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表面增强拉曼散射(surface-enhanced Raman scattering, SERS)在分析检测领域中具有重要地位, 然而随着其不断发展, 贵金属SERS基底在实际应用中受到限制. 基于C, Ti, Zn, Cu, Mo, W等非贵金属纳米材料的SERS基底相比于贵金属基底具有更优异的经济性、稳定性、选择性以及生物相容性等, 逐渐被广泛研究和应用. 并且由于其化学增强占主导的特性, 非贵金属基底为SERS化学增强机理的研究提供了理想的平台. 因此, 本文对近年来非贵金属SERS基底的发展进行了综述, 讨论了不同材料的增强机理及SERS性能, 并探讨了其未来的研究与发展方向.
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关键词:
- 非贵金属材料 /
- 表面增强拉曼散射基底 /
- 半导体 /
- 拉曼光谱
Surface-enhanced Raman scattering (SERS) is of great importance in analytical science, the noble-metal such as gold and silver are widely used in SERS research and applications. However, noble-metal based substrates are hampered in practical application. As for comparison, the Non-noble metal especially the semiconductor materials are the emerging SERS research frontier. Non-noble metal (such as C, Ti, Zn, Cu, Mo, W, etc.) nanomaterials based SERS substrate have been widely studied and applied due to their superior stability, selectivity, biocompatibility and low cost comparing to noble metal materials. As the chemical enhancement dominate its total SERS signals, it also provides an ideal platform for the investigation of chemical enhancement mechanism. In this review, we explored the development of non-noble metal SERS substrates, focusing on its enhancement mechanism and SERS performance of different materials as well as the future development direction.-
Keywords:
- non-noble metal materials /
- surface-enhanced Raman scattering substrate /
- semiconductor /
- Raman spectroscopy
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图 1 (a) 不同pH下, 4-MBA分子在TiO2基底上的SERS光谱[21]; (b) 4-MBA分子在不同Zn掺杂程度TiO2基底上的SERS光谱[22]; (c) 4-MBA分子在不同体系中的能级图[24]; (d) TiO2球形谐振器(T-rex)的制备流程和T-rex 100样品的SEM图像[26]
Fig. 1. (a) SERS spectra of 4-MBA adsorbed on TiO2 nanoparticles under the different pH values[21]; (b) SERS spectra of 4-MBA adsorbed on TiO2 and Zn-doped TiO2[22]; (c) schematic diagram of the HOMO and LUMO of 4-MBA, 4-MBA@a-TiO2, and 4-MBA@c-TiO2[24]; (d) scheme of preparation of TiO2 spherical resonators (Trex). SEM image of T-rex100 sample[26].
图 2 (a) a-ZnO NCs和c-ZnO NCs的制备过程; (b) a-和c-ZnO NCs的TEM图像和高分辨透射电镜(High-resolution TEM, HRTEM)显微照片; (c)—(e) 单个a-和c-ZnO NCs上的4-MBA, 4-MPY, 4-ATP分子(10-4 M)的SERS光谱, 实测的(M)和模拟的(S)[32]
Fig. 2. (a) A schematic of the fabrication of a- and c-ZnO NCs; (b) SEM and TEM images of a- and c-ZnO NCs.; (c)-(e) SERS spectra of 4-MBA, 4-MPY, and 4-ATP (10-4 M) molecules adsorbed onto a single a- and c-ZnO NC, Measured (M) and simulated (S)[32]
图 3 (a) 4-NBT分子分别在{100}单立方、{110}十二面体和{111}八面体Cu2O粒子上的SERS谱[36]; (b) 分别为立方Cu2O、八面体Cu2O、十二面体Cu2O结构的SEM图[36]; (c) Cu2O立方型超结构的自组装过程[37]
Fig. 3. (a) SERS spectra of 4-NBT molecule obtained on single {100}-cubic, {110}-dodecahedral, and {111}-octahedral Cu2O particle, respectively [36]; (b) the SEM images of the cubic Cu2O, octahedral Cu2O, and dodecahedral Cu2O structures[36]; (c) self-assembly process for the formation of Cu2O cube-like superstructures[37].
图 5 (a) 哑铃状MoO2纳米晶的TEM图[12]; (b) 2D MoS2上4-MPy的范德华相互作用的模型示意图[7]; (c) MoO2, MoO2-x纳米粒子的XRD图谱和单斜MoO2晶体结构示意图[43]
Fig. 5. (a) TEM images of the MoO2 powders[12]; (b) schematic model of the van der Waals interaction of 4-MPy on top of the 2D MoS2[7]; (c) XRD patterns of MoO2 and MoO2-x nanoparticles; Schematic illustrating the crystal structure of monoclinic MoO2[43].
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[1] Fleischmann M, Hendra P J, McQuillan A J 1974 Chem. Phys. Lett. 26 163Google Scholar
[2] Moskovits M 1978 J. Chem. Phys. 69 4159Google Scholar
[3] Kneipp K, Wang Y, Kneipp H, Perelman L T, Itzkan I, Dasari R R, Feld M S 1997 Phys. Rev. Lett. 78 1667Google Scholar
[4] Ji W, Zhao B, Ozaki Y 2016 J. Raman Spectrosc. 47 51Google Scholar
[5] Ling X, Xie L, Fang Y, Xu H, Zhang H, Kong J, Dresselhaus M S, Zhang J, Liu Z 2010 Nano Lett. 10 553Google Scholar
[6] Xue X, Ji W, Mao Z, Mao H, Wang Y, Wang X, Ruan W, Zhao B, Lombardi J R 2012 J. Phys. Chem. C 116 8792Google Scholar
[7] Muehlethaler C, Considine C R, Menon V, Lin W C, Lee Y H, Lombardi J R 2016 ACS Photonics 3 1164Google Scholar
[8] Tan Y, Gu J, Xu W, Chen Z, Liu D, Liu Q, Zhang D 2013 ACS Appl. Mater. Interfaces 5 9878Google Scholar
[9] Daglar B, Khudiyev T, Demirel G B, Buyukserin F, Bayindir M 2013 J. Mater. Chem. C 1 7842Google Scholar
[10] 赵冰, 徐蔚青, 阮伟东, 韩晓霞 2008 高等学校化学学报 29 2591Google Scholar
Zhao B, Xu W Q, Ruan W D, Han X X 2008 Chem. J. Chin. Univ. 29 2591Google Scholar
[11] Wang X, Guo L 2020 Angew. Chem. Int. Ed. 59 4231Google Scholar
[12] Zhang Q, Li X, Ma Q, Zhang Q, Bai H, Yi W, Liu J, Han J, Xi G 2017 Nat. Commun. 8 14903Google Scholar
[13] Shi L, Tuzer T U, Fenollosa R, Meseguer F 2012 Adv. Mater. 24 5934Google Scholar
[14] Ji W, Li L, Song W, Wang X, Zhao B, Ozaki Y 2019 Angew. Chem. Int. Ed. 58 14452Google Scholar
[15] Yang L, Jiang X, Ruan W, Zhao B, Xu W, Lombardi J R 2008 J. Phys. Chem. C 112 20095Google Scholar
[16] Jung N, Crowthe A C, Kim N, Kim P, Brus L 2010 ACS Nano 4 7005Google Scholar
[17] Feng S, Santos M C D, Carvalho B R, et al. 2016 Sci. Adv. 2 1600322Google Scholar
[18] Huang S, Ling X, Liang L, Song Y, Fang W, Zhang J, Kong J, Meunier V, Dresselhaus M S 2015 Nano Lett. 15 2892Google Scholar
[19] Begliarbekov M, Sul O, Santanello J, Ai N, Zhang X, Yang E H, Strauf S 2011 Nano Lett. 11 1254Google Scholar
[20] Papadakis D, Diamantopoulou A, Pantazopoulos P A, et al. 2019 Nanoscale 11 21542Google Scholar
[21] Yang L, Jiang X, Ruan W, Zhao B, Xu W, Lombardi J R 2009 J. Raman Spectrosc. 40 2004Google Scholar
[22] Yang L, Zhang Y, Ruan W, Zhao B, Xu W, Lombardi J R 2010 J. Raman Spectrosc. 41 721Google Scholar
[23] Keshavarz M, Kassanos P, Tan B, Venkatakrishnan K 2020 Nanoscale Horiz. 5 294Google Scholar
[24] Wang X, Shi W, Wang S, Zhao H, Lin J, Yang Z, Chen M, Guo L 2019 J. Am. Chem. Soc. 141 5856Google Scholar
[25] Lin J, Ren W, Li A, Yao C, Chen T, Ma X, Wang X, Wu A 2020 ACS Appl. Mater. Interfaces 12 4204Google Scholar
[26] Alessandri I 2013 J. Am. Chem. Soc. 135 5541Google Scholar
[27] Qi D, Lu L, Wang L, Zhang J 2014 J. Am. Chem. Soc. 136 9886Google Scholar
[28] Sarycheva A, Makaryan T, Maleski K, et al. 2017 J. Phys. Chem. C 121 19983Google Scholar
[29] Ye Y T, Yi W C, Liu W, Zhou Y, Bai H, Li J F, Xi G C 2020 Sci. China Mater. 63 794Google Scholar
[30] Wen H, He T J, Xu C Y, Zuo J, Liu F C 1996 Mol. Phys. 88 281Google Scholar
[31] Sun Z, Zhao B, Lombardi J R 2007 Appl. Phys. Lett. 91 221106Google Scholar
[32] Wang X, Shi W, Jin Z, Huang W, Lin J, Ma G, Li S, Guo L 2017 Angew. Chem. Int. Ed. 56 9851Google Scholar
[33] Zhao X, Deng M, Rao G, et al. 2018 Small 14 1802477Google Scholar
[34] Li X, Shang Y, Lin J, Li A, Wang X, Li B, Guo L 2018 Adv. Funct. Mater. 28 1801868Google Scholar
[35] Li X, Ren X, Zhang Y, Choy W C, Wei B 2015 Nanoscale 7 11291Google Scholar
[36] Wang R C, Li C H 2011 Acta Mater. 59 822Google Scholar
[37] Lin J, Hao W, Shang Y, Wang X, Qiu D, Ma G, Chen C, Li S, Guo L 2018 Small 14 1703274Google Scholar
[38] Lin J, Shang Y, Li X, Yu J, Wang X, Guo L 2017 Adv. Mater. 29 10Google Scholar
[39] Qiu C, Zhang L, Wang H, Jiang C 2012 J. Phys. Chem. Lett. 3 651Google Scholar
[40] Jiang L, You T, Yin P, Shang Y, Zhang D, Guo L, Yang S 2013 Nanoscale 5 2784Google Scholar
[41] Zhang Q, Li X, Yi W, Li W, Bai H, Liu J, Xi G 2017 Anal. Chem. 89 11765Google Scholar
[42] Wu H, Zhou X, Li J, Li X, Li B, Fei W, Zhou J, Yin J, Guo W 2018 Small 14 1802276Google Scholar
[43] Cao Y, Liang P, Dong Q, Wang D, Zhang, Tang L, Wang L, Jin S, Ni D, Yu Z 2019 Anal. Chem. 91 8683Google Scholar
[44] Zheng Z, Cong S, Gong W, Xuan J, Li G, Lu W, Geng F, Zhao Z 2017 Nat. Commun. 8 1993Google Scholar
[45] Cong S, Yuan Y, Chen Z, Hou J, Yang M, Su Y, Zhang Y, Li L, Li Q, Geng F, Zhao Z 2015 Nat. Commun. 6 7800Google Scholar
[46] Fan X, Li M, Hao Q, Zhu M, Hou X, Huang H, Ma L, Schmidt O G, Qiu T 2019 Adv. Mater. Interfaces 6 1901133Google Scholar
[47] Zhou C L, Sun L F, Zhang F Q, Gu C J, Zeng S W, Jiang T, Shen X, Ang D S, Zhou J 2019 ACS Appl. Mater. Interfaces 11 34091Google Scholar
[48] Ye Y T, Bai H, Li M C, Tian Z, Du R F, Fan W H, Xi G C 2019 Adv. Mater. Technol. 4 1900282Google Scholar
[49] Hou X Y, Luo X G, Fan X C, Peng Z H, Qiu T 2019 Phys. Chem. Chem. Phys. 21 2611Google Scholar
[50] Wang X, Shi W, She G, Mu L 2011 J. Am. Chem. Soc. 133 16518Google Scholar
[51] 侯近龙, 贾祥非, 薛向欣, 陈雷, 宋微, 徐蔚青, 赵冰 2012 高等学校化学学报 33 139Google Scholar
Hou J L, Jia X F, Xue X X, Chen L, Song W, Xu W Q, Zhao B 2012 Chem. J. Chin. Univ. 33 139Google Scholar
[52] Miao P, Wu J, Du Y, Sun Y, Xu P 2018 J. Mater. Chem. C 6 10855Google Scholar
[53] Miao P, Qin J K, Shen Y, Su H, Dai J, Song B, Du Y, Sun M, Zhang W, Wang H L, Xu C Y, Xu P 2018 Small 14 1704079Google Scholar
[54] Gao M, Miao P, Han X, Sun C, Ma Y, Gao Y, Xu P 2019 Inorg. Chem. Front. 6 2318Google Scholar
[55] Lee N, Schuck P J, Nico P S, Gilbert B 2015 J. Phys. Chem. Lett. 6 970Google Scholar
[56] Fu X, Pan Y, Wang X, Lombardi J R 2011 J. Chem. Phys. 134 024707Google Scholar
[57] Quagliano L G 2004 J. Am. Chem. Soc. 126 7393Google Scholar
[58] Livingstone R, Zhou X, Tamargo M C, Lombardi J R, Quagliano L C, Jean M F 2010 J. Phys. Chem. C 114 17460Google Scholar
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