多组分纳米纤维体系中载流子动力学的有效级联调制及其高效光催化产氢性能研究

doi:10.3866/PKU.WHXB202207045

物理化学学报 >> 2023, Vol. 39 >> Issue (4): 2207045.doi: 10.3866/PKU.WHXB202207045

所属专题：庆祝谢有畅教授九十华诞专刊

多组分纳米纤维体系中载流子动力学的有效级联调制及其高效光催化产氢性能研究

吕娜, 荆雪东, 许瑶, 鲁巍, 刘奎朝, 张振翼()

大连民族大学国家民委新能源与稀土资源利用重点实验室, 辽宁省光敏材料与器件重点实验室, 物理与材料工程学院, 辽宁大连 116600

收稿日期:2022-07-22 录用日期:2022-08-30 发布日期:2022-08-31
通讯作者: 张振翼 E-mail:zhangzy@dlnu.edu.cn
作者简介:第一联系人：
^†These authors contributed equally to this work.
基金资助:
国家自然科学基金(62005036);国家自然科学基金(12074055);国家自然科学基金(11904046);辽宁省优秀青年科学基金(2022-YQ-13);辽宁省“百千万人才工程”, 辽宁省自然科学基金(2020-MZLH-15);大连市青年科技之星(2020RQ131)

Effective Cascade Modulation of Charge-Carrier Kinetics in the Well-Designed Multi-Component Nanofiber System for Highly-Efficient Photocatalytic Hydrogen Generation

Na Lu, Xuedong Jing, Yao Xu, Wei Lu, Kuichao Liu, Zhenyi Zhang()

Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission; Key Laboratory of Photosensitive Materials and Devices of Liaoning Province, School of Physics and Materials Engineering, Dalian Minzu University, Dalian 116600, Liaoning Province, China

Received:2022-07-22 Accepted:2022-08-30 Published:2022-08-31
Contact: Zhenyi Zhang E-mail:zhangzy@dlnu.edu.cn
Supported by:
the National Natural Science Foundation of China(62005036);the National Natural Science Foundation of China(12074055);the National Natural Science Foundation of China(11904046);Natural Science Foundation of Liaoning Province for Excellent Young Scholars, China(2022-YQ-13);Liaoning BaiQianWan Talents Program, China, Natural Science Foundation of Liaoning Province, China(2020-MZLH-15);Program for Dalian Excellent Talents, China(2020RQ131)

摘要/Abstract

摘要：

利用半导体作为催化剂，将水光催化还原为H₂，为缓解全球能源危机以及环境污染问题提供了一种经济环保的途径。优化调控载流子动力学行为对提高半导体光催化分解水还原为绿色燃料-H₂的活性具有十分重要的意义。目前，基于半导体异质结效应或局域表面等离激元共振的敏化过程来设计和调控半导体基异质结构体系已成为调控载流子动力学行为的一种经典策略。然而，通过精细设计异质结构，合理耦合上述敏化过程，实现载流子动力学的级联调制，从而获得高效的光催化产H₂活性仍然任重道远。在本文中，我们通过原位氧化(g-C₃N₄的剥离和Ag₂S)和还原(Ag)反应，将等离激元Ag纳米颗粒(NPs)和两种不同的半导体Ag₂S NPs和g-C₃N₄纳米片(NSs)组装在电纺TiO₂纳米纤维(NFs)中，形成了一种新型四元异质组分纳米纤维(HNFs)体系。结合时间分辨光致发光光谱，3D时域有限差分模拟以及对照实验，我们证明了等离激元Ag NPs和g-C₃N₄ NSs由于吸收光谱重叠可以诱导从Ag NPs到与其相邻的g-C₃N₄ NSs上的等离激元共振能量转移，从而促进上述四元HNFs体系中g-C₃N₄上光生载流子的产生。同时，由Ag NPs产生的等离激元热电子能够进一步转移到与其相接触的TiO₂、g-C₃N₄、以及Ag₂S组分上，促进体系中光生载流子的产生和分离。而且，g-C₃N₄/TiO₂异质界面处的能带结构属于“II型”异质结，而TiO₂/Ag₂S异质界面处的能带结构属于“I型”异质结。这样可以在g-C₃N₄/TiO₂/Ag₂S异质界面构建连续的“能带阶梯”，使光生电子从g-C₃N₄跨越TiO₂转移到Ag₂S上，从而促进光生电荷-载流子的分离和迁移。因此，将等离激元共振能量转移，热电子转移过程和连续的“能带阶梯”诱导的载流子分离过程合理地整合在所制备的四元Ag/Ag₂S/g-C₃N₄/TiO₂ HNFs中，从而实现了光生载流子产生、分离和迁移的有效级联调制。因此，在模拟太阳光的照射下，最优的Ag/Ag₂S/g-C₃N₄/TiO₂ HNFs光催化产H₂速率与等比例随机机械混合的TiO₂ NFs、g-C₃N₄ NSs、Ag NPs和Ag₂S NPs光催化产H₂速率相比高~9倍。这种新颖的载流子动力学级联调制为开发高光活性半导体基异质结构体系，实现太阳能-燃料转换提供了一条崭新的途径。

关键词: 级联调制, 载流子动力学, Ag/Ag₂S/g-C₃N₄/TiO₂异质结复合纳米纤维, 宽光谱响应, 光催化产氢

Abstract:

The photocatalytic reduction of water to hydrogen (H₂) over semiconductors potentially offers an economic way to alleviate the global energy crisis and environmental pollution. Optimal modulation of charge-carrier kinetics is of great importance for enhancing the photocatalytic activity of semiconductors for reducing water to green H₂. The design and manufacture of semiconductor-based heterostructure systems have emerged as promising tactics for modulating charge-carrier kinetics based on sensitization either via the semiconductor heterojunction effect or localized surface plasmon resonance. However, the cascade modulation of charge-carrier kinetics is still difficult to achieve through rationally coupling the abovementioned sensitization processes in well-designed heterostructures for highly-efficient photocatalytic H₂ generation. In this study, we developed a novel quaternary hetero-component nanofibers (HNFs) system by assembling plasmonic Ag nanoparticles (NPs) and two different semiconductors of Ag₂S NPs and g-C₃N₄ nanosheets (NSs) into the electrospun TiO₂ nanofibers (NFs) via in situ oxidation (for g-C₃N₄ exfoliation and Ag₂S) and reduction (for Ag) reactions. By combining time-resolved photoluminescence spectroscopy, three-dimensional finite-difference-time-domain simulation, and control experiments, we found that the overlapping absorption peak of plasmonic Ag NPs and g-C₃N₄ NSs could induce plasmonic resonant energy transfer from the Ag NPs to the neighboring g-C₃N₄, thereby improving the generation of photoinduced charge carriers of g-C₃N₄ in the quaternary HNFs system. Simultaneously, plasmonic hot electrons could be generated on the Ag NPs and transferred to the near-by hetero-components of TiO₂, g-C₃N₄, and Ag₂S, to boost the generation and separation of photoinduced charge carriers in the system. Furthermore, the energy band structure at the g-C₃N₄/TiO₂ hetero-interface belongs to the "type II" heterojunction, while the energy band structure at the TiO₂/Ag₂S hetero-interface can be classified as a "type I" heterojunction. This way, the successive "energy band step" could be constructed at the g-C₃N₄/TiO₂/Ag₂S hetero-interface, resulting in improved separation and migration of photoinduced charge carriers through the transfer of photoinduced electrons from g-C₃N₄ to Ag₂S across TiO₂. Thus, the plasmonic resonant energy transfer, hot electron transfer, and successive energy-band-step-induced charge separation processes were integrated into the as-synthesized quaternary Ag/Ag₂S/g-C₃N₄/TiO₂ HNFs system, thereby achieving the effective cascade modulation of the generation, separation, and migration of photoinduced charge carriers. As such, the photocatalytic H₂-generation rate of the optimal Ag/Ag₂S/g-C₃N₄/TiO₂ HNFs system was higher than that of the mechanically mixed TiO₂ NFs, g-C₃N₄ NSs, Ag NPs, and Ag₂S NPs, with the same amounts as the optimal Ag/Ag₂S/g-C₃N₄/TiO₂ HNFs photocatalyst, by approximately 9-fold under simulated sunlight irradiation. This interesting cascade modulation of charge-carrier kinetics might open new avenues for the development of highly active semiconductor-based heterostructure system for solar-to-fuels conversion.

Key words: Cascade modulation, Charge-carrier kinetics, Ag/Ag₂S/g-C₃N₄/TiO₂ hetero-component nanofibers, Broad spectral response, Photocatalytic H₂ generation

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吕娜, 荆雪东, 许瑶, 鲁巍, 刘奎朝, 张振翼. 多组分纳米纤维体系中载流子动力学的有效级联调制及其高效光催化产氢性能研究[J]. 物理化学学报, 2023, 39(4), 2207045. doi: 10.3866/PKU.WHXB202207045

Na Lu, Xuedong Jing, Yao Xu, Wei Lu, Kuichao Liu, Zhenyi Zhang. Effective Cascade Modulation of Charge-Carrier Kinetics in the Well-Designed Multi-Component Nanofiber System for Highly-Efficient Photocatalytic Hydrogen Generation[J]. Acta Phys. -Chim. Sin. 2023, 39(4), 2207045. doi: 10.3866/PKU.WHXB202207045

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202207045

https://www.whxb.pku.edu.cn/CN/Y2023/V39/I4/2207045

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参考文献 47

1	Dong, X. B.; Wang, S. X.; Wu, Q.; Liu, K. Y.; Kong, F. G.; Liu, J. X. J. Alloy. Compd. 2021, 875, 160032. doi: 10.1016/j.jallcom.2021.160032
2	Shan, Z. C.; Clayton, D.; Pan, S. L.; Archana, P. S.; Gupta, A. J. Phys. Chem. B 2014, 118, 14037. doi: 10.1021/jp504346k
3	Kisch, H. Angew. Chem. Int. Ed. 2013, 52, 812. doi: 10.1002/anie.201201200
4	Yu, W. L.; Yin, J.; Li, Y.; Lai, B.; Jiang, T.; Li, Y. Y.; Liu, H. W.; Liu, J. L.; Zhao, C.; Singh, S. C.; et al ACS Appl. Energy Mater. 2019, 2, 2751. doi: 10.1021/acsaem.9b00091
5	Liu, J. Y.; Chen, G.; Sun, J. X. ACS Appl. Nano Mater. 2020, 3, 11017. doi: 10.1021/acsanm.0c02240
6	An, S. F.; Zhang, G. H.; Li, K, Y.; Huang, Z. N.; Wang, X.; Guo, Y. K.; Hou, J. G.; Song, C. S.; Guo, X. W. Adv. Mater. 2021, 33, 2104361. doi: 10.1002/adma.202104361
7	Shuang, S.; Lv, R. T.; Cui, X. Y.; Xie, Z.; Zheng, J.; Zhang, Z. J. RSC Adv. 2018, 8, 5784. doi: 10.1039/c7ra13501g
8	Xue, B.; Jiang, H. Y.; Sun, T.; Mao, F.; Ma, C. C.; Wu, J. K. J. Photochem. Photobiol. A 2018, 353, 557. doi: 10.1016/j.jphotochem.2017.12.021
9	Wei, X. B.; Shao, C. L.; Li, X. H.; Lu, N.; Wang, K. X.; Zhang, Z. Y.; Liu, Y. C. Nanoscale 2016, 8, 11034. doi: 10.1039/c6nr01491g
10	Zhang, Z. Y.; Huang, Y. Z.; Liu, K. C.; Guo, L. J.; Yuan, Q.; Dong, B. Adv. Mater. 2015, 27, 5906. doi: 10.1002/adma.201502203
11	Hou, W. B.; Cronin, S. B. Adv. Funct. Mater. 2012, 23, 1612. doi: 10.1002/adfm.201202148
12	Wang, J.; Sun, Z. G.; Jiang, X. Y.; Yuan, Q.; Dong, D. P.; Zhang, P.; Zhang, Z. Y. Dalton Trans. 2021, 50, 6152. doi: 10.1039/d1dt00743b
13	Yan, J. Q.; Li, P.; Bian, H.; Wu, H.; Liu, S. Z. Sustain. Energ. Fules 2017, 1, 95. doi: 10.1039/c6se00048g
14	Wang, Y. J.; Wu, Q. H.; Li, Y.; Liu, L. M.; Geng, Z. L.; Li, Y. M.; Chen, J.; Bai, W. K.; Jiang, G. Y.; Zhao, Z. J. Mater. Sci. 2018, 53, 11015. doi: 10.1007/s10853-018-2368-3
15	Ong, W. L.; Lim, Y. F.; Ong, J. L. T.; Ho, G. W. J. Mater. Chem. A 2015, 3, 6509. doi: 10.1039/c4ta06674j
16	Wang, Y. Q.; Shen, S. H. Acta Phys. -Chim. Sin. 2020, 36, 1905080.
	王亦清, 沈少华物理化学学报, 2020, 36, 1905080. doi: 10.3866/PKU.WHXB201905080
17	Cao, S. W.; Low, J. X.; Yu, J. G.; Jaroniec, M. Adv. Mater. 2015, 27, 2150. doi: 10.1002/adma.201500033
18	Cao, S. W.; Yu, J. G. J. Phys. Chem. Lett. 2014, 5, 2101. doi: 10.1021/jz500546b
19	Gao, S.; Zhang, Z. Y.; Liu, K. C.; Dong, B. Appl. Catal. B: Environ. 2016, 188, 245. doi: 10.1016/j.apcatb.2016.01.074
20	Lu, N.; Zhang, M. Y.; Jing, X. D.; Zhang, P.; Zhu, Y. A.; Zhang, Z. Y. Energy Environ. Mater. 2022, 0, 1. doi: 10.1002/eem2.12338
21	Jiang, D. L.; Chen, L. L.; Xie, J. M.; Chen, M. Dalton Trans. 2014, 43, 4878. doi: 10.1039/c3dt53526f
22	Zhang, N.; Li, M. J.; Tan, C. F.; Peh, C. K. N.; Sum, T. C.; Ho, G. W. J. Mater. Chem. A 2017, 5, 21570. doi: 10.1039/c7ta06473j
23	Lim, W. P.; Zhang, Z. H.; Low, H. Y. L.; Chin, W. S. Angew. Chem. Int. Ed. 2004, 43, 5685. doi: 10.1002/anie.200460566
24	An, S. F.; Guo, Y. K.; He, X. Y.; Gao, P.; Hou, G. J.; Hou, J. G.; Song, C. S.; Guo. X. W. Appl. Catal. B: Environ. 2022, 310, 121323. doi: 10.1016/j.apcatb.2022.121323
25	Lu, W.; Ding, T.; Lu, N.; Zhang, J. M.; Yun, K.; Zhang, P.; Zhang, Z. Y. Appl. Surf. Sci. 2022, 592, 153348. doi: 10.1016/j.apsusc.2022.153348
26	Hou, S. C.; Lu, N.; Zhu, Y. A.; Zhang, J. M.; Zhang, X. L.; Yan, Y.; Zhang, P.; Zhang, Z. Y. J. Alloy. Compd. 2022, 900, 163409. doi: 10.1016/j.jallcom.2021.163409
27	Lu, N.; Jing, X. D.; Zhang, J. M.; Zhang, P.; Qiao, Q.; Zhang, Z. Y. Chem. Eng. J. 2022, 431, 134001. doi: 10.1016/j.cej.2021.134001
28	Wu, J. L.; Zhang, Z. Y.; Fang, Y. R.; Liu, K. C.; Huang, J. D.; Yuan, Q.; Dong, B. Chem. Eng. J. 2022, 437, 135308. doi: 10.1016/j.cej.2022.135308
29	Waterhouse, G. I. N.; Bowmaker, G. A.; Metson, J. B. Phys. Chem. Chem. Phys. 2001, 3, 3838. doi: 10.1039/b103226g
30	Lin, D. D.; Wu, H.; Zhang, R; Pan, W. Chem. Mater. 2009, 21, 3479. doi: 10.1021/cm900225p
31	Wen, X. G.; Wang, S. H.; Xie, Y. T; Li, X. Y.; Yang, S. H. J. Phys. Chem. B 2005, 109, 10100. doi: 10.1021/jp050126o
32	Mei, Z. H.; Wang, G. H.; Yan, S. D.; Wang, J. Acta Phys. -Chim. Sin. 2021, 37, 2009097.
	梅子慧, 王国宏, 严素定, 王娟物理化学学报, 2021, 37, 2009097. doi: 10.3866/PKU.WHXB202009097
33	Wang, J. L.; Feng, H.; Chen, K. M.; Fan, W. L.; Yang, Q. Dalton Trans. 2014, 43, 3990. doi: 10.1039/c3dt52693c
34	Peng, C. C.; Wang, W. Z.; Zhang, W. W.; Liang, Y. J.; Zhuo, L. Appl. Surf. Sci. 2017, 420, 286. doi: 10.1016/j.apsusc.2017.05.101
35	Zhao, S.; Wu, J. B.; Xu, Y.; Zhang, X.; Han, Y. D.; Xing, H. Z. Dalton Trans. 2021, 50, 3253. doi: 10.1039/d0dt04292g
36	Lin, L.; Cao, C.; Jin, Q.; Xu, G. S.; Shen, Y. H.; Yuan, Y. P. J. Mater. Chem. A 2015, 3, 10205. doi: 10.1039/c5ta01078k
37	Zhang, M. Y.; Shao. C. L.; Guo, Z. C.; Zhang, Z. Y.; Mu, J. B.; Cao, T. P.; Liu, Y. C. ACS Appl. Mater. Interfaces 2011, 3, 369. doi: 10.1021/am100989a
38	Wei, C. C.; Zhang, W.; Wang, X. P.; Li, A. H.; Guo, J. P.; Liu, B. Catal. Lett. 2021, 151, 1961. doi: 10.1007/s10562-020-03462-y
39	Wang, C. H.; Shao, C. L.; Zhang, X. T.; Liu, Y. C. Inorg. Chem. 2009, 48, 7261. doi: 10.1021/ic9005983
40	Zhang, Z. Y.; Liu, K. C.; Feng, Z. Q.; Bao, Y. N.; Dong, B. Sci. Rep. 2016, 6, 19221. doi: 10.1038/srep19221
41	Li, G. M.; Wang, B.; Wang, R. Chin. J. Struct. Chem. 2020, 39, 1675. doi: 10.14102/j.cnki.0254-5861.2011-2685
42	Wu, J. L.; Zhang, Y.; Lu, P.; Fang, G. Q.; Li, X.; Yu, W. W.; Zhang, Z. Y.; Dong, B. Appl. Catal. B: Environ. 2021, 286, 119944. doi: 10.1016/j.apcatb.2021.119944
43	Xia, P. F.; Zhu, B. C.; Yu, J. G.; CaO, S. W.; Jaroniec, M. J. Mater. Chem. A 2017, 5, 3230. doi: 10.1039/c6ta08310b
44	Gao, D. Q.; Xu, Q.; Zhang, J.; Yang, Z. L.; Si, M. S.; Yan, Z. J.; Xue, D. S. Nanoscale 2014, 6, 2577. doi: 10.1039/c3nr04743a
45	Feng, N. D.; Wang, Q.; Zheng, A. M.; Zhang, Z. F.; Fan, J.; Liu, S. B.; Amoureux, J. P.; Deng, F. J. Am. Chem. Soc. 2013, 135, 4, 1607. doi: 10.1021/ja312205c
46	Wang, Y. Z.; Chen, D.; Qin, L. S.; Liang, J. H.; Huang, Y. X. Phys. Chem. Chem. Phys. 2019, 21, 25484. doi: 10.1039/c9cp04709c
47	Jing, X. D.; Lu, N.; Huang, J. D.; Zhang, P.; Zhang, Z. Y. J. Energy Chem. 2021, 58, 397. doi: 10.1016/j.jechem.2020.10.032

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多组分纳米纤维体系中载流子动力学的有效级联调制及其高效光催化产氢性能研究

Effective Cascade Modulation of Charge-Carrier Kinetics in the Well-Designed Multi-Component Nanofiber System for Highly-Efficient Photocatalytic Hydrogen Generation

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