利用地球上丰富的炭黑和NiS<sub>2</sub>双助催化剂修饰提高CdS纳米片体系的可见光产氢活性

引用本文: 马松, 徐兴民, 谢君, 李鑫. 利用地球上丰富的炭黑和NiS₂双助催化剂修饰提高CdS纳米片体系的可见光产氢活性[J]. 催化学报, 2017, 38(12): 1970-1980. doi: 10.1016/S1872-2067(17)62965-6 shu

Citation: Song Ma, Xingmin Xu, Jun Xie, Xin Li. Improved visible-light photocatalytic H₂ generation over CdS nanosheets decorated by NiS₂ and metallic carbon black as dual earth-abundant cocatalysts[J]. Chinese Journal of Catalysis, 2017, 38(12): 1970-1980. doi: 10.1016/S1872-2067(17)62965-6 shu

利用地球上丰富的炭黑和NiS₂双助催化剂修饰提高CdS纳米片体系的可见光产氢活性

马松 ^a, ,
徐兴民 ^a, ,
谢君 ^a,b, ,
李鑫 ^a,b,

a 华南农业大学材料与能源学院, 广东广州 510642;
b 华南农业大学林学与风景园林学院, 农业部能源植物资源与利用重点实验室, 广东广州 510642
基金项目:
国家自然科学基金（51672089）；广东省科技计划（2015B020215011）；武汉理工大学材料复合新技术国家重点实验室开放基金（2015-KF-7）.

摘要: 光催化产氢技术是目前解决能源和环境问题的最有潜力的方法之一，因此制备安全高效的光催化剂已成为目前的研究热点.在目前研究的各种光催化剂中，CdS光催化剂因为具有较窄的带隙（2.4 eV）和合适的导带位置，所以在可见光催化产氢领域受到广泛关注.然而，光生电子/空穴对易复合和光腐蚀作用极大地限制了CdS光催化剂的放大应用.因此，人们采用众多改性策略以提高CdS光催化剂的可见光产氢活性，其中构建CdS纳米结构和负载助催化剂被认为是最有效的方式.构建CdS纳米结构既可以缩短载流子的迁移路径，也可以减少CdS晶体中的缺陷.很多不同纳米结构的CdS光催化剂已经被开发，例如纳米线、纳米颗粒和纳米棒等.因为制备过程极为复杂繁琐，所以CdS纳米片的研究鲜见报道.
本文采用乙酸鎘和硫脲为原材料，通过简单的溶剂热法合成了CdS纳米片.在CdS的各类助催化剂中，由于常用的Pt，Ag和Au等贵金属的高成本和低储量等问题严重限制了它们的实际应用，所以近年来众多非贵金属助催化剂（例如MoS₂，WS₂，NiS，NiO和WC等）得到了广泛关注.由于非贵金属助催化剂存在弱电导率和低功函数等问题，影响了对光生电子的收集和利用.纳米碳材料具有极高的电导率、强可见光吸收、有效的载流子分离和较多的反应位点等优点，因此组合纳米碳材料和非贵金属助催化剂被认为是一种有效的解决方案.本文首次采用炭黑和NiS₂作为双助催化剂改性CdS纳米片，通过简单的溶剂热/沉淀两步法成功合成了廉价高效的CdS/CB/NiS₂三元光催化体系.光催化产氢性能测试表明，CdS-0.5% CB-1% NiS₂展现出最高的光催化效率（166.7 μmol h^-1），分别是CdS NSs和CdS-1.0% NiS₂的5.16和1.87倍.X射线衍射、高分辨电子显微镜和X射线光电子能谱结果证实了CdS催化剂的片状结构，且炭黑和NiS₂成功负载在CdS纳米片表面.紫外-可见漫反射结果表明，随着炭黑和NiS₂的负载，复合催化剂的吸收边缘产生明显的红移，且对可见光的吸收增强.荧光光谱、阻抗和瞬态光电流曲线测试结果证明，炭黑和NiS₂的加入可以有效地促进光生电子/空穴对分离.极化曲线结果表明，加入炭黑和NiS₂可以降低CdS的产氢过电势，因此加速表面产氢动力学.总之，炭黑和NiS₂之间显著的协同效应极大地提高了可见光吸收，促进光生电子/空穴对分离，加速表面产氢动力学，最终得到了三元光催化体系极高的光催化产氢活性.

关键词:

English

Improved visible-light photocatalytic H₂ generation over CdS nanosheets decorated by NiS₂ and metallic carbon black as dual earth-abundant cocatalysts

a College of Materials and Energy, South China Agricultural University, Guangzhou 510642, Guangdong, China;
b College of Forestry and Landscape Architecture, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, South China Agricultural University, Guangzhou 510642, Guangdong, China
Received Date: 09 October 2017
Revised Date: 31 October 2017
Fund Project:
The work was supported by the National Natural Science Foundation of China (51672089), the Science and Technology Planning Project of Guangdong Province (2015B020215011), and the State Key Laboratory of Advanced Technology for Material Synthesis and Processing (Wuhan University of Technology) (2015-KF-7).

Abstract: CdS nanosheets (NSs) photocatalysts modified with dual earth-abundant co-catalysts of metallic carbon black (CB) and NiS₂ were synthesized by a two-step solvother-mal/impregnation method. All the experiment results demonstrated that the co-loading of CB and NiS₂ could significantly enhance the photocatalytic H₂-evolution activity of CdS NSs. The photocatalytic performance of the as-prepared CdS/CB/NiS₂ samples was tested under visible light (λ ≥ 420 nm) by using an aqueous solution containing 0.25 mol L^-1 Na₂S-Na₂SO₃ as the sacrifice agent. The CdS-0.5% CB-1.0%NiS₂ composite photocatalysts exhibited the highest H₂-evolution rate of 166.7 μmol h^-1, which was approximately 5.16 and 1.87 times higher than those of pure CdS NSs and CdS-1.0%NiS₂, respectively. The possible mechanism for the enhanced H₂-evolution activity of CdS/CB/NiS₂ composite photocatalysts was proposed. The results showed that the enhanced photocatalytic H₂-evolution activities could be ascribed to the co-loading of metallic CB and NiS₂ as co-catalysts onto the surface of CdS NSs. The excellent synergetic effect between the CB and NiS₂ could obviously improve visible light absorption, promote separation of photogenerated electron-hole pairs and boost the H₂-evolution kinetics, thus leading to an enhanced activity for H₂ evolution. More interestingly, the metallic CB could not only act as a cocatalyst for H₂ evolution, but also serve as a conductive electron bridge to promote the charge migration. This work not only demonstrates that loading CB as a co-catalyst is a promising strategy to further boost the photocatalytic activity of CdS/NiS₂ composites, but also offers a new mechanistic insight into the construction of highly efficient and stable CdS NSs-based hybrid photocatalysts with dual earth-abundant co-catalysts for photocatalytic applications.

Key words:

1. [1] J. X. Low, J. G. Yu, M. Jaroniec, S. Wageh, A. A. Al-Ghamdi, Adv. Mater., 2017, 29, 1601694.
2. [2] X. Li, J. G. Yu, J. X. Low, Y. P. Fang, J. Xiao, X. B. Chen, J. Mater. Chem. A, 2015, 3, 2485-2534.
3. [3] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
4. [4] T. T. Wu, X. D. Kang, M. W. Kadi, I. Ismail, G. Liu, H. M. Cheng, Chin. J. Catal., 2015, 36, 2103-2108.
5. [5] Y. X. Liu, Z. L. Wang, W. X. Huang, Appl. Surf. Sci., 2016, 389, 760-767.
6. [6] J. Q. Wen, X. Li, W. Liu, Y. P. Fang, J. Xie, Y. H. Xu, Chin. J. Catal., 2015, 36, 2049-2070.
7. [7] 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.
8. [8] W. J. Dai, J. Q. Yan, K. Dai, L. D. Li, N. J. Guan, Chin. J. Catal., 2015, 36, 1968-1975.
9. [9] Q. Li, B. D. Guo, J. G. Yu, J. R. Ran, B. H. Zhang, H. J. Yan, J. R. Gong, J. Am. Chem. Soc., 2011, 133, 10878-10884.
10. [10] Y. Peng, L. Shang, Y. T. Cao, Q. Wang, Y. F. Zhao, C. Zhou, T. Bian, L. Z. Wu, C. H. Tung, T. R. Zhang, Appl. Surf. Sci., 2015, 358, 485-490.
11. [11] S. Ma, J. Xie, J. Q. Wen, K. L. He, X. Li, W. Liu, X. C. Zhang, Appl. Surf. Sci., 2017, 391, 580-591.
12. [12] G. Hitoki, A. Ishikawa, T. Takata, J. N. Kondo, M. Hara, K. Domen, Chem. Lett., 2002, 31, 736-737.
13. [13] L. J. Shen, R. W. Liang, L. Wu, Chin. J. Catal., 2015, 36, 2071-2088.
14. [14] M. S. Akple, J. Low, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, J. Zhang, Appl. Surf. Sci., 2015, 358, 196-203.
15. [15] Y. J. Cui, Y. X. Wang, H. Wang, F. Cao, F. Y. Chen, Chin. J. Catal., 2016,37, 1899-1906.
16. [16] 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.
17. [17] Z. Z. Lin, L. H. Lin, X. C. Wang, Chin. J. Catal., 2015, 36, 2089-2094.
18. [18] J. Q. Wen, J. Xie, X. B. Chen, X. Li, Appl. Surf. Sci., 2017, 391, 72-123.
19. [19] J. F. Zhang, S. Wageh, A. Al-Ghamdi, J. G. Yu, Appl. Catal. B, 2016, 192, 101-107.
20. [20] Q. Li, X. Li, S. Wageh, A. A. Al-Ghamdi, J. Yu, Adv. Energy Mater., 2015, 5, 1500010.
21. [21] H. Du, Y. N. Liu, C. C. Shen, A. W. Xu, Chin. J. Catal., 2017, 38, 1295-1306.
22. [22] Q. J. Xiang, B. Cheng, J. G. Yu, Appl. Catal. B, 2013, 138, 299-303.
23. [23] J. G. Yu, Y. F. Yu, P. Zhou, W. Xiao, B. Cheng, Appl. Catal. B, 2014, 156, 184-191.
24. [24] D. Zhao, Q. Wu, C. F. Yang, R. T. Koodali, Appl. Surf. Sci., 2015, 356, 308-316.
25. [25] X. Li, J. G. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-2636.
26. [26] H. G. Yu, F. Y. Chen, F. Chen, X. F. Wang, Appl. Surf. Sci., 2015, 358, 385-392.
27. [27] J. J. Zhou, R. Wang, X. L. Liu, F. M. Peng, C. H. Li, F. Teng, Y. P. Yuan, Appl. Surf. Sci., 2015, 346, 278-283.
28. [28] Y. J. Cui, Chin. J. Catal., 2015, 36, 372-379.
29. [29] J. Z. Su, T. Zhang, L. Wang, J. W. Shi, Y. B. Chen, Chin. J. Catal., 2017, 38, 489-497.
30. [30] L. J. Zhang, S. Li, B. K. Liu, D. J. Wang, T. F. Xie, ACS Catal., 2014, 4, 3724-3729.
31. [31] L. Zou, H. R. Wang, X. Wang, ACS Sustain. Chem. Eng., 2016, 5, 303-309.
32. [32] X. L. Yin, J. Liu, W. J. Jiang, X. Zhang, J. S. Hu, L. J. Wan, Chem. Commun., 2015, 51, 13842-13845.
33. [33] Q. Li, H. Meng, P. Zhou, Y. Q. Zheng, J. Wang, J. G. Yu, J. R. Gong, ACS Catal., 2013, 3, 882-889.
34. [34] J. Zhang, F. Huang, Appl. Surf. Sci., 2015, 358, 287-295.
35. [35] Q. L. Xu, B. Cheng, J. Yu, G. Liu, Carbon, 2017, 118, 241-249.
36. [36] X. Li, R. C. Shen, S. Ma, X. B. Chen, J. Xie, Appl. Surf. Sci., 2018, 430, 53-107.
37. [37] X. Li, J. G. Yu, S. Wageh, A. A. Al-Ghamdi, J. Xie, Small, 2016, 12, 6640-6696.
38. [38] Y. Xu, R. Xu, Appl. Surf. Sci., 2015, 351, 779-793.
39. [39] T. M. Di, B. C. Zhu, J. Zhang, B. Cheng, J. G. Yu, Appl. Surf. Sci., 2016, 389, 775-782.
40. [40] S. W. Cao, Y. P. Yuan, J. Fang, M. M. Shahjamali, F. Y. C. Boey, J. Barber, S. C. Joachim Loo, C. Xue, Int. J. Hydrogen Energy, 2013, 38, 1258-1266.
41. [41] J. L. Yuan, J. Q. Wen, Q. Z. Gao, S. C. Chen, J. M. Li, X. Li, Y. P. Fang, Dalton Trans., 2015, 44, 1680-1689.
42. [42] J. Zhang, S. Z. Qiao, L. Qi, J. G. Yu, Phys. Chem. Chem. Phys., 2013, 15, 12088-12094.
43. [43] J. Jin, J. G. Yu, D. P. Guo, C. Cui, W. Ho, Small, 2015, 11, 5262-5271.
44. [44] Y. Xu, W. W. Zhao, R. Xu, Y. M. Shi, B. Zhang, Chem. Commun., 2013, 49, 9803-9805.
45. [45] S. Iqbal, Z. W. Pan, K. B. Zhou, Nanoscale, 2017, 9, 6638-6642.
46. [46] H. J. Yan, J. H. Yang, G. J. Ma, G. P. Wu, X. Zong, Z. B. Lei, J. X. Shi, C. Li, J. Catal., 2009, 266, 165-168.
47. [47] R. B. Wei, P. Y. Kuang, H. Cheng, Y. B. Chen, J. Y. Long, M. Y. Zhang, Z. Q. Liu, ACS Sustain. Chem. Eng., 2017, 5, 4249-4257.
48. [48] P. Y. Kuang, P. X. Zheng, Z. Q. Liu, J. L. Lei, H. Wu, N. Li, T. Y. Ma, Small, 2016, 12, 6735-6744.
49. [49] K. Chang, M. Li, T. Wang, S. Ouyang, P. Li, L. Liu, J. Ye, Adv. Energy Mater., 2015, 5, 1402279.
50. [50] Q. J. Xiang, F. Y. Cheng, D. Lang, ChemSusChem, 2016, 9, 996-1002.
51. [51] X. Zong, J. F. Han, G. J. Ma, H. J. Yan, G. P. Wu, C. Li, J. Phys. Chem. C, 2011, 115, 12202-12208.
52. [52] W. Zhang, Y. B. Wang, Z. Wang, Z. Y. Zhong, R. Xu, Chem. Commun., 2010, 46, 7631-7633.
53. [53] Y. X. Pan, T. H. Zhou, J. Y. Han, J. D. Hong, Y. B. Wang, W. Zhang, R. Xu, Catal. Sci. Technol., 2016, 6, 2206-2213.
54. [54] F. Y. Cheng, Q. J. Xiang, RSC Adv., 2016, 6, 76269-76272.
55. [55] H. G. Yu, X. Huang, P. Wang, J. G. Yu, J. Phys. Chem. C, 2016, 120, 3722-3730.
56. [56] D. Lang, F. Y. Cheng, Q. J. Xiang, Catal. Sci. Technol., 2016, 6, 6207-6216.
57. [57] Y. P. Yuan, S. W. Cao, L. S. Yin, L. Xu, C. Xue, Int. J. Hydrogen Energy, 2013, 38, 7218-7223.
58. [58] L. S. Yin, Y. P. Yuan, S. W. Cao, Z. Zhang, C. Xue, RSC Adv., 2014, 4, 6127.
59. [59] F. Chen, H. Yang, X. F. Wang, H. G. Yu, Chin. J. Catal., 2017, 38, 296-304.
60. [60] H. Pang, C. Z. Wei, X. X. Li, G. C. Li, Y. H. Ma, S. J. Li, J. Chen, J. S. Zhang, Sci. Rep., 2014, 4, 3577.
61. [61] J. Q. Wen, J. Xie, Z. H. Yang, R. C. Shen, H. Y. Li, X. Y. Luo, X. B. Chen, X. Li, ACS Sustain. Chem. Eng., 2017, 5, 2224-2236.
62. [62] J. Q. Wen, X. Li, H. Q. Li, S. Ma, K. L. He, Y. Xu, Y. H. Fang, W. Liu, Q. Z. Gao, Appl. Surf. Sci., 2015, 358, 204-212.
63. [63] G. C. Bi, J. Q. Wen, X. Li, W. Liu, J. Xie, Y. P. Fang, W. W. Zhang, RSC Adv., 2016, 6, 31497-31506.
64. [64] J. Wen, X. Li, H. Li, S. Ma, K. He, Y. Xu, Y. Fang, W. Liu, Q. Gao, Appl. Surf. Sci., 2015, 358, 204-212.
65. [65] M. Zhukovskyi, P. Tongying, H. Yashan, Y. X. Wang, M. Kuno, ACS Catal., 2015, 5, 6615-6623.
66. [66] J. He, L. Chen, Z. Q. Yi, C. T. Au, S. F. Yin, Ind. Eng. Chem. Res., 2016, 55, 8327-8333.
67. [67] N. Zhang, Y. H. Zhang, X. Y. Pan, X. Z. Fu, S. Q. Liu, Y. J. Xu, J. Phys. Chem. C, 2011, 115, 23501-23511.
68. [68] X. L. Yin, L. L. Li, W. J. Jiang, Y. Zhang, X. Zhang, L. J. Wan, J. S. Hu, ACS Appl. Mater. Interfaces, 2016, 8, 15258-15266.
69. [69] S. Zou, Z. H. Fu, C. Xiang, W. F. Wu, S. P. Tang, Y. C. Liu, D. L. Yin, Chin. J. Catal., 2015, 36, 1077-1085.
70. [70] 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.
71. [71] K. L. He, J. Xie, Z. H. Yang, R. C. Shen, Y. P. Fang, S. Ma, X. B. Chen, X. Li, Catal. Sci. Technol., 2017, 7, 1193-1202.
72. [72] 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.

扫一扫看文章

计量

PDF下载量: 3
文章访问数: 1220
HTML全文浏览量: 118

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

利用地球上丰富的炭黑和NiS₂双助催化剂修饰提高CdS纳米片体系的可见光产氢活性

English

Improved visible-light photocatalytic H₂ generation over CdS nanosheets decorated by NiS₂ and metallic carbon black as dual earth-abundant cocatalysts

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

利用地球上丰富的炭黑和NiS2双助催化剂修饰提高CdS纳米片体系的可见光产氢活性

English

Improved visible-light photocatalytic H2 generation over CdS nanosheets decorated by NiS2 and metallic carbon black as dual earth-abundant cocatalysts

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

利用地球上丰富的炭黑和NiS₂双助催化剂修饰提高CdS纳米片体系的可见光产氢活性

Improved visible-light photocatalytic H₂ generation over CdS nanosheets decorated by NiS₂ and metallic carbon black as dual earth-abundant cocatalysts

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs