. Y.; Cheng, B.; Yu, J. G.; Ho, W. K. ChemCatChem 2019, 11 (24), 6301. doi: 10.1002/cctc.201901486
46. [46]
  Zhang, T.; Low, J. X.; Yu, J. G.; Tyryshkin, A. M.; Mikmekova, E.; Asefa, T. Angew. Chem. Int. Ed. 2020, 59 (35), 15000. doi: 10.1002/anie.202005143
47. [47]
  Xu, F. Y.; Meng, K.; Cheng, B.; Wang, S. Y.; Xu, J. S.; Yu, J. G. Nat. Commun. 2020, 11, 4613. doi: 10.1038/s41467-020-18350-7
48. [48]
  Xu, Q. L.; Zhang, L. Y.; Cheng, B.; Fan, J. J.; Yu, J. G. Chem 2020, 6 (7), 1543. doi: 10.1016/j.chempr.2020.06.010

扫一扫看文章

计量

PDF下载量: 47
文章访问数: 2152
HTML全文浏览量: 513

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

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

通讯作者: 王国宏, wanggh2003@163.com

English

Rapid Microwave-Assisted Synthesis of 2D/1D ZnIn₂S₄/TiO₂ S-Scheme Heterojunction for Catalyzing Photocatalytic Hydrogen Evolution

Corresponding author: Guohong Wang, E-mail: wanggh2003@163.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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处