CuO修饰改性沸石咪唑框架催化剂的构建及其光催化产氢性能

引用本文: 樊凯, 靳治良, 袁红, 胡红岩, 毕迎普. CuO修饰改性沸石咪唑框架催化剂的构建及其光催化产氢性能[J]. 催化学报, 2017, 38(12): 2056-2066. doi: 10.1016/S1872-2067(17)62969-3 shu

Citation: Kai Fan, Zhiliang Jin, Hong Yuan, Hongyan Hu, Yingpubi. Construction of CuO-modified zeolitic imidazolate framework-9 for photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2017, 38(12): 2056-2066. doi: 10.1016/S1872-2067(17)62969-3 shu

CuO修饰改性沸石咪唑框架催化剂的构建及其光催化产氢性能

樊凯 ^a, ,
靳治良 ^a, ,
袁红 ^a, ,
胡红岩 ^b, ,
毕迎普 ^b,

a 北方民族大学化学与化学工程学院, 宁夏银川 750021;
b 中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000
基金项目:
国家自然科学基金（21433007，21603274，41663012）；北方民族大学“宁夏低品位资源高值化利用及环境化工一体化技术”创新团队项目.

摘要: 新型金属有机骨架（MOFs）材料是一类比较新颖的可用作光催化剂的潜在材料.它是由金属离子或金属簇单元与有机配体通过配位作用自组装形成的一类具有周期性多维网络结构的多孔晶态材料.MOFs结构具有高度的有序性、一定程度上的可设计性和可剪裁性，其高度发达的孔结构使得它具有超高的比表面积.MOFs结构中的金属簇被认为可以扮演半导体量子点的角色，同时其有机配体基于"天线效应"，在光激发条件下用来活化这些金属簇，从而使得MOFs成为可能的光催化剂.
ZIF-9由角共享四面体CoN₄单元组成，其中Co²⁺阳离子和苯并咪唑阴离子之间的配位键是N供体配体，因而具有良好的热稳定性和较高的碳氮含量.本文在一定浓度的甲醇溶液中通过光沉积法将CuO附着于ZIF-9表面上，用于光催化活性测试，并与g-C₃N₄/CuO催化剂进行了比较.结果表明，ZIF-9/CuO催化剂活性是g-C₃N₄/CuO催化剂的19.4倍.这是由于比表面积的不同，导致所吸附的染料与暴露的活性位点的不同.通过SEM，TEM，EDS，XRD，XPS，UV-Vis和稳态瞬态荧光等手段系统研究了催化剂反应动力学行为及内在机理.稳态荧光结果表明，染料的荧光发射峰和ZIF-9的吸收峰之间没有明显的重叠，染料的激发电子可以在该反应系统中从染料分子转移到ZIF-9上.除了一部分电子直接传输到达ZIF-9表面，更多的电子将最终通过CuO到达催化剂表面，最后与反应溶液中的H⁺结合生成H₂，EY-ZIF-9/CuO（40%）的荧光衰减可以用双指数荧光衰减动力学即动态淬火机理.表明CuO的引入可以增强染料EY分子的聚集，从而增加该催化剂活性.

关键词:

ZIF-9
/ CuO
/ 染料
/ 敏化途径
/ 产氢
/ 反应优化

English

Construction of CuO-modified zeolitic imidazolate framework-9 for photocatalytic hydrogen evolution

a School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, Ningxia, China;
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
Received Date: 01 October 2017
Revised Date: 31 October 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21433007, 21603274, 41663012) and the Ningxia Low-Grade Resource High Value Utilization and Environmental Chemical Integration Technology Innovation Team Project, North Minzu University.

Abstract: An efficient CuO-modified zeolitic imidazolate framework-9 (ZIF-9) photocatalyst is successfully prepared at room temperature under mild conditions. It is observed that the ZIF-9/CuO photocatalyst is effective for H₂ generation under visible light with sacrificial agent conditions. When the CuO is introduced, the photocatalytic properties of ZIF-9 are greatly improved and when the content of CuO is 40%, the photocatalytic activity reaches a maximum of 78.74 μmol after 5 h. This results from the 200-300 nm cube structure of ZIF-9 being able to adsorb more dye molecules and the CuO, which connects with ZIF-9, greatly improving the electronic transmission efficiency. Moreover, the interaction between the dye molecule Eosin Y (EY) and the catalyst is also studied by transient fluorescence spectroscopy. A series of characterizations, such as SEM, TEM, XPS, XRD, UV-vis, FTIR, transient fluorescence and photocurrent, are conducted, and the results are in good agreement with the experimental result. In addition, the possible reaction mechanism over EY-sensitized ZIF-9/CuO under visible light irradiation is proposed.

Key words:

1. [1] M. I. Hoffert, K. Caldeira, A. K. Jain, E. F. Haites, L. D. Harvey, S. D. Potter, M. E. Schlesinger, S. H. Schneider, R. G. Watts, T. M. L. Wigley, D. J. Wuebbles, Nature, 1998, 395, 881-884.
2. [2] D. D. Liu, Z. L. Jin, H. X. Li, G. X. Lu, Appl. Surf. Sci., 2017, 423, 255-265.
3. [3] Y. J. Cui, G. G. Zhang, Z. Z. Lin, X. C. Wang, Appl. Catal. B, 2016, 181, 413-419.
4. [4] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
5. [5] J. P. Shi, R. Tong, X. B. Zhou, Y. Gong, Z. P. Zhang, Q. Q. Ji, Y. Zhang, Q. Y. Fang, L. Gu, X. N. Wang, Z. Liu, Y. F. Zhang, Adv. Mater., 2016, 28, 10664-10672.
6. [6] Q. Huang, J. G. Yu, S. W. Cao, C. Cui, B. Cheng, Appl. Surf. Sci., 2015, 358, 350-355.
7. [7] J. X. Low, J. G. Yu, M. Jaroniec, S. Wageh, A. A. Al-Ghamdi, Adv. Ma-ter., 2017, 29, 1601694.
8. [8] M. S. Akple, J. X. Low, Z. Qin, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Liu, Chin. J. Catal., 2015, 36, 2127-2134.
9. [9] M. Dinc, A. F. Yu, J. R. Long, J. Am. Chem. Soc., 2006, 128, 8904-8913.
10. [10] O. M. Yaghi, M. O. Keeffe, N. W. Ockwig, H. K. Chae, M. Eddaoudi, J. Kim, Nature, 2003, 423, 705-714.
11. [11] L. J. Murray, M. Dinc, J. R. Long, Chem. Soc. Rev., 2009, 38, 1294-1314.
12. [12] H. C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev., 2012, 112, 673-674.
13. [13] M. Alvaro, E. Carbonell, B. Ferrer, F. X. Llabrés i. Xamena, H. Garcia, Chem. Eur. J., 2007, 13, 5106-5112.
14. [14] N. W. Ockwig, O. Delgado-Friedrichs, M. O'Keefe, O. M. Yaghi, Acc. Chem. Res., 2005, 38, 176-182.
15. [15] C. Wang, Z. G. Xie, K. E. Clekraff, W. B. Lin, J. Am. Chem. Soc., 2011, 133, 13445-13454.
16. [16] Y. H. Fu, D. R. Sun, Y. J. Chen, R. K. Huang, Z. X. Ding, X. Z. Fu, Z. H. Li, Angew. Chem. Int. Ed., 2012, 51, 3364-3367.
17. [17] L. J. Shen, S. J. Liang, W. M. Wu, R. W. Liang, L. Wu, J. Mater. Chem. A, 2013, 1, 11473-11482.
18. [18] Y. P. Yuan, L. S. Yin, S. W. Cao, G. S. Xu, C. H. Li, C. Xue, Appl. Catal. B, 2015, 168, 572-576.
19. [19] L. He, L. Li, T. T. Wang, H. Gao, G. Z. Li, X. T. Wu, Z. W. Su, C. G. Wang, Dalton Trans., 2014, 43, 16981-16985.
20. [20] S. Hashemian, A. Sedrpoushan, F. H. Eshbala, Catal. Lett., 2017, 147, 196-203.
21. [21] S. Hermes, M. K. Schröter, R. Schmid, L. Khodeir, M. Muhler, A. Tissler, R. A. Fischer, Angew. Chem. Int. Ed., 2005, 44, 6237-6241.
22. [22] J. M. Yan, Z. L. Wang, L. Gu, S. J. Li, H. L. Wang, W. T. Zheng, Q. Jiang, Adv. Energy Mater., 2015, 5, 1500107/1-1500107/6.
23. [23] W. T. Koo, S. J. Choi, S. J. Kim, J. S. Jang, H. L. Tuller, I. D. Kim, J. Am. Chem. Soc., 2016, 138, 13431-13437.
24. [24] L. J. Shen, R. W. Liang, L. Wu, Chin. J. Catal., 2015, 36, 2071-2088.
25. [25] W. Chaikittisilp, N. L. Torad, C. Li, M. Imura, N. Suzuki, S. Ishi-hara, Y. Yamauchi, Chem. Eur. J., 2014, 20, 4217-4221.
26. [26] Q. M. Li, H. Kim, Fuel Process Technol., 2012, 100, 43-48.
27. [27] Q. Q. Hu, J. Q. Huang, G. J. Li, Y. B. Jiang, H. Lan, W. Guo, Y. G. Cao, Appl. Surf. Sci., 2016, 382, 170-177.
28. [28] M. Dong, P. Zhou, C. J. Jiang, B. Cheng, J. G. Yu, Chem. Phys. Lett., 2017, 668, 1-6.
29. [29] Y. F. Li, W. P. Zhang, X. Shen, P. F. Peng, L. B. Xiong, Y. Yu, Chin. J. Catal., 2015, 36, 2229-2236.
30. [30] H. W. Wu, S. Y. Lee, W. C. Lu, K. S. Chang, Appl. Surf. Sci., 2015, 344, 236-241.
31. [31] J. W. Fu, S. W. Cao, J. G. Yu, J. Materiomics, 2015, 1, 124-133.
32. [32] G. H. Li, N. M. Dimitrijevic, L. Chen, T. Rajh, K. A. Gray, J. Phys. Chem. C, 2008, 112, 19040-19044.
33. [33] Z. J. Li, Y. Qu, G. He, M. Humayun, S. Y. Chen, L. Q. Jing, App. Surf. Sci., 2015, 351, 681-685.
34. [34] H. J. Choi, M. Kang, Int. J. Hydrogen Energy, 2007, 32, 3841-3848.
35. [35] R. Michal, E. Dworniczek, M. Caplovicova, O. Monfort, P. Lianos, L. Caplovic, G. Plesch, Appl. Surf. Sci., 2016, 371, 538-546.
36. [36] Q. Q. Hu, J. Q. Huang, G. J. Li, J. Chen, Z. J. Zhang, Z. H. Deng, Y. B. Jiang, W. Guo, Y. G. Cao, Appl. Surf. Sci., 2016, 369, 201-206.
37. [37] Y. Q. Wang, T. T. Jiang, D. W. Meng, D. G. Wang, M. H. Yu, Appl. Surf. Sci., 2015, 355, 191-196.
38. [38] S. P. Xu, D. D. Sun, Int. J. Hydrogen Energy, 2009, 34, 6096-6104.
39. [39] Z. K. He, J. W. Fu, B. Cheng, J. G. Yu, S. W. Cao, Appl. Catal. B, 2017, 205, 104-111.
40. [40] S. R. Venna, J. B. Jasinski, M. A. Carreon, J. Am. Chem. Soc., 2010, 132, 18030-18033.
41. [41] L. T. L. Nguyen, K. K. A. Le, H. X. Truong, N. T. Sphan, Catal. Sci. Technol., 2012, 2, 521-528.
42. [42] B. X. Li, Y. F. Wang, Superlattice Microstruct., 2010, 47, 615-623.
43. [43] X. Q. Du, J. W. Huang, Y. Y. Feng, Y. Ding, Chin. J. Catal., 2016, 37, 123-134.
44. [44] Y. Y. Cui, Y. X. Wang, H. Wang, F. Cao, F. Y. Chen, Chin. J. Catal., 2016, 37, 1899-1906.
45. [45] K. Kalyanasundaram, J. Kiwi, M. Grätze, Helv. Chim. Acta, 1978, 61, 2720-2730.
46. [46] S. X. Min, G. X. Lu, Int. J. Hydrogen Energy, 2012, 37, 10564-10574.
47. [47] S. G. Kumar, K. S. R. K. Rao, Appl. Surf. Sci., 2017, 391, 124-148.
48. [48] X. Q. Hao, Z. L. Jin, S. X. Min, G. X. Lu, RSC Adv., 2016, 6, 23709-23717.
49. [49] M. Tonigold, Y. Lu, B. Bredenkötter, B. Rieger, S. Bahnmüller, J. Hitzbleck, G. Langstein, D. Volkmer, Angew. Chem. Int. Ed., 2009, 48, 7546-7550.
50. [50] Q. Y. Li, L. Chen, G. X. Lu, J. Phys. Chem. C, 2007, 111, 11494-11499.
51. [51] Q. Y. Li, Z. L. Jin, Z. G. Peng Y. X. Li, S. B. Li, G. X. Lu, J. Phys. Chem. C, 2007, 111, 8237-8241.
52. [52] Y. Liu, C. Y. Liu, Y. Liu, Appl. Surf. Sci., 2011, 257, 5513-5518.
53. [53] S. X. Min, G. X. Lu, J. Phys. Chem. C, 2012, 116, 25415-25424.
54. [54] Y. Liu, C. Liu, Y. Liu, Appl. Surf. Sci., 2011, 257, 5513
55. [55] X. Q. Hao, Z. L. Jin, F. Wang, J. Xu, S. X. Min, H. Yan, G. X. Lu, Superlattice Microstruct., 2015, 82, 599-611.

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 1114
HTML全文浏览量: 84

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

CuO修饰改性沸石咪唑框架催化剂的构建及其光催化产氢性能

English

Construction of CuO-modified zeolitic imidazolate framework-9 for photocatalytic hydrogen evolution

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

CuO修饰改性沸石咪唑框架催化剂的构建及其光催化产氢性能

English

Construction of CuO-modified zeolitic imidazolate framework-9 for photocatalytic hydrogen evolution

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

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs