一种稳定二维配位聚合物用于光催化还原Cr(VI)及降解有机污染物

引用本文: 王茀学, 衣晓虹, 王崇臣, 邓积光. 一种稳定二维配位聚合物用于光催化还原Cr(VI)及降解有机污染物[J]. 催化学报, 2017, 38(12): 2141-2149. doi: 10.1016/S1872-2067(17)62947-4 shu

Citation: Fu-Xue Wang, Xiao-Hong Yi, Chong-Chen Wang, Ji-Guang Deng. Photocatalytic Cr(VI) reduction and organic-pollutant degradation in a stable 2D coordination polymer[J]. Chinese Journal of Catalysis, 2017, 38(12): 2141-2149. doi: 10.1016/S1872-2067(17)62947-4 shu

一种稳定二维配位聚合物用于光催化还原Cr(VI)及降解有机污染物

a 北京建筑大学, 建筑结构与环境修复功能材料北京重点实验室/中荷未来污水处理技术研究中心, 北京 100044;
b 北京工业大学环境与能源工程学院, 化学与化工系, 北京 100022
基金项目:
国家自然科学基金（51578034）；北京自然科学基金重点项目暨北京市教委重点项目（KZ201410016018）；北京百千万人才工程培养经费（2016023）；北京市属高校高层次人才引进与培养计划及创新团队与教师职业发展计划（IDHT20170508）.

摘要: 工厂运行过程产生的大量含重金属离子和有机污染物的废水，对环境和人体造成很大的危害.光催化法是一种有效、无二次污染且成本较低的水处理技术，能将有机物分解为生化性强的小分子并降低毒性，甚至完全矿化成二氧化碳和水；此外还能将剧毒的重金属转变为其它低毒或无毒形态，如可将Cr（VI）还原为Cr（Ⅲ），或将As（Ⅲ）氧化为As（V）.传统的光催化剂往往面临效率低、重复性差等问题，限制了其实际应用.例如，二氧化钛虽然廉价、毒性低，但巨大的比表面积能使其极易发生团聚，导致活性下降.因此开发超高效光催化活性的催化剂具有重要意义.
本文利用水热法合成了一种新型配位聚合物Zn（bpy）L（BUC-21）（H₂L=顺1，3-二苄基咪唑-2-酮-4，5-二羧酸，bpy=4，4'-联吡啶）.对BUC-21进行了包括傅里叶变换红外光谱（FTIR）、热重（TGA）、CNH元素分析和紫外-可见漫反射（UV-vis DRS）在内的系列表征，并选择Cr（VI）和四种典型有机染料作为目标污染物探究了BUC-21的光催化性能.
结果表明，BUC-21在340 ℃以下时能保持骨架稳定，其带隙值（E_g）为3.4 eV.紫外光照射30 min后，BUC-21对Cr（VI）还原效率可达到96%，远高于相同条件下的商业二氧化钛P25（39%）.此外，BUC-21还能高效降解亚甲基蓝（MB）、罗丹明B（Rh B）、甲基橙（MO）和活性红X-3B（X-3B）等有机染料污染物，其降解速率同样优于P25.比如，在紫外光照射下，P25完全降解X-3B需要21 min，而BUC-21仅需9 min，表明BUC-21具有比P25更好的光催化活性.将BUC-21用于同时光催化还原Cr（VI）与降解X-3B反应，结果表明，较单一污染物组分而言，Cr（VI）还原效率不变而染料降解效率降低.活性物质捕捉实验结果证明，造成上述现象的原因在于Cr（VI）消耗了光生电子，抑制超氧自由基（·O₂^-）的生成，而·O₂^-是降解X-3B的主要活性物质.此外，BUC-21具有很好的耐酸耐碱性能，能在pH值为2-12范围内保持稳定，且表现出超高的光催化活性。循环实验表明，BUC-21具有良好的稳定性和重复利用性.

关键词:

English

Photocatalytic Cr(VI) reduction and organic-pollutant degradation in a stable 2D coordination polymer

a Beijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation/Sino-Dutch R & D Centre for Future Wastewater Treatment Technologies, Beijing University of Civil Engineering and Architecture, Beijing 100044, China;
b Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100022, China
Received Date: 04 October 2017
Revised Date: 26 October 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (51578034), the Beijing Natural Science Foundation & Scientific Research Key Program of Beijing Municipal Commission of Education (KZ201410016018), Beijing Talent Project (2016023), and Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges Under Beijing Municipality (IDHT20170508).

Abstract: A new coordination polymer, Zn(bpy)L (BUC-21), (H₂L=cis-1,3-dibenzyl-2-imidazolidone-4,5-dicarboxylic acid, bpy=4,4'-bipyridine), has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray analysis, Fourier transform infrared spectroscopy, thermogravimetric analyses, CNH elemental analysis and UV-Vis diffuse reflectance spectroscopy. BUC-21 exhibited an excellent performance for photocatalytic Cr(VI) reduction with a conversion efficiency of 96%, better than that of commercial P25 (39%), under UV light irradiation for 30 min. BUC-21 could also be used to conduct photocatalytic degradation of organic dyes including methylene blue, rhodamine B, methyl orange and reactive red X-3B. Also, the photocatalytic activity of BUC-21 remained high across a wide pH range from 2.0 to 12.0. It is interesting to note, however, that BUC-21 was unable to achieve simultaneous reduction of Cr(VI) and degradation of an organic pollutant in a mixed matrix, which can be attributed to the competition between Cr(VI) and the organic dyes for access to the photo-excited electrons.

Key words:

1. [1] W. L. Yang, Y. Liu, Y. Hu, M. J. Zhou, H. S. Qian, J. Mater. Chem., 2012, 22, 13895-13898.
2. [2] G. D. Chen, M. Sun, Q. Wei, Z. M. Ma, B. Du, Appl. Catal. B, 2012, 125, 282-287.
3. [3] E. PetersonRoth, M. Reynolds, G. Quievryn, A. Zhitkovich, Mol. Cell. Biol., 2005, 25, 3596-3607.
4. [4] C. Liu, R. N. Jin, X. K. Ouyang, Y. G. Wang, Appl. Surf. Sci., 2017, 408, 77-87.
5. [5] A. M. Zayed, N. Terry, Plant Soil, 2003, 249, 139-156.
6. [6] S. Pipileima, S. Ray, L. Menan Devi, R. Mohan B, G. Srinikethan, B.C. Meikap (Eds.) Materials, Energy and Environment Engineering:Select Proceedings of ICACE 2015, Springer Singapore, Singapore, 2017, 137-144.
7. [7] C. C. Wang, J. R. Li, X. L. Lv, Y. Q. Zhang, G. S. Guo, Energy Environ. Sci., 2014, 7, 2831-2867.
8. [8] D. Z. Shen, J. X. Fan, W. Z. Zhou, B. Y. Gao, Q. Y. Yue, K. Qi, J. Hazard. Mater., 2009, 172, 99-107.
9. [9] C. C. Wang, X. D. Du, J. Li, X. X. Guo, P. Wang, J. Zhang, Appl. Catal. B, 2016, 193, 198-216.
10. [10] L. A. M. Ruotolo, J. C. Gubulin, Chem. Eng. J., 2009, 149, 334-339.
11. [11] F. Rodriguez-Valadez, C. Ortiz-Exiga, J. G. Ibanez, A. Alator-re-Ordaz, S. Gutierrez-Granados, Environ. Sci. Technol., 2005, 39, 1875-1879.
12. [12] C. Barrera-Díaz, V. Lugo-Lugo, G. Roa-Morales, R. Natividad, S. A. Martínez-Delgadillo, J. Hazard. Mater., 2011, 185, 1362-1368.
13. [13] C. E. Barrera, J. Hazard. Mater., 2012, 223-224, 1-12.
14. [14] H. L. Ma, Y. W. Zhang, Q. H. Hu, D. Yan, Z. Z. Yu, M. L. Zhai, J. Mater. Chem., 2012, 22, 5914-5916.
15. [15] R. D. Ludwig, C. M. Su, T. R. Lee, R.T. Wilkin, S. D. Acree, R. R. Ross, A. Keeley, Environ. Sci. Technol., 2007, 41, 5299-5305.
16. [16] P. V. A. Padmanabhan, K. P. Sreekumar, T. K. Thiyagarajan, R. U. Satpute, K. Bhanumurthy, P. Sengupta, G. K. Dey, K. G. K. Warrier, Vacuum, 2006, 80, 1252-1255.
17. [17] J. J. Testa, M. A. Grela, M. I. Litter, Environ. Sci. Technol., 2004, 38, 1589-1594.
18. [18] L. M. Wang, N. Wang, L. H. Zhu, H. W. Yu, H. Q. Tang, J. Hazard. Mater., 2008, 152, 93-99.
19. [19] Z. H. Diao, X. R. Xu, D. Jiang, J. J. Liu, L. J. Kong, G. Li, L. Z. Zuo, Q. H. Wu, Chem. Eng. J., 2017, 315, 167-176.
20. [20] M. N. Chong, B. Jin, C. W. K. Chow, C. Saint, Water Res., 2010, 44, 2997-3027.
21. [21] H. Tong, S. X. Ouyang, Y. P. Bi, N. Umezawa, M. Oshikiri, J. H. Ye, Adv. Mater., 2012, 24, 229-251.
22. [22] X. J. Liu, L. K. Pan, T. Lv, G. Zhu, Z. Sun, C. Q. Sun, Chem. Comm., 2011, 47, 11984-11986.
23. [23] J. F. Qu, D. Y. Chen, N. J. Li, Q. F. Xu, H. Li, J. H. He, J. M. Lu, Appl. Catal. B, 2017, 207, 404-411.
24. [24] L. X. Yang, Y. Xiao, S. H. Liu, Y. Li, Q. Y. Cai, S. L. Luo, G. M. Zeng, Appl. Catal. B, 2010, 94, 142-149.
25. [25] W. Zhang, Y. B. Wang, Z. Wang, Z. Y. Zhong, R. Xu, Chem. Comm., 2010, 46, 7631-7633.
26. [26] H. H. Chen, X. Q. Xiong, L. L. Hao, X. Zhang, Y. M. Xu, Appl. Surf. Sci., 2016, 389, 491-495.
27. [27] P. Wang, Y. Sheng, F. Z. Wang, H. G. Yu, Appl. Catal. B, 2018, 220, 561-569.
28. [28] Y. Lu, G. Liu, J. Zhang, Z. C. Feng, C. Li, Z. Li, Chin. J. Catal., 2016, 37, 349-358.
29. [29] K. L. He, J. Xie, X. Y. Luo, J. Q. Wen, S. Ma, X. Li, Y. P. Fang, X. C. Zhang, Chin. J. Catal., 2017, 38, 240-252.
30. [30] D. Z. Lu, W. Q. Chai, M. C. Yang, P. F. Fang, W. H. Wu, B. Zhao, R. Y. Xiong, H. M. Wang, Appl. Catal. B, 2016, 190, 44-65.
31. [31] L. Shi, X. G. Meng, T. Wang, H. B. Zhang, K. Chang, H. M. Liu, J. H. Ye, Adv. Sci., 2015, 2, 1500006.
32. [32] M. A. Nasalevich, M. Van Der Veen, F. Kapteijn, J. Gascon, CrystEngComm, 2014, 16, 4919-4926.
33. [33] A. M. Kirillov, Y. Y. Karabach, M. V. Kirillova, M. Haukka, A. J. L. Pombeiro, Cryst. Growth Des., 2012, 12, 1069-1074.
34. [34] M. Ranocchiari, J. A. van Bokhoven, Phys. Chem. Chem. Phys., 2011, 13, 6388-6396.
35. [35] S. Horike, Y. Inubushi, T. Hori, T. Fukushima, S. Kitagawa, Chem. Sci., 2011, 3, 116-120.
36. [36] Z. J. Li, J. Yao, Q. Tao, L. Jiang, T. B. Lu, Inorg. Chem., 2013, 52, 11694-11696.
37. [37] P. Kanoo, G. Mostafa, R. Matsuda, S. Kitagawa, T. K. Maji, Chem. Commun., 2011, 47, 8106-8108.
38. [38] A. C. Kizzie, A. G. Wong-Foy, A. J. Matzger, Langmuir, 2011, 27, 6368-6373.
39. [39] B. Liu, H. Miao, L. Y. Pang, L. Hou, Y. Y. Wang, Q. Z. Shi, CrystEngComm, 2012, 14, 2954-2958.
40. [40] R. J. Kuppler, D. J. Timmons, Q. R. Fang, J. R. Li, T. A. Makal, M. D. Young, D. Q. Yuan, D. Zhao, W. J. Zhuang, H. C. Zhou, Coord. Chem. Rev., 2009, 253, 3042-3066.
41. [41] J. J. Li, C. C. Wang, H. F. Fu, J. R. Cui, P. Xu, J. Guo, J. R. Li, Dalton Trans., 2017, 46, 10197-10201.
42. [42] X. D. Du, C. C. Wang, J. Zhong, J. G. Liu, Y. X. Li, P. Wang, J. Environ. Chem. Eng., 2017, 5, 1866-1873.
43. [43] D. Chisca, L. Croitor, E. B. Coropceanu, O. Petuhov, G. F. Volodina, S. G. Baca, K. Krämer, J. Hauser, S. Decurtins, S. X. Liu, M. S. Fonari, Cryst. Growth Des., 2016, 16, 7011-7024.
44. [44] L. P. Zhang, J. F. Ma, J. Yang, Y. Y. Pang, J. C. Ma, Inorg. Chem., 2010, 49, 1535-1550.
45. [45] J. Wang, Y. H. Zhang, H. X. Li, Z. J. Lin, M. L. Tong, Cryst. Growth Des., 2015, 7, 2352-2360.
46. [46] S. B. Wang, X. C. Wang, Small, 2015, 11, 3097-3112.
47. [47] M. Rakibuddin, R. Ananthakrishnan, Appl. Surf. Sci., 2016, 362, 265-273.
48. [48] W. Y. Huang, N. Liu, X. D. Zhang, M. H. Wu, L. Tang, Appl. Surf. Sci., 2017, 425, 107-116.
49. [49] R. Y. Zhang, W. C. Wan, D. W. Li, F. Dong, Y. Zhou, Chin. J. Catal., 2016, 38, 313-320.
50. [50] L. J. Shen, R. W. Liang, L. Wu, Chin. J. Catal., 2015, 36, 2071-2088.
51. [51] H. M. Zhao, Q. S. Xia, H. Z. Xing, D. S. Chen, H. Wang, ACS Sustain. Chem. Eng., 2017, 5, 4449-4456.
52. [52] L. J. Shen, W. M. Wu, R. W. Liang, R. Lin, L. Wu, Nanoscale, 2013, 5, 9374-9382.
53. [53] X. B. Wang, J. Liu, S. Leong, X. C. Lin, J. Wei, B. Kong, Y. F. Xu, Z. X. Low, J. F. Yao, H. T. Wang, ACS Appl. Mater. Interfaces, 2016, 8, 9080-9087.
54. [54] J. X. Low, S. W. Cao, J. G. Yu, S. Wageh, Chem. Comm., 2014, 50, 10768-10777.
55. [55] Y. J. Cui, Y. X. Wang, H. Wang, F. Cao, F. Y. Chen, Chin. J. Catal., 2016, 37, 1899-1906.
56. [56] M. S. Akple, J. X. Low, Z. Y. Qin, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Liu, Chin. J. Catal., 2015, 36, 2127-2134.
57. [57] Bruker AXS, SMART, Version 5.611, Bruker AXS, Madison, WI, USA, 2000.
58. [58] Bruker AXS, SAINT, Version 6.28, Bruker AXS, Madison, WI, USA, 2003.
59. [59] SADABS, V2.03, Bruker AXS, Madison, WI, 2000.
60. [60] G. M. Sheldrick, SHELX-97, Göttingen University, Germany, 1997.
61. [61] X. L. Chen, B. Zhang, H. M. Hu, F. Fu, X. L. Wu, T. Qin, M. L. Yang, G. L. Xue, J. W. Wang, Cryst. Growth Des., 2008, 8, 3706-3712.
62. [62] T. Ma, M. X. Li, Z. X. Wang, J. C. Zhang, M. Shao, X. He, Cryst. Growth Des., 2014, 14, 4155-4165.
63. [63] C. G. Silva, A. Corma, H. García, J. Mater. Chem., 2010, 20, 3141-3156.
64. [64] J. L. Wang, C. Wang, W. B. Lin, ACS Catal., 2012, 2, 2630-2640.
65. [65] J. Guo, J. F. Ma, B. Liu, W. Q. Kan, J. Yang, Cryst. Growth Des., 2011, 11, 3609-3621.
66. [66] Y. Ku, I. L. Jung, Water Res., 2001, 35, 135-142.
67. [67] S. J. Yang, J. H. Im, T. Kim, K. Lee, C. R. Park, J. Hazard. Mater., 2011, 186, 376-382.
68. [68] J. Guo, J. Yang, Y. Y. Liu, J. F. Ma, CrystEngComm, 2012, 14, 6609-6617.
69. [69] Z. Zhang, J. Yang, Y. Y. Liu, J. F. Ma, CrystEngComm, 2013, 15, 3843-3853.
70. [70] Y. Park, Y. Na, D. Pradhan, B. K. Min, Y. Sohn, CrystEngComm, 2014, 16, 3155-3167.
71. [71] X. H. Qi, Z. H. Wang, Y. Y. Zhuang, Y. Yu, J. L. Li, J. Hazard. Mater., 2005, 118, 219-225.
72. [72] T. Alammar, A. V. Mudring, ChemSusChem, 2011, 4, 1796-1804.
73. [73] Y. Wu, J. Feng, B. Xie, L. K. Zou, Y. L. Li, Z. Q. Li, J. Inorg. Organ-omet. Polym. Mater., 2017, 27, 1243-1251.
74. [74] Z. H. Ai, J. L. Wang, L. Z. Zhang, Chin. J. Catal., 2015, 36, 2145-2154.
75. [75] X. Y. Tang, Z. C. Fan, C. Wen, Y. H. Hu, W. Y. Yin, H. J. Cheng, Y. S. Ma, R. X. Yuan, Inorg. Chim. Acta, 2016, 451, 148-156.
76. [76] S. F. Li, X. Wang, Q. Q. He, Q. Chen, Y. L. Xu, H. B. Yang, M. M. Lü, F. Y. Wei, X. T. Liu, Chin. J. Catal., 2016, 37, 367-377.
77. [77] X. F. Hu, H. H. Ji, F. Chang, Y. M. Luo, Catal. Today, 2014, 224, 34-40.
78. [78] S. G. Schrank, H. J. José, R. F. P. M. Moreira, J. Photochem. Pho-tobiol. A Chem., 2002, 147, 71-76.
79. [79] X. Zhao, J. H. Qu, H. J. Liu, C. Hu, Environ. Sci. Technol., 2007, 41, 6802-6807.
80. [80] Y. S. Cao, J. X. Chen, L. Huang, Y. L. Wang, Y. Hou, Y. T. Lu, J. Mol. Catal. A Chem., 2005, 233, 61-66.
81. [81] M. Alvaro, E. Carbonell, B. Ferrer, F. X. Llabres Qi Xamera, H. Garcia, Chem. Eur. J., 2007, 13, 5106-5112.
82. [82] C. Gao, J. Wang, H. X. Xu, Y. J. Xiong, Chem. Soc. Rev., 2017, 46, 2799-2823.
83. [83] E. M. Dias, C. Petit, J. Mater. Chem. A, 2015, 3, 22484-22506.

扫一扫看文章

计量

PDF下载量: 4
文章访问数: 1244
HTML全文浏览量: 109

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

一种稳定二维配位聚合物用于光催化还原Cr(VI)及降解有机污染物

English

Photocatalytic Cr(VI) reduction and organic-pollutant degradation in a stable 2D coordination polymer

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

一种稳定二维配位聚合物用于光催化还原Cr(VI)及降解有机污染物

English

Photocatalytic Cr(VI) reduction and organic-pollutant degradation in a stable 2D coordination polymer

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