单层ZIF67纳米颗粒修饰的C<sub>3</sub>N<sub>4</sub>在可见光下光催化降解有机污染物

引用本文: 苏佩东, 张俊珂, 肖轲, 赵燊, Ridha Djellabi, 李学伟, 杨波, 赵旭. 单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物[J]. 催化学报, 2020, 41(12): 1894-1905. doi: 10.1016/S1872-2067(20)63620-8 shu

Citation: Peidong Su, Junke Zhang, Ke Xiao, Shen Zhao, Ridha Djellabi, Xuewei Li, Bo Yang, Xu Zhao. C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light[J]. Chinese Journal of Catalysis, 2020, 41(12): 1894-1905. doi: 10.1016/S1872-2067(20)63620-8 shu

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

苏佩东 ^a,b, ,
张俊珂 ^a, ,
肖轲 ^c, ,
赵燊 ^b, ,
Ridha Djellabi ^a, ,
李学伟 ^a,b, ,
杨波 ^a, ,
赵旭 ^b,

a 深圳大学化学与环境工程学院, 广东深圳 518060, 中国;
b 中国科学院生态环境研究中心, 中国科学院饮用水科学与技术重点实验室, 北京 100085, 中国;
c 杰克逊州立大学土木与环境工程学院, 杰克逊 39217, 美国
基金项目:
国家自然科学基金（21707154）；国家重大水污染控制科学技术计划（2017ZX07202）.

摘要: 随着全球工业化水平的提高，有机污染物引起的水环境问题也日益严重.针对有机污染物表现出的持久性和难降解性等问题，全球科研工作者提出了不同的方法去治理相关环境问题.其中利用光催化降解有机污染物作为一种新兴技术，因处理成本低、污染物降解效率高、光催化剂可回收利用等优点受到越来越多的关注.在诸多的光催化剂中，氮化碳（C₃N₄）拥有2.7eV的能带宽度，且其合成简单，价格低廉，环境友好，以及在可见光下即可催化降解污染物等特点而被广泛研究.但是，比表面积小和易与光激发电荷载流子结合等缺点也制约C₃N₄的广泛应用.针对上述问题，本文将具有巨大比表面积的金属骨架材料ZIF67引入到C₃N₄之中，合成了均匀分布的单层ZIF67衍生的C₃N₄（ZIF67-C₃N₄），并将其应用于可见光下的亚甲基蓝（MB）光催化降解.结果表明，所制得的ZIF67-C₃N₄的最大比表面积可达541.392m²/g，远高于未加工的C₃N₄的97.291m²/g.ZIF67-C₃N₄光催化活性结果表明，2.57g ZIF67和0.3g C₃N₄即ZIF67-C₃N₄（0.3）表现出优异的光催化活性.加入0.01g的ZIF67-C₃N₄（0.3）可以在70min内降解90%以上的浓度为10mg/L的亚甲基蓝，而原C₃N₄在同等条件下处理相同浓度的亚甲基蓝所需的时间超过140min.同时，本文还考察了溶液的pH值，亚甲基蓝的初始浓度和ZIF67-C₃N₄复合材料中C₃N₄的含量等因素对亚甲基蓝光催化降解的影响.结果显示，ZIF67-C₃N₄（0.3）在碱性条件下降解亚甲基蓝的效率高于中性条件.在pH=12的情况下，ZIF67-C₃N₄（0.3）可以在10min内完全降解100mL的浓度为10mg/L的亚甲基蓝.此外，在酸性条件下亚甲基蓝的降解效果很差，说明ZIF67-C₃N₄（0.3）在酸性条件下容易失活.通过对亚甲基蓝初始浓度对光催化反应的研究显示，当亚甲基蓝的初始浓度为20mg/L时，经140min反应后，亚甲基蓝的去除率小于90%；当亚甲基蓝的浓度降至15 mg/L时，其在120min的降解效率超过92%；而10mg/L的亚甲基蓝可在120min内完全降解.对制备的五种催化剂对亚甲基蓝的降解效果分析得出ZIF67-C₃N₄（0.3）比其他四种催化剂的效果更好.为了揭示ZIF67-C₃N₄（0.3）在可见光条件下催化降解亚甲基蓝的反应机理，本文利用叔丁醇、甲酸以及对苯醌进行淬灭实验.结果表明，光致空穴（h⁺）和超氧自由基（O₂^-·）是降解亚甲基蓝的主要活性物质.

关键词:

English

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

a College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China;
b Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China;
c Department of Civil and Environmental Engineering, Jackson State University, Jackson, MS 39217, USA
Received Date: 05 March 2020
Revised Date: 17 April 2020
Fund Project:
This work was jointly funded by the National Natural Science Foundation of China (21707154) and the National Major Science & Technology Program for Water Pollution Control & Treatment (2017ZX07202).

Abstract: Uniformly distributed single layer of ZIF67-derived C₃N₄ (ZIF67-C₃N₄) was synthesized and applied to the photocatalytic degradation of methylene blue (MB) under visible light. Results indicated that the obtained ZIF67-C₃N₄has a maximum specific surface area of 541.392 m²/g, which is much larger than that of raw C₃N₄ of 97.291 m²/g. The investigation of C₃N₄ amount involved in ZIF67-C₃N₄on the photoactivity revealed that 2.57 g ZIF67 with 0.3 g C₃N₄, which named ZIF67-C₃N₄(0.3) exhibited superior photocatalytic activities. More than 90% of MB at 10 mg/L was degraded within 70 min with the addition of 0.01 g ZIF67-C₃N₄(0.3), while this time required for raw C₃N₄ was over 140 min. The effects of pH of solution, initial concentration of MB and dosage of C₃N₄ in ZIF67-C₃N₄composites on the photocatalytic efficiency for MB degradation were also evaluated. Quenching experiments indicated that the photo-induced holes (h⁺) and superoxide radicals (O^2-·) were mainly responsible for MB degradation. It is anticipated that the insertion of ZIF67 nanoparticles not only increases the adsorption capacity of C₃N₄ but also promotes the generation and migration of the photo-induced active species.

Key words:

1. [1] K. T. Carvalho, A. E. Nogueira, O. F. Lopes, G. Byzynski, C. Ribeiro, Cera. Int., 2017, 43, 3521-3530.
2. [2] Y. Sheng, Z. Wei, H. Miao, W. Yao, H. Li, Y. Zhu, Chem. Engineering J., 2019, 370, 287-294.
3. [3] S. N. Ahmed, W. Haider, Nanotechnology, 2018, 29, 342001.
4. [4] D. B. Miklos, C. Remy, M. Jekel, K. G. Linden, J. E. Drewes, U. Hübner, Water Res., 2018, 139, 118-131.
5. [5] D. S. Babu, V. Srivastava, P. V. Nidheesh, M. S. Kumar, Sci. Total Environ., 2019, 696, 133961.
6. [6] R. Hao, G. Wang, H. Tang, L. Sun, C. Xu, D. Han, Appl. Catal. B, 2016, 187, 47-58.
7. [7] C. Pan, J. Jia, X. Hu, J. Fan, E. Liu, Appl. Surf. Sci., 2018, 430, 283-292.
8. [8] Q. Tang, X. Meng, Z. Wang, J. Zhou, H. Tang, Appl. Surf. Sci., 2018, 430, 253-262.
9. [9] Y. Zhang, P. Su, D. Weathersby, Q. Zhang, J. Zheng, R. Fan, J. Zhang, Q. Dai, Appl. Surf. Sci., 2020, 501, 144217.
10. [10] S. Borthakur, L. Saikia, J. Environ. Chem. Eng., 2019, 7, 103035.
11. [11] X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen, M. Antonietti, Nat. Mater., 2009, 8, 76.
12. [12] M. Zhang, W. Jiang, D. Liu, J. Wang, Y. Liu, Y. Zhu, Y. Zhu, Appl. Catal. B, 2016, 183, 263-268.
13. [13] T. Arumugham, R. G. Amimodu, N. J. Kaleekkal, D. Rana, J. Environ. Sci., 2019, 82, 57-69.
14. [14] J. Fu, J. Yu, C. Jiang, B. Cheng, Adv. Energy Mater., 2018, 8, 1701503.
15. [15] Z. Jiang, W. Wan, H. Li, S. Yuan, H. Zhao, P. K. Wong, Adv. Mater., 2018, 30, 1706108.
16. [16] Y. Wang, R. Shi, J. Lin, Y. Zhu, Energy Environ. Sci., 2011, 4, 2922-2929.
17. [17] Y. He, Y. Wang, L. Zhang, B. Teng, M. Fan, Appl. Catal. B, 2015, 168, 1-8.
18. [18] Q. Sun, K. Lv, Z. Zhang, M. Li, B. Li, Appl. Catal. B, 2015, 164, 420-427.
19. [19] J. Yan, H. Wu, H. Chen, Y. Zhang, F. Zhang, S. F. Liu, Appl. Catal. B, 2016, 191, 130-137.
20. [20] L. Ge, C. Han, J. Liu, Appl. Catal. B, 2011, 108, 100-107.
21. [21] J. Wang, L. Tang, G. Zeng, Y. Liu, Y. Zhou, Y. Deng, J. Wang, B. Peng, ACS Sustainable Chem. Eng., 5, 2016, 1062-1072.
22. [22] M. Zhang, Y. Zhang, L. Tang, G. Zeng, J. Wang, Y. Zhu, C. Feng, Y. Deng, W. He, J. Colloid Interface Sci., 2018, 539, 654-664.
23. [23] G. Miao, D. Huang, X. Ren, X. Li, Z. Li, J. Xiao, Appl. Catal. B, 2016, 192, 72-79.
24. [24] M. Ou, S. Wan, Q. Zhong, S. Zhang, Y. Song, L. Guo, W. Cai, Y. Xu, Appl. Catal. B, 2018, 221, 97-107.
25. [25] Z. Sun, Z. Yu, Y. Liu, C. Shi, M. Zhu, A. Wang, J. Colloid Interface Sci., 2019, 533, 251-258.
26. [26] N. Stock, S. Biswas, Chem. Rev., 2011, 112, 933-969.
27. [27] X. Xu, R. Cao, S. Jeong, J. Cho, Nano Lett., 2012, 12, 4988-4991.
28. [28] W. Chaikittisilp, K. Ariga, Y. Yamauchi, J. Mater. Chem. A, 2013, 1, 14-19.
29. [29] D. Liu, D. Chen, N. Li, Q. Xu, H. Li, J. He, J. Lu, Small, 2019, 1902291.
30. [30] J. Qian, F. Sun, L. Qin, Mater. Lett., 2012, 82, 220-223.
31. [31] J. Navarro-Sánchez, N. Almora-Barrios, B. Lerma-Berlanga, J. J. Ruiz-Pernía, V. A. Lorenz-Fonfria, I. Tuñón, C. Martí-Gastaldo, Chem. Sci., 2019, 10, 4082-4088.
32. [32] Y. Chen, D. Wang, X. Deng, Z. Li, Catal. Sci. Technol., 2017, 7, 4893-4904.
33. [33] C. Wang, J. Kim, V. Malgras, J. Na, J. Lin, J. You, M. Zhang, J. Li, Y. Yamauchi, Small, 2019, 15, 1900744.
34. [34] G. Zhou, M. F. Wu, Q. J. Xing, F. Li, H. Liu, X. B. Luo, J. P. Zou, J. M. Luo, A. Q. Zhang, Appl. Catal. B, 2018, 220, 607-614.
35. [35] K. Y. A. Lin, H. A. Chang, J. Taiwan Inst. Chem. Eng., 2015, 53, 40-45.
36. [36] J. S. M. Lee, Y. I. Fujiwara, S. Kitagawa, S. Horike, Chem. Mater., 2019, 31, 4205-4212.
37. [37] Y. Pan, K. Sun, S. Liu, X. Cao, K. Wu, W. C. Cheong, Z. Chen, Y. Wang, Y. Li, Y. Liu, D. Wang, Q. Peng, C. Chen, Y. Li, J. Am. Chem. Soc., 2018, 140, 2610-2618.
38. [38] L. Shang, H. Yu, X. Huang, T. Bian, R. Shi, Y. Zhao, G. I. N. Waterhouse, T. Zhang, Adv. Mater., 2016, 28, 1668-1674.
39. [39] Z. Mao, J. Chen, Y. Yang, D. Wang, L. Bie, B. D. Fahlman, ACS Appl. Mater. Interfaces, 2017, 9, 12427-12435.
40. [40] Y. Luo, X. Wei, B. Gao, W. Zou, Y. Zheng, Y. Yang, Y. Zhang, Q. Tong, L. Dong, Chem. Eng. J., 2019, 122019.
41. [41] G. W. Roberts, C. N. Satterfield, Ind. Eng. Chem. Fund., 1965, 4, 288-293.
42. [42] N. G. Asenjo, R. Santamaria, C. Blanco, M. Granda, P. Alvarez, R. Menéndez, Carbon, 2013, 55, 62-69.
43. [43] Y. Deng, Chem. Eng. J., 2018, 337, 220-227.
44. [44] J. Tang, Z. Zou, J. Yin, J. Ye, Chem. Phys. Lett., 2003, 382, 175-179.
45. [45] S. C. Yan, Z. S. Li, Z. G. Zou, Langmuir, 2010, 26, 3894-3901.
46. [46] Q. Xiang, J. Yu, M. Jaroniec, J. Phys. Chem. C, 2011, 115, 7355-7363.
47. [47] W. J. Ong, L. L. Tan, Y. H. Ng, S. T. Yong, S. P. Chai, Chem. Rev., 2016, 116, 7159-7329.
48. [48] Y. Feng, S. Lin, S. Huang, S. Shrestha, G. Conibeer, J. Appl. Phys., 2015, 117, 125701.
49. [49] P. Soni, V. V. S. Murty, K. K. Kushwaha, J. Nanosci. Nanoeng. Appl., 2018, 8, 69-74.
50. [50] F. Wei, Z. Deng, S. Sun, N. T. P. Hartono, H. L. Seng, T. Buonassisi, P. D. Bristowe, A. K. Cheetham, Chem. Commun., 2019, 55, 3721-3724.
51. [51] R. Su, Q. Li, Y. Chen, B. Gao, Q. Yue, W. Zhou, J. Cleaner Prod., 2019, 209, 20-29.
52. [52] R. Djellabi, M. F. Ghorab, A. Smara, C. L. Bianchi, G. Cerrato, X. Zhao, B. Yang, In:Green Materials for Wastewater Treatment, M. Naushad, E. Lichtfouse, eds., Springer, 2020, 291-319.
53. [53] Q. Hao, Y. Huang, D. Chen, Y. Liu, W Wei, B. J. Ni, Chin. J. Catal., 2020, 41, 249-258.
54. [54] Q. Hao, G. Jia, W. Wei, A. Vinu, Y. Wang, H. Arandiyan, B. J. Ni, Nano Res., 2020, 13, 18-37.
55. [55] J. Qian, F. Sun, L. Qin, Mater. Lett., 2012, 82, 220-223.
56. [56] S. C. Yan, Z. S. Li, Z. G. Zou, Langmuir, 2009, 25, 10397-10401.

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沈阳化工大学材料科学与工程学院沈阳 110142

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

English

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

单层ZIF67纳米颗粒修饰的C3N4在可见光下光催化降解有机污染物

English

C3N4 modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

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？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

单层ZIF67纳米颗粒修饰的C₃N₄在可见光下光催化降解有机污染物

C₃N₄ modified with single layer ZIF67 nanoparticles for efficient photocatalytic degradation of organic pollutants under visible light

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs