三元NiS/CQDs/ZnIn2S4光催化体系的合理设计及其产氢性能

doi:10.1016/S1872-2067(18)63159-6

催化学报 ›› 2019, Vol. 40 ›› Issue (3): 335-342.DOI: 10.1016/S1872-2067(18)63159-6

三元NiS/CQDs/ZnIn₂S₄光催化体系的合理设计及其产氢性能

王冰清, 丁瑶, 邓子榕, 李朝晖

福州大学化学学院, 能源与环境光催化国家重点实验室, 催化研究所, 福建福州 350116

收稿日期:2018-08-11 修回日期:2018-09-06 出版日期:2019-03-18 发布日期:2019-02-22
通讯作者: 李朝晖
基金资助:
国家重点基础研究发展计划（973计划，2014CB239303）；国家自然科学基金（21872031，U1705251）；闽江学者奖励计划.

Rational design of ternary NiS/CQDs/ZnIn₂S₄ nanocomposites as efficient noble-metal-free photocatalyst for hydrogen evolution under visible light

Bingqing Wang, Yao Ding, Zirong Deng, Zhaohui Li

Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116, Fujian, China

Received:2018-08-11 Revised:2018-09-06 Online:2019-03-18 Published:2019-02-22
Supported by:
This work was supported by the National Key Basic Research Program of China (973 Program, 2014CB239303), the National Natural Science Foundation of China (21872031, U1705251) and the Award Program for Minjiang Scholar Professorship.

摘要/Abstract

摘要：

氢气是一种清洁能源，利用半导体光催化技术将水转化成氢气是解决全球能源危机和环境污染问题的有效途径之一.开发高效的光催化体系以实现水分解产氢是目前能源领域中的一个研究热点.六方相的ZnIn₂S₄是一种三元金属硫化物，因其具有能够吸收可见光的窄带隙（约2.4 eV）和良好的化学稳定性，在光催化产氢方面得到了较好应用.在半导体光催化产氢体系中，往往需要加入助催化剂来提供产氢活性位并降低产氢反应的过电位，这种半导体/助催化剂体系中光催化产氢效率不仅取决于助催化剂的组成和结构，还受二者界面之间光生电子传输效率的影响.我们课题组前期研究发现，NiS作为一种廉价的非贵金属助催化剂能够提高ZnIn₂S₄在可见光下的光催化产氢活性.考虑到碳量子点（CQDs）是一种具有良好导电能力的纳米材料，并已被负载于半导体光催化剂上来促进半导体表面光生电子的传输，本文将CQDs作为光生电子传输的"桥梁"引入到NiS/ZnIn₂S₄体系中，用来促进光生电子从ZnIn₂S₄到NiS的定向传输，从而提高其光催化产氢效率.
实验首先合成NiS/CQDs复合材料，然后在其存在下进行ZnIn₂S₄的自组装制得NiS/CQDs/ZnIn₂S₄.利用X射线粉末衍射、扫描电镜、透射电镜、傅立叶红外光谱、X射线光电子能谱和紫外-可见漫反射光谱对催化剂的组成、结构及光学性质进行了详细表征，考察了其在可见光下以三乙醇胺（TEOA）为牺牲剂时的光催化分解水产氢性能.结果表明，含有CQDs的NiS/CQDs/ZnIn₂S₄光催化剂在光照5 h后的产氢总量达到142 μmol，分别为相同条件下ZnIn₂S₄和NiS/ZnIn₂S₄产氢总量的5.5和1.6倍.相比于通过将NiS沉积在预先合成的CQDs/ZnIn₂S₄上所获得的CQDs/NiS/ZnIn₂S₄光催化剂，NiS/CQDs/ZnIn₂S₄显示出更优越的光催化产氢活性.TEM观测发现，在NiS/CQDs/ZnIn₂S₄中CQDs与ZnIn₂S₄和NiS均有明显的接触，表明CQDs作为"桥梁"连接了ZnIn₂S₄和NiS，这种结构有利于光生电子由ZnIn₂S₄至NiS定向传输.而CQDs/NiS/ZnIn₂S₄光催化剂中的CQDs和NiS没有直接接触.电化学交流阻抗实验发现，NiS/CQDs/ZnIn₂S₄中电子的传导能力比CQDs/NiS/ZnIn₂S₄中的强，说明相比于CQDs/NiS/ZnIn₂S₄，在NiS/CQDs/ZnIn₂S₄中的CQDs更有效地促进了光生电子由ZnIn₂S₄至NiS定向传输.该研究提供了一种以CQDs作为促进光生电子定向传输的"桥梁"来构筑高效产氢光催化体系的方法.

关键词: 光催化, 制氢, 硫化镍, 碳量子点, ZnIn₂S₄

Abstract:

The NiS/CQDs nanocomposite (CQDs represents carbon quantum dots), with a mass ratio of NiS/CQDs to be 1.19:1 based on the ICP result, was obtained via a facile hydrothermal method from a mixture of CQDs, Ni(OAc)₂ and Na₂S. The self-assembly of ZnIn₂S₄ microspheres on the surface of NiS/CQDs was realized under microwave conditions to obtain a ternary NiS/CQDs/ZnIn₂S₄ nanocomposite. The as-obtained NiS/CQDs/ZnIn₂S₄ nanocomposite was fully characterized, and its photocatalytic hydrogen evolution under visible light irradiation was investigated. The ternary NiS/CQDs/ZnIn₂S₄ nanocomposite showed superior photocatalytic activity for hydrogen evolution than ternary CQDs/NiS/ZnIn₂S₄, which was obtained by deposition of NiS in the preformed CQDs/ZnIn₂S₄. The superior photocatalytic performance of ternary NiS/CQDs/ZnIn₂S₄ is ascribed to the introduction of CQDs, which act as a bridge to promote the vectorial transfer of photo-generated electrons from ZnIn₂S₄ to NiS. This result suggests that the rational design and fabrication of ternary CQDs-based systems are important for the efficient photocatalytic hydrogen evolution. This study provides a strategy for developing highly efficient noble-metal-free photocatalysts for hydrogen evolution using CQDs as a bridge to promote the charge transfer in the nanocomposite.

Key words: Photocatalysis, Hydrogen evolution, NiS, Carbon quantum dots, ZnIn₂S₄

王冰清, 丁瑶, 邓子榕, 李朝晖. 三元NiS/CQDs/ZnIn₂S₄光催化体系的合理设计及其产氢性能[J]. 催化学报, 2019, 40(3): 335-342.

Bingqing Wang, Yao Ding, Zirong Deng, Zhaohui Li. Rational design of ternary NiS/CQDs/ZnIn₂S₄ nanocomposites as efficient noble-metal-free photocatalyst for hydrogen evolution under visible light[J]. Chinese Journal of Catalysis, 2019, 40(3): 335-342.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(18)63159-6

https://www.cjcatal.com/CN/Y2019/V40/I3/335

参考文献

[1] Q. Xiang, J. Yu, M. Jaroniec, Chem. Soc. Rev., 2012, 41, 782-796.
[2] A. Kudo, Y. Miseki, Chem. Soc. Rev., 2009, 38, 253-278.
[3] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[4] L. Jing, W. Zhou, G. Tian, H. Fu, Chem. Soc. Rev., 2013, 42, 9509-9549.
[5] G. Zhang, G. Liu, L. Wang, J. T. Irvine, Chem. Soc. Rev., 2016, 45, 5951-5984.
[6] H. Li, W. Tu, Y. Zhou, Z. Zou, Adv. Sci., 2016, 3, 1500389.
[7] X. Chen, S. Shen, L. Guo, S. Mao, Chem. Rev., 2010, 110, 6503-6570.
[8] Y. Moriya, T. Takata, K. Domen, Coord. Chem. Rev., 2013, 257, 1957-1969.
[9] Y. Wang, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2012, 51, 68-89.
[10] J. Zhang, L. Qi, J. Ran, J. Yu, S. Qiao, Adv. Energy Mater., 2014, 4, 1301925.
[11] J. Yuan, J. Wen, Y. Zhong, X. Li, Y. Fang, S. Zhang, W. Liu, J. Mater. Chem. A, 2015, 3, 18244-18255.
[12] Y. Xia, Q. Li, K. Lv, D. Tang, M. Li, Appl. Catal. B, 2017, 206, 344-352.
[13] Z. Lei, W. You, M. Liu, G. Zhou, T. Takata, M. Hara, K. Domen, C. Li, Chem. Commun., 2003, 9, 2142-2143.
[14] L. Xu, X. Deng, Z. Li, Appl. Catal. B, 2018, 234, 50-55.
[15] L. Shang, C. Zhou, T. Bian, H. Yu, L. Z. Wu, C. H. Tung, T. Zhang, J. Mater. Chem. A, 2013, 1, 4552-4558.
[16] B. Wang, Z. Deng, X. Fu, C. Xu, Z. Li, Appl. Catal. B, 2018, 237, 970-975.
[17] L. Ye, Z. Li, ChemCatChem, 2014, 6, 2540-2543.
[18] Y. Ma, X. Wang, Y. Jia, X. Chen, H. Han, C. Li, Chem. Rev., 2014, 114, 9987-10043.
[19] S. Chen, T. Takata, K. Domen, Nat. Rev. Mater., 2017, 2, 17050.
[20] Y. Hou, Y. Zhu, Y. Xu, X. Wang, Appl. Catal. B, 2014, 156-157, 122-127.
[21] T. Su, Q. Shao, Z. Qin, Z. Guo, Z. Wu, ACS Catal., 2018, 8, 2253-2276.
[22] Z. Wang, J. Peng, X. Feng, Z. Ding, Z. Li, Catal. Sci. Technol., 2017, 7, 2524-2530.
[23] J. Ran, J. Zhang, J. Yu, M. Jaroniec, S. Z. Qiao, Chem. Soc. Rev., 2014, 43, 7787-7812.
[24] W. Zhang, Y. Wang, Z. Wang, Z. Zhong, R. Xu, Chem. Commun., 2010, 46, 7631-7633.
[25] L. Wei, Y. Chen, J. Zhao, Z. Li, Beilstein J. Nanotechnol., 2013, 4, 949-955.
[26] K. Chang, Z. Mei, T. Wang, Q. Kang, S. Ouyang, J. Ye, ACS Nano, 2014, 8, 7078-7087.
[27] Y. Yuan, J. Tu, Z. Ye, D. Chen, B. Hu, Y. Huang, T. Chen, D. Cao, Z. Yu, Z. Zou, Appl. Catal. B, 2016, 188, 13-22.
[28] S. Y. Lim, W. Shen, Z. Gao, Chem. Soc. Rev., 2015, 44, 362-381.
[29] H. Yu, R. Shi, Y. Zhao, G. I. Waterhouse, L. Wu, C. Tung, T. Zhang, Adv. Mater., 2016, 28, 9454-9477.
[30] J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S. T. Lee, J. Zhong, Z. Kang, Science, 2015, 347, 970-974.
[31] S. T. Yang, L. Cao, P. Luo, F. Lu, X. Wang, H. Wang, M. J. Meziani, Y. Liu, G. Qi, Y. Sun, J. Am. Chem. Soc., 2009, 131, 11308-11309.
[32] S. Zhu, Q. Meng, L. Wang, J. Zhang, Y. Song, H. Jin, K. Zhang, H. Sun, H. Wang, B. Yang, Angew. Chem., Int. Ed., 2013, 52, 3953-3957.
[33] Y. Wang, X. Liu, J. Liu, B. Han, X. Hu, F. Yang, Z. Xu, Y. Li, S. Jia, Z. Li, Y. Zhao, Angew. Chem. Int. Ed., 2018, 57, 5765-5771.
[34] H. Zhang, H. Huang, H. Ming, H. Li, L. Zhang, Y. Liu, Z. Kang, J. Mater. Chem., 2012, 22, 10501-10506.
[35] H. Li, X. Zhang, D. R. MacFarlane, Adv. Energy Mater., 2015, 5, 1401077.
[36] C. Guo, D. Zhao, Q. Zhao, P. Wang, X. Lu, Chem. Commun., 2014, 50, 7318-7321.
[37] X. Liu, X. Liang, P. Wang, B. Huang, X. Qi, X. Zhang, Y. Dai, Appl. Catal. B, 2017, 203, 282-288.
[38] B. C. M. Martindale, G. A. M. Hutton, C. A. Caputo, E. Reisner, J. Am. Chem. Soc., 2015, 137, 6018-6025.
[39] L. Ye, Z. Li, Appl. Catal. B, 2014, 160-161, 552-557.
[40] Y. Gao, H. Lin, S. Zhang, Z. Li, RSC Adv., 2016, 6, 6072-6076.
[41] Y. Xia, Q. Li, K. Lv, M. Li, Appl. Surf. Sci., 2017, 398, 81-88.
[42] H. Yu, Y. Zhao, C. Zhou, L. Shang, Y. Peng, Y. Cao, L. Wu, C. Tung, T. Zhang, J. Mater. Chem. A, 2014, 2, 3344-3351.
[43] K. He, J. Xie, M. Li, X. Li, Appl. Surf. Sci., 2018, 430, 208-217.
[44] F. Chen, H. Yang, X. Wang, H. Yu, Chin. J. Catal., 2017, 38, 296-304.
[45] W. Yang, B. Liu, T. Fang, W. A. Jennifer, L. Christophe, Z. Li, X. Zhang, X. Jiang, Nanoscale, 2016, 8, 18197-18203.
[46] B. Chai, C. Liu, C. Wang, J. Yan, Z. Ren, Chin. J. Catal., 2017, 38, 2067-2075.
[47] Y. Chen, S. Hu, W. Liu, X. Chen, L. Wu, X. Wang, P. Liu, Z. Li, Dalton Trans., 2011, 40, 2607-2613.
[48] L. Ye, J. Fu, Z. Xu, R. Yuan, Z. Li, ACS Appl. Mater. Interfaces, 2014, 6, 3483-3490.
[49] X. Han, Y. Han, H. Huang, H. Zhang, X. Zhang, R. Liu, Y. Liu, Z. Kang, Dalton Trans., 2013, 42, 103807-10383.
[50] D. Jiang, L. Zhu, R. M. Irfan, L. Zhang, P. Du, Chin. J. Catal., 2017, 38, 2102-2109.
[51] M. Sun, X. Zhao, Q. Zeng, T. Yan, P. Ji, T. Wu, D. Wei, B. Du, Appl. Surf. Sci., 2017, 407, 328-336.
[52] Q. Li, C. Cui, H. Meng, J. Yu, Chem. Asian J., 2014, 9, 1766-1770.
[53] S. Ma, X. Xu, J. Xie, X. Li, Chin. J. Catal., 2017, 38, 1970-1980.

三元NiS/CQDs/ZnIn₂S₄光催化体系的合理设计及其产氢性能

Rational design of ternary NiS/CQDs/ZnIn₂S₄ nanocomposites as efficient noble-metal-free photocatalyst for hydrogen evolution under visible light

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[5]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[6]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[7]	乔蔚, 于立策, 常进法, 杨甫林, 冯立纲. MoSe₂纳米片耦合Pt纳米颗粒用于高效双功能催化甲醇辅助水电解制氢[J]. 催化学报, 2023, 51(8): 113-123.
[8]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[9]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[10]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[11]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[12]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[13]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.
[14]	袁鑫, 范海滨, 刘杰, 覃龙州, 王剑, 段秀, 邱江凯, 郭凯. 连续流技术在光氧化还原催化转化的最新进展[J]. 催化学报, 2023, 50(7): 175-194.
[15]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.