陷阱态对Ag-TiO2光诱导界面电荷转移的影响：电化学、光电化学和光谱表征

doi:10.13208/j.electrochem.2208101

摘要/Abstract

摘要：

在基于金属-半导体异质结构的等离激元介导化学反应中，了解其中的电荷转移和复合机制进而调控界面、提高界面电荷分离，对于提高等离激元催化反应效率至关重要。但电化学体系中固液界面上的等离激元光电催化反应是一个多过程、多时间尺度、多影响因素的复杂体系，光生载流子在界面间传递机制的研究仍面临着巨大的挑战。由于光电化学信号的产生和变化包含了诸多体相和界面过程，因此光电化学方法是探究等离激元催化反应过程中的界面电荷转移机制的有效手段之一。本文合成了TiO₂和Ag-TiO₂纳米粒子，以光电化学方法作为主要研究手段，并结合电化学和各种谱学表征手段，探究了电极陷阱态对界面电荷转移机制的影响。结果表明，在Ag负载在TiO₂表面后，电极的陷阱态显著增加。结合XPS以及PL光谱，陷阱态增加可主要归咎于表面羟基。陷阱态的增加导致了荧光的猝灭和光电响应的减弱，但增加的陷阱态复合过程也延长了载流子的寿命。陷阱态的调控必然会影响界面电荷转移，从而改变热载流子的数量和寿命，进而调控后续Ag界面上的等离激元反应。在反应位点位于金属的基于金属-半导体复合体系的等离激元催化反应中，认识到半导体陷阱态对于界面电荷转移的作用有助于在等离激元介导化学反应中更好地利用载流子、提高反应效率。

关键词: 等离激元, Ag-TiO₂, 陷阱态, 电荷转移, 光电化学表征

Abstract:

In the field of metal-semiconductor composites based plasmon-mediated chemical reactions, a clear and in-depth understanding of charge transfer and recombination mechanisms is crucial for improving plasmonic photocatalytic efficiency. However, the plasmonic photocatalytic reactions at the solid-liquid interface of the electrochemical systems involve complex processes with multiple elementary steps, multiple time scales, and multiple controlling factors. Herein, the combination of photoelectrochemical and electrochemical as well as spectroscopic characterizations has been successfully used to study the effects of traps on the photo-induced interfacial charge transfer of silver-titanium dioxide (Ag-TiO₂). The results show that the increase of surface hydroxyl groups may be the key reason leading to the increase of traps after the Ag deposition on the surface of TiO₂. The increased traps of Ag-TiO₂, including deep and shallow traps, subsequently lead to the quenching of fluorescence and the reduction of photocurrent in the UV region. But the enhanced trap recombination may also prolong the lifetime of carriers. The modulation of traps is bound to affect the interfacial charge transfer, and thus, change the amount and lifetime of hot carriers, which can be exploited to manipulate the molecular reactions at the Ag surface. Our work highlights the importance of traps at metal-semiconductor electrodes that may help utilize the hot carriers in plasmonic mediated chemical reactions.

Key words: Plasmonic, Silver-titanium dioxide, Trap state, Charge transfer, Photoelectrochemical Characterization

梁志豪, 王家正, 王丹, 周剑章, 吴德印. 陷阱态对Ag-TiO₂光诱导界面电荷转移的影响：电化学、光电化学和光谱表征[J]. 电化学（中英文）, 2023, 29(8): 2208101.

Zhi-Hao Liang, Jia-Zheng Wang, Dan Wang, Jian-Zhang Zhou, De-Yin Wu. Effects of Traps on Photo-induced Interfacial Charge Transfer of Ag-TiO₂: Photoelectrochemical, Electrochemical and Spectroscopic Characterizations[J]. Journal of Electrochemistry, 2023, 29(8): 2208101.

图/表 12

参考文献 27

[1]	Zhan C, Chen X J, Yi J, Li J F, Wu D Y, Tian Z Q. From plasmon-enhanced molecular spectroscopy to plasmon-mediated chemical reactions[J]. Nat. Rev. Chem., 2018, 2(9): 216-230. doi: 10.1038/s41570-018-0031-9
[2]	Zhang Y C, He S, Guo W X, Hu Y, Huang J W, Mulcahy J R, Wei W D. Surface-plasmon-driven hot electron photochemistry[J]. Chem. Rev., 2018, 118(6): 2927-2954. doi: 10.1021/acs.chemrev.7b00430 pmid: 29190069
[3]	Gelle A, Jin T, de la Garza L, Price G D, Besteiro L V, Moores A. Applications of plasmon-enhanced nanocatalysis to organic transformations[J]. Chem. Rev., 2020, 120(2): 986-1041. doi: 10.1021/acs.chemrev.9b00187 pmid: 31725267
[4]	Brongersma M L, Halas N J, Nordlander P. Plasmon-induced hot carrier science and technology[J]. Nat. Nanotechnol., 2015, 10(1): 25-34. doi: 10.1038/nnano.2014.311 pmid: 25559968
[5]	Moon C W, Choi M J, Hyun J K, Jang H W. Enhancing photoelectrochemical water splitting with plasmonic Au nanoparticles[J]. Nanoscale Adv., 2021, 3(21): 5981-6006. doi: 10.1039/d1na00500f pmid: 36133946
[6]	Ingram D B, Linic S. Water splitting on composite plasmonic-metal/semiconductor photoelectrodes: Evidence for selective plasmon-induced formation of charge carriers near the semiconductor surface[J]. J. Am. Chem. Soc., 2011, 133(14): 5202-5205. doi: 10.1021/ja200086g pmid: 21425795
[7]	Wang S J, Zhang X Y, Su D, Yan X, Zhou H L, Xue X M, Wang Y F, Zhang T. Enhanced photocatalytic reactions via plasmonic metal-semiconductor heterostructures combing with solid-liquid-gas interfaces[J]. Appl. Catal. B-Environ., 2022, 306: 121102. doi: 10.1016/j.apcatb.2022.121102 URL
[8]	Kim Y, Creel E B, Corson E R, McCloskey B D, Urban J J, Kostecki R. Surface-plasmon-assisted photoelectrochemical reduction of CO₂ and NO₃^- on nanostructured silver electrodes[J]. Adv. Energy Mater., 2018, 8(22): 1800363
[9]	Huang H N, Shi R, Li Z H, Zhao J Q, Su C L, Zhang T R. Triphase photocatalytic CO₂ reduction over silver-decorated titanium oxide at a gas-water boundary[J]. Angew. Chem. Int. Ed., 2022, 61(17): e202200802.
[10]	Saravanan R, Manoj D, Qin J Q, Naushad M, Gracia F, Lee A F, Khan M M, Gracia-Pinilla M A. Mechanothermal synthesis of Ag/TiO₂ for photocatalytic methyl orange degradation and hydrogen production[J]. Process Saf. Enivron. Protect., 2018, 120: 339-347.
[11]	Christopher P, Ingram D B, Linic S. Enhancing photochemical activity of semiconductor nanoparticles with optically active Ag nanostructures: Photochemistry mediated by Ag surface plasmons[J]. J. Phys. Chem. C, 2010, 114(19): 9173-9177. doi: 10.1021/jp101633u URL
[12]	Furube A, Du L, Hara K, Katoh R, Tachiya M. Ultrafast plasmon-induced electron transfer from gold nanodots into TiO₂ nanoparticles[J]. J. Am. Chem. Soc., 2007, 129(48): 14852-14853. doi: 10.1021/ja076134v URL
[13]	Zhang Y C, Guo W X, Zhang Y L, Wei W D. Plasmonic photoelectrochemistry: In view of hot carriers[J]. Adv. Mater., 2021, 33(46): 2006654.
[14]	Ichinose H, Terasaki M, Katsuki H. Properties of peroxotitanium acid solution and peroxo-modified anatase sol derived from peroxotitanium hydrate[J]. J. Sol-Gel Sci. Technol., 2001, 22(1-2): 33-40. doi: 10.1023/A:1011256118320 URL
[15]	Damato T C, de Oliveira C C S, Ando R A, Camargo P H C. A facile approach to TiO₂ colloidal spheres decorated with Au nanoparticles displaying well-defined sizes and uniform dispersion[J]. Langmuir, 2013, 29(5): 1642-1649. doi: 10.1021/la3045219 URL
[16]	Yang L B, Jiang X, Ruan W D, Yang J X, Zhao B, Xu W Q, Lombardi J R. Charge-transfer-induced surface-enhanced raman scattering on Ag-TiO₂ nanocomposites[J]. J. Phys. Chem. C, 2009, 113(36): 16226-16231. doi: 10.1021/jp903600r URL
[17]	Zhang Y, Chen J R, Tang H, Xiao Y G, Qiu S F, Li S J, Cao S S. Hierarchically-structured SiO₂-Ag@TiO₂ hollow spheres with excellent photocatalytic activity and recyclability[J]. J. Hazard. Mater., 2018, 354: 17-26. doi: S0304-3894(18)30297-8 pmid: 29723759
[18]	Hong D C, Lyu L M, Koga K, Shimoyama Y, Kon Y. Plasmonic Ag@TiO₂ core-shell nanoparticles for enhanced CO₂ photoconversion to CH₄[J]. ACS Sustain. Chem. Eng., 2019, 7(23): 18955-18964. doi: 10.1021/acssuschemeng.9b04345 URL
[19]	Kohtani S, Kawashima A, Miyabe H. Reactivity of trapped and accumulated electrons in titanium dioxide photocatalysis[J]. Catalysts, 2017, 7(10): 303 doi: 10.3390/catal7100303 URL
[20]	Zhang L W, Mohamed H H, Dillert R, Bahnemann D. Kinetics and mechanisms of charge transfer processes in photocatalytic systems: A review[J]. J. Photochem. Photobiol. C-Photochem. Rev., 2012, 13(4): 263-276. doi: 10.1016/j.jphotochemrev.2012.07.002 URL
[21]	Mercado C, Seeley Z, Bandyopadhyay A, Bose S, McHale J L. Photoluminescence of dense nanocrystalline titanium dioxide thin films: Effect of doping and thickness and relation to gas sensing[J]. ACS Appl. Mater. Interfaces, 2011, 3(7): 2281-2288. doi: 10.1021/am2006433 URL
[22]	Wang H L, He J J, Boschloo G, Lindström H, Hagfeldt A, Lindquist S E. Electrochemical investigation of traps in a nanostructured TiO₂ film[J]. J. Phys. Chem. B, 2001, 105(13): 2529-2533. doi: 10.1021/jp0036083 URL
[23]	Naseri N, Kim H, Choi W, Moshfegh A Z. Optimal Ag concentration for H₂ production via Ag: TiO₂ nanocomposite thin film photoanode[J]. Int. J. Hydrog. Energy, 2012, 37(4): 3056-3065. doi: 10.1016/j.ijhydene.2011.11.041 URL
[24]	Hernández S, Gerardi G, Bejtka K, Fina A, Russo N. Evaluation of the charge transfer kinetics of spin-coated BiVO₄ thin films for sun-driven water photoelectrolysis[J]. Appl. Catal. B, 2016, 190: 66-74. doi: 10.1016/j.apcatb.2016.02.059 URL
[25]	DuChene J S, Sweeny B C, Johnston-Peck A C, Su D, Stach E A, Wei W D. Prolonged hot electron dynamics in plasmonic-metal/semiconductor heterostructures with implications for solar photocatalysis[J]. Angew. Chem. Int. Ed., 2014, 53(30): 7887-7891. doi: 10.1002/anie.201404259 pmid: 24920227
[26]	Moon S Y, Song H C, Gwag E H, Nedrygailov I I, Lee C, Kim J J, Doh W H, Park J Y. Plasmonic hot carrier-driven oxygen evolution reaction on Au nanoparticles/TiO₂ nanotube arrays[J]. Nanoscale, 2018, 10(47): 22180-22188. doi: 10.1039/c8nr05144e pmid: 30484456
[27]	Moser J E. Perovskite photovoltaics: Slow recombination unveiled[J]. Nat. Mater, 2017, 16(1): 4-6. doi: 10.1038/nmat4796

Wavelength/nm	K_tr/K_rec
Wavelength/nm	TiO₂	Ag-TiO₂
365-370	-2.51	0.97
385-390	2.85	0.47
420-430	6.14	0.45
460-470	/	0.38
520-530	/	0.35

Wavelength/nm	Sample	A₁	τ₁/s	A₂	τ₂/s	τ_m/s
365-370	TiO₂	-0.261	1.59	-0.067	15.60	1.44
365-370	Ag-TiO₂	-0.0009	2.51	-0.012	36.84	2.34
460-470	TiO₂	-0.015	5.82	-0.083	38.89	5.06
460-470	Ag-TiO₂	-2.930×10^-3	4.229	-1.415×10^-2	30.84	3.72
	Ag	-0.006	2.85	-0.005	29.34	2.59

陷阱态对Ag-TiO₂光诱导界面电荷转移的影响：电化学、光电化学和光谱表征

Effects of Traps on Photo-induced Interfacial Charge Transfer of Ag-TiO₂: Photoelectrochemical, Electrochemical and Spectroscopic Characterizations

RichHTML

PDF (PC)

补充材料

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 27

相关文章 11

Metrics

[1]	李响, 黄秋安, 李伟恒, 白玉轩, 王佳, 刘杨, 赵玉峰, 王娟, 张久俊. 宏观均相多孔电极电化学阻抗谱基础[J]. 电化学（中英文）, 2021, 27(5): 467-497.
[2]	王晓晓, 周子睿, 单强, 张增明, 黄俊, 刘欲文, 陈胜利. 锂离子电池多孔电极理论的回顾与新思考[J]. 电化学（中英文）, 2020, 26(5): 596-606.
[3]	马洪运, 姚晓辉, 妙孟姚, 易阳, 伍绍中, 周江. 高镍正极材料(LiNi_0.83Co_0.12Mn_0.05O₂)45°C循环失效机理研究[J]. 电化学（中英文）, 2020, 26(3): 431-440.
[4]	方亚辉, 刘智攀. 固液界面双电层的理论计算模拟[J]. 电化学（中英文）, 2020, 26(1): 32-40.
[5]	孙琳琳, 王伟, 陈洪渊. 结合光学成像技术研究单颗粒碰撞电化学[J]. 电化学（中英文）, 2019, 25(3): 386-399.
[6]	张伶潇，赵惠慧，张丽娟，付予. Ag-TiO₂-MnO₂复合材料的制备与电化学性能研究[J]. 电化学（中英文）, 2018, 24(3): 292-299.
[7]	吴元菲，庞然，张檬，周剑章，任斌，田中群，吴德印. SPR银金电极上光电化学反应和EC-SERS理论研究[J]. 电化学（中英文）, 2016, 22(4): 356-367.
[8]	顾菁，乔永辉，朱新宇，阴笑弘，张欣，陈烨，朱志伟，邵元华*. 液/液界面电化学及其进展[J]. 电化学（中英文）, 2014, 20(3): 234-242.
[9]	杨术明，王纪超，寇慧芝，薛洪滨，王红军，郭玉玲. 4-叔丁基吡啶对纳米晶TiO2电极的能带结构及光电化学性质的影响[J]. 电化学（中英文）, 2011, 17(2): 204-211.
[10]	赵刘斌;吴德印;任斌;田中群;. 电化学界面SERS光谱的密度泛函理论研究[J]. 电化学（中英文）, 2010, 16(3): 334-342.
[11]	刘峰名, 韩琪, 陈艳霞, 钟起玲, 任斌, 田中群. 电化学析氢反应诱导的电荷传递SERS效应(英文)[J]. 电化学（中英文）, 2001, 7(1): 74-77.