以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)<sub>2</sub>助催化剂用于光催化产氢

引用本文: 李丹丹, 董玉明, 王光丽, 蒋平平, 张飞燕, 张会珍, 李激, 吕金泽, 王燕, 刘青云. 以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)₂助催化剂用于光催化产氢[J]. 催化学报, 2020, 41(5): 889-897. doi: S1872-2067(19)63499-6 shu

Citation: Dandan Li, Yuming Dong, Guangli Wang, Pingping Jiang, Feiyan Zhang, Huizhen Zhang, Ji Li, Jinze Lyu, Yan Wang, Qingyun Liu. Controllable photochemical synthesis of amorphous Ni(OH)₂ as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent[J]. Chinese Journal of Catalysis, 2020, 41(5): 889-897. doi: S1872-2067(19)63499-6 shu

以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)₂助催化剂用于光催化产氢

李丹丹 ^a, ,
董玉明 ^a, ,
王光丽 ^a, ,
蒋平平 ^a, ,
张飞燕 ^a, ,
张会珍 ^a, ,
李激 ^b, ,
吕金泽 ^b, ,
王燕 ^b, ,
刘青云 ^c,

a 江南大学化学与材料工程学院, 光响应分子材料国家级国际联合研究中心, 江苏无锡 214122;
b 江南大学环境与土木工程学院, 江苏省厌氧生物技术重点实验室, 江苏无锡 214122;
c 山东科技大学化学与环境工程学院, 山东青岛 266590
基金项目:
国家自然科学基金（21676123，21575052）；江苏省自然科学基金（BK20161127）；中央高校基本科研业务费专项资金（JUSRP51623A）；食品科学与技术国家一流学科计划（JUFSTR20180301）；山东省精细化学品清洁合成重点实验室开放研究基金（ZDSYS-KF201504）；江南大学生物质转化技术国际联合实验室和教育部111引智基地（B13025）；江苏省研究生科研与实践创新计划项目（KYCX19_1874）.

摘要: 随着环境污染和能源危机的加剧，发展可持续能源迫在眉睫.氢气被认为是可以替代化石能源的最有前途的能源之一，且光催化分解水产氢是一种可以将太阳能转化为氢能的环境友好的方法.n型半导体材料石墨C₃N₄（g-C₃N₄）是一种被广泛用作光催化产氢的吸光材料，然而，纯g-C₃N₄的光生电子-空穴对会迅速重组，其光催化活性非常低.负载助催化剂能够有效抑制光生载流子的复合，是提高光催化产氢速率的有效方法.助催化剂的作用是将电子和空穴转移给相应的反应物，因此除了助催化剂和光吸收材料之间的能级匹配之外，助催化剂负载的位置也是非常重要的.通过常规方法制备的助催化剂一般是随机分布的，而光化学方法可以将助催化剂沉积在电子和空穴的出口处，从而有利于下一步的光催化反应.使用光化学沉积法，可以通过光化学氧化制备氧化型助催化剂，也可以通过光化学还原制备还原型助催化剂.光化学法是还原贵金属助催化剂的一种常用方法，但是对于制备非贵金属助催化剂来说，它仍然是一种相对新颖的方法.光化学法目前正处于发展阶段，依然缺乏成分调控的手段，因此我们致力于发展相对准确、可控的光沉积方法.H₂PO₂^-由于其特殊的性质被用于光化学还原过渡金属，然而，在H₂PO₂^-存在下形成的颗粒非常大且高度结晶，这可能抑制光催化剂的活性.本文设计了一种利用其他磷酸盐光沉积合成光催化剂的新方法，旨在制备可控的弱结晶和小尺寸的助催化剂，以提高产氢活性.
首先以不同磷酸盐为原料制备催化剂，发现以H₂PO₃^-为无机牺牲剂制得的催化剂的光催化产氢活性非常突出，而且制得的催化剂具有无定形结构并且平均尺寸约为10nm.通过XRD，XPS等多种表征，证实了该条件下得到的产物是Ni（OH）₂/g-C₃N₄.同时，通过设计对照实验，发现在使用H₂PO₃^-作为牺牲剂，NiCl₂作为镍源，g-C₃N₄作为光吸收材料条件下才能制得效果最好的催化剂.然后对光沉时间，原料添加量，产氢牺牲剂等多组条件进行了优化，得到最优的复合光催化剂Ni（OH）₂/g-C₃N₄（4.36wt%）的光催化产氢速率为13707.86μmol·g^-1·h^-1，甚至高于Pt-4.36 wt%/g-C₃N₄的活性（11210.93μmol·g^-1·h^-1）.最后，通过PL，TR-PL，SPV，I-V等多种表征对反应机理进行探究，结果表明，光催化产氢性能提升主要原因是Ni（OH）₂的负载可以有效提高光生电荷的分离和转移效率，抑制光生电子对的重组.

关键词:

English

Controllable photochemical synthesis of amorphous Ni(OH)₂ as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent

a International Joint Research Center for Photo-responsive Molecules and Materials, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China;
b Jiangsu Key Laboratory of Anaerobic Biotechnology, School of Environment and Civil Engineering, Jiangnan University, Wuxi 214122, Jiangsu, China;
c College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
Received Date: 20 August 2019
Revised Date: 04 September 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21676123, 21575052), the Natural Science Foundation of Jiangsu Province (BK20161127), the Fundamental Research Funds for the Central Universities (JUSRP51623A), the National First-class Discipline Program of Food Science and Technology (JUFSTR20180301), the Opening Foundation of Shandong Provincial Key Laboratory of Clean Production of Fine Chemicals (ZDSYS-KF201504) from Shandong Normal University, the MOE &

Abstract: Loading of cocatalysts can effectively inhibit the recombination of photogenerated carriers in photocatalysts and greatly improve the photocatalytic hydrogen production rate. Cocatalysts can be deposited at the outlet points of electrons using a photochemical method, which is beneficial for the following photocatalytic hydrogen production reaction. H₂PO₂^- has been used in the photochemical reduction of transition metals because of its special properties. However, the particles formed in the presence of H₂PO₂^- are very large and highly crystalline, which may inhibit the activity of photocatalysts. In this study, we designed a new method for synthesizing photocatalysts by photodeposition using some other phosphates, aiming to prepare controllable weakly crystalline and small-size cocatalysts to improve the hydrogen production activity. The cocatalyst prepared using H₂PO₃^- as an inorganic sacrificial agent has an amorphous structure and an average size of about 10 nm. The optimal photocatalytic hydrogen production rate of the obtained Ni(OH)₂/g-C₃N₄ (4.36 wt%) is 13707.86 μmol·g^-1·h^-1, which is even higher than the activity of Pt-4.36 wt%/g-C₃N₄ (11210.93 μmol·g^-1·h^-1). Mechanistic studies show that loading of Ni(OH)₂ can efficiently accelerate the separation and transfer efficiency of photogenerated charge carriers.

Key words:

1. [1] B. Tian, B. N. Tian, B. Smith, M. C. Scott, R. N. Hua, Q. Lei, Y. Tian, Nat. Commun., 2018, 9, 1397.
2. [2] B. Lin, H. An, X. Q. Yan, T. X. Zhang, J. J. Wei, G. D. Yang, Appl. Catal. B, 2017, 210, 173-183.
3. [3] Y. Y. Kang, Y. Q. Yang, L. C. Yin, X. D. Kang, G. Liu, H. M. Cheng, Adv. Mater., 2015, 27, 4572-4577.
4. [4] D. Qu, J. Liu, X. Miao, M. M. Han, H. C. Zhang, Z. Cui, S. R. Sun, Z. H. Kang, H. Y. Fan, Appl. Catal. B, 2018, 227, 418-424.
5. [5] S. W. Cao, H. Li, T. Tong, H. C. Chen, A. C. Yu, J. G. Yu, H. M. Chen, Adv. Funct. Mater., 2018, 28, 1802169.
6. [6] X. Li, J. G. Yu, M. Jaroniec, X. B. Chen, Chem. Rev., 2019, 119, 3962-4179.
7. [7] J. Q. Ma, Q. F. Yang, Y. Z. Wen, W. P. Liu, Appl. Catal. B, 2017, 201, 232-240.
8. [8] L. Zhou, L. Z. Wang, J. Y. Lei, Y. D. Liu, J. L. Zhang, Catal. Commun., 2017, 89, 125-128.
9. [9] L. G. Kong, Y. M. Dong, P. P. Jiang, G. L. Wang, H. Z. Zhang, N. Zhao, J. Mater. Chem. A, 2016, 4, 9998-10007.
10. [10] J. Q. Wen, J. Xie, H. D. Zhang, A. P. Zhang, Y. J. Liu, X. B. Chen, X. Li, ACS Appl. Mater. Interfaces, 2017, 9, 14031-14042.
11. [11] R. C. Shen, J. Xie, Q. J. Xiang, X. B. Chen, J. Z. Jiang, X. Li, Chin. J. Catal., 2019, 40, 240-288.
12. [12] X. X. Yan, Z. Y. Jia, H. B. Che, S. Q. Chen, P. Hua, J. S. Wang, L. Z. Wang, Appl. Catal. B, 2018, 234, 19-25.
13. [13] M. S. Fan, C. J. Song, T. J. Chen, X. Yan, D. B, Xu, W. Gu, W. D. Shi, L. S. Xiao, RSC Adv., 2016, 6, 34633-34640.
14. [14] Z. P. Huang, Z. Z. Chen, Z. B. Chen, C. C. Lv, M. G. Humphrey, C. Zhang, Nano Energy, 2014, 9, 373-382.
15. [15] B. Tian, Z. Li, W. L. Zhen, G. X. Lu, J. Phys. Chem. C, 2016, 120, 6409-6415.
16. [16] Y. M. Dong, L. G. Kong, G. L. Wang, P. P. Jiang, N. Zhao, H. Z. Zhang, Appl. Catal. B, 2017, 211, 245-251.
17. [17] D. S. Dai, H. Xu, L. Ge, C. C. Han, Y. Q. Gao, S. S. Li, Y. Lu, Appl. Catal. B, 2017, 217, 429-436.
18. [18] Y. M. Dong, L. G. Kong, P. P. Jiang, G. L. Wang, N. Zhao, H. Z. Zhang, B. Tang, ACS Sustainable Chem. Eng., 2017, 5, 6845-6853.
19. [19] S. Q. Peng, Y. Yang, J. N. Tan, C. Gan, Y. X. Li, Appl. Surf. Sci., 2018, 447, 822-828.
20. [20] T. F. Wu, P. F. Wang, Y. H. Ao, C. Wang, J. Colloid Interf. Sci., 2018, 525, 107-114.
21. [21] H. Zhao, S. N. Sun, P. P. Jiang, Z. C. J. Xu, Chem. Eng. J., 2017, 315, 296-303.
22. [22] J. L. Yuan, J. Q. Wen, Y. M. Zhong, X. Li, Y. P. Fang, S. S. Zhang, W. Liu, J. Mater. Chem. A, 2015, 3, 18244-18255.
23. [23] S. D. Guan, X. L. Fu, Y. Zhang, Z. J. Peng, Chem. Sci., 2018, 9, 1574-1585.
24. [24] H. Zhao, H. Z. Zhang, G. W. Cui, Y. M. Dong, G. L. Wang, P. P. Jiang, X. M. Wu, N. Zhao, Appl. Catal. B, 2018, 225, 284-290.
25. [25] J. Q Wen, J. Xie, Z. H. Yang, R. C. Shen, H. Y. Li, X. Y. Luo, X. B. Chen, X. Li, ACS Sustainable Chem. Eng., 2017, 5, 2224-2236.
26. [26] K. L. He, J. Xie, M. L. Li, X. Li, Appl. Surf. Sci., 2018, 430, 208-217.
27. [27] P. Wang, S. Q. Xu, F. Chen, H. G. Yu, Chin. J. Catal., 2019, 40, 343-351.
28. [28] J. J. Yi, H. P. Li, Y. J. Gong, X. J. She, Y. H. Song, Y. G. Xu, J. J. Deng, S. Q. Yuan, H. Xua, H. M. Li, Appl. Catal. B, 2019, 243, 330-336.
29. [29] H. Zhao, Y. M. Dong, P. P. Jiang, H. Y. Miao, G. L. Wang, J. J. Zhang, J. Mater. Chem. A, 2015, 3, 7375-7381.
30. [30] S. Ma, J. Xie, J. Q. Wen, K. L. He, X. Li, W. Liu, X. C. Zhang, Appl. Surf. Sci., 2017, 391, 580-591.
31. [31] 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.
32. [32] J. J. Zhu, H. Y. Yin, Z. Z. Cui, D. Y. Qin, J. Y. Gong, Q. L. Nie, Appl. Surf. Sci., 2017, 420, 323-330.
33. [33] J. Q. Yan, H. Wu, H. Chen, L. Q. Pang, Y. X. Zhang, R. B. Jiang, L. D. Li, S. Z. Liu, Appl. Catal. B, 2016, 194, 74-83.
34. [34] X. Y. Lu, J. Xie, S. Y. Liu, A. Adamski, X. B. Chen, X. Li, ACS Sustainable Chem. Eng., 2018, 6, 13140-13150.
35. [35] W. Zhang, H. W. Zhang, J. Z. Xu, H. Q. Zhuang, J. L. Long, Chin. J. Catal., 2019, 40, 320-325.
36. [36] R. T. Chen, S. Pang, H. Y. An, J. Zhu, S. Ye, Y. Y. Gao, F. T. Fan, C. Li, Nat. Energy, 2018, 3, 655-663.
37. [37] R. G. Li, F. X. Zhang, D. E. Wang, J. X. Yang, M. R. Li, J. Zhu, X. Zhou, H. X. Han, C. Li, Nat. Commun., 2013, 4, 1432.
38. [38] R. G. Li, H. X. Han, F. X. Zhang, D. E. Wang, C. Li, Energy Environ. Sci., 2014, 7, 1369-1376.
39. [39] A. Y. Meng, J. Zhang, D. F. Xu, B. Cheng, J. G. Yu, Appl. Catal. B, 2016, 198, 286-294.
40. [40] N. Zhao, L. G. Kong, Y. M. Dong, G. L. Wang, X. M. Wu, P. P. Jiang, ACS Appl. Mater. Interfaces, 2018, 10, 9522-9531.
41. [41] W. J. Wang, J. C. Yu, D. H. Xia, P. K. Wong, Y. C. Li, Environ. Sci. Technol., 2013, 47, 8724-8732.
42. [42] P. Niu, L. L. Zhang, G. Liu, H. M. Cheng, Adv. Funct. Mater., 2012, 22, 4763-4770.
43. [43] S. S. Yi, J. M. Yan, B. R. Wulan, S. J. Li, K. H. Liu, Q. Jiang, Appl. Catal. B, 2017, 200, 477-483.
44. [44] S. B. Yang, Y. J. Gong, J. S. Zhang, L. Zhan, L. L. Ma, Z. Y. Fang, R. Vajtai, X. C. Wang, P. M. Ajayan, Adv. Mater., 2013, 25, 2452-2456.
45. [45] J. R. Ran, W. W. Guo, H. L. Wang, B. C. Zhu, J. G. Yu, S. Z. Qiao, Adv. Mater., 2018, 30, 1800128-1800133.
46. [46] L. Zhang, Y. B. Li, C. L. Li, Q. Chen, Z. Zhen, X. Jiang, M. Zhong, F. X. Zhang, H. W. Zhu, ACS Nano, 2017, 11, 12753-12763.

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沈阳化工大学材料科学与工程学院沈阳 110142

以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)₂助催化剂用于光催化产氢

English

Controllable photochemical synthesis of amorphous Ni(OH)₂ as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent

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

以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)2助催化剂用于光催化产氢

English

Controllable photochemical synthesis of amorphous Ni(OH)2 as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent

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

以无机亚磷酸为牺牲剂光化学法制备无定形Ni(OH)₂助催化剂用于光催化产氢

Controllable photochemical synthesis of amorphous Ni(OH)₂ as hydrogen production cocatalyst using inorganic phosphorous acid as sacrificial agent

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs