本實驗以尺寸相近的金奈米棒與金奈米雙三角錐為起始物，在表面生長銀 外殼，形成不同形貌的金/銀-核/殼結構，再以此作為犧牲模板，使用 K2PtCl4與 PtCl4分別作為Pt(II)與 Pt(IV)的前驅物，進行賈凡尼置換反應，因為鉑前驅物的 價數不同而形成不同形貌的三金屬奈米補光器。將這些材料用於光催化產氫反 應，整體效果的趨勢為置換程度越高，產氫效果越好，使用Pt(II)前驅物時比使 用Pt(IV)前驅物時效果好，以金奈米雙三角錐為起始物時效果又比使用金奈米 棒為起始物時更好，照光後過電位降低約0.045 V，證明表面電漿子金屬奈米材 料，可有效的被利用於光催化反應。透過EDX mapping 確認元素的分布情形，
金分佈於原來的位置，少部分擴散至周圍，銀則是在端點及角落的位置居多，
而鉑分佈於整個奈米結構中，包含表面及端點。最後使用ICP-MS 進行元素定 量分析，證實以少量的鉑負載量就可以達到優異的催化效果。
47
參考文獻
1. 牟中原; 陳家俊, 奈米材料研究發展. 科學發展 2000, 4 (8), 281-288.
2. Edvinsson, T., Optical quantum confinement and photocatalytic properties in two-, one- and zero-dimensional nanostructures. R Soc Open Sci 2018, 5 (9), 180387.
3. Hulla, J. E.; Sahu, S. C.; Hayes, A. W., Nanotechnology: History and future.
Hum Exp Toxicol 2015, 34 (12), 1318-1321.
4. Cao, J.; Sun, T.; Grattan, K. T. V., Gold nanorod-based localized surface plasmon resonance biosensors: A review. Sensors and Actuators B: Chemical 2014, 195, 332-351.
5. Wu, B.; Liu, D.; Mubeen, S.; Chuong, T. T.; Moskovits, M.; Stucky, G.
D., Anisotropic Growth of TiO2 onto Gold Nanorods for Plasmon-Enhanced Hydrogen Production from Water Reduction. J Am Chem Soc 2016, 138 (4), 1114-1147.
6. Kuo, T.-R.; Lee, Y.-C.; Chou, H.-L.; M G, S.; Wei, C.-Y.; Wen, C.-Y.;
Chang, Y.-H.; Pan, X.-Y.; Wang, D.-Y., Plasmon-Enhanced Hydrogen Evolution on Specific Facet of Silver Nanocrystals. Chemistry of Materials 2019, 31 (10), 3722-3728.
7. Yu, S.; Wilson, A. J.; Heo, J.; Jain, P. K., Plasmonic Control of Multi-Electron Transfer and C-C Coupling in Visible-Light-Driven CO2 Reduction on Au Nanoparticles. Nano Lett 2018, 18 (4), 2189-2194.
8. Wang, F.; Li, C.; Chen, H.; Jiang, R.; Sun, L. D.; Li, Q.; Wang, J.;
Yu, J. C.; Yan, C. H., Plasmonic harvesting of light energy for Suzuki coupling reactions. J Am Chem Soc 2013, 135 (15), 5588-5601.
9. Zheng, Z.; Tachikawa, T.; Majima, T., Single-particle study of Pt-modified Au nanorods for plasmon-enhanced hydrogen generation in visible to near-infrared region. J Am Chem Soc 2014, 136 (19), 6870-6873.
10. Yin, Y.; Yang, Y.; Zhang, L.; Li, Y.; Li, Z.; Lei, W.; Ma, Y.; Huang, Z.,
48
Facile synthesis of Au/Pd nano-dogbones and their plasmon-enhanced visible-to-NIR light photocatalytic performance. RSC Advances 2017, 7 (59), 36923-36928.
11. Nedrygailov, II; Moon, S. Y.; Park, J. Y., Hot electron-driven electrocatalytic hydrogen evolution reaction on metal-semiconductor nanodiode electrodes. Sci Rep 2019, 9 (1), 6208.
12. Zhang, H. X.; Li, Y.; Li, M. Y.; Zhang, H.; Zhang, J., Boosting electrocatalytic hydrogen evolution by plasmon-driven hot-electron excitation.
Nanoscale 2018, 10 (5), 2236-2241.
13. Shi, Y.; Wang, J.; Wang, C.; Zhai, T. T.; Bao, W. J.; Xu, J. J.; Xia, X.
H.; Chen, H. Y., Hot electron of Au nanorods activates the electrocatalysis of
hydrogen evolution on MoS2 nanosheets. J Am Chem Soc 2015, 137 (23), 7365-7370.
14. Liu, K.-K.; Tadepalli, S.; Tian, L.; Singamaneni, S., Size-Dependent Surface Enhanced Raman Scattering Activity of Plasmonic Nanorattles. Chemistry of
Materials 2015, 27 (15), 5261-5270.
15. Singh, P.; Konig, T. A. F.; Jaiswal, A., NIR-Active Plasmonic Gold Nanocapsules Synthesized Using Thermally Induced Seed Twinning for Surface-Enhanced Raman Scattering Applications. ACS Appl Mater Interfaces 2018, 10 (45), 39380-39390.
16. Zhang, T.; Gao, N.; Li, S.; Lang, M. J.; Xu, Q. H., Single-Particle Spectroscopic Study on Fluorescence Enhancement by Plasmon Coupled Gold Nanorod Dimers Assembled on DNA Origami. J Phys Chem Lett 2015, 6 (11), 2043-2049.
17. Yin, D.; Li, X.; Ma, Y.; Liu, Z., Targeted cancer imaging and photothermal therapy via monosaccharide-imprinted gold nanorods. Chem Commun (Camb) 2017, 53 (50), 6716-6719.
18. Feng, J.; Chen, L.; Xia, Y.; Xing, J.; Li, Z.; Qian, Q.; Wang, Y.; Wu, A.; Zeng, L.; Zhou, Y., Bioconjugation of Gold Nanobipyramids for SERS
Detection and Targeted Photothermal Therapy in Breast Cancer. ACS Biomaterials Science & Engineering 2017, 3 (4), 608-618.
49
19. Wi, J. S.; Park, J.; Kang, H.; Jung, D.; Lee, S. W.; Lee, T. G., Stacked Gold Nanodisks for Bimodal Photoacoustic and Optical Coherence Imaging. ACS Nano 2017, 11 (6), 6225-6232.
20. Ye, X.; Jin, L.; Caglayan, H.; Chen, J.; Xing, G.; Zheng, C.; Doan-Nguyen, V.; Kang, Y.; Engheta, N.; Kagan, C. R.; Murray, C. B., Improved Size-Tunable Synthesis of Monodisperse Gold Nanorods through the Use of Aromatic Additives. ACS Nano 2012, 6, 2804-2817.
21. Ye, X.; Zheng, C.; Chen, J.; Gao, Y.; Murray, C. B., Using binary surfactant mixtures to simultaneously improve the dimensional tunability and monodispersity in the seeded growth of gold nanorods. Nano Lett 2013, 13 (2), 765-771.
22. Chang, H. H.; Murphy, C. J., Mini Gold Nanorods with Tunable Plasmonic Peaks beyond 1000 nm. Chem Mater 2018, 30 (4), 1427-1435.
23. Vigderman, L.; Zubarev, E. R., High-Yield Synthesis of Gold Nanorods with Longitudinal SPR Peak Greater than 1200 nm Using Hydroquinone as a Reducing Agent. Chemistry of Materials 2013, 25 (8), 1450-1457.
24. Li, Q.; Zhuo, X.; Li, S.; Ruan, Q.; Xu, Q. H.; Wang, J., Production of Monodisperse Gold Nanobipyramids with Number Percentages Approaching 100%
and Evaluation of Their Plasmonic Properties. Advanced Optical Materials 2015, 6, 801-812.
25. Lee, S.; Mayer, K. M.; Hafner, J. H., Improved Localized Surface Plasmon Resonance Immunoassay with Gold Bipyramid Substrates. Anal. Chem. 2009, 81, 4450-4455.
26. Lidor-Shalev, O.; Elani, Z., Controlled Crystallization of Gold Nanocrystals. In Advanced Topics in Crystallization, 2015.
27. Grzelczak, M.; Perez-Juste, J.; Mulvaney, P.; Liz-Marzan, L. M., Shape control in gold nanoparticle synthesis. Chem Soc Rev 2008, 37 (9), 1783-1791.
28. Personick, M. L.; Langille, M. R.; Zhang, J.; Mirkin, C. A., Shape control of gold nanoparticles by silver underpotential deposition. Nano Lett 2011, 11 (8), 3394-3398.
50
29. Rodrı´guez-Ferna´ndez, J.; Pe´rez-Juste, J.; Mulvaney, P.; Liz-Marza´n, L.
M., Spatially-Directed Oxidation of Gold Nanoparticles by Au(III)-CTAB Complexes.
J. Phys. Chem. B 2005, 109, 14257-14261.
30. Tebbe, M.; Kuttner, C.; Mayer, M.; Maennel, M.; Pazos-Perez, N.;
Konig, T. A.; Fery, A., Silver-Overgrowth-Induced Changes in Intrinsic Optical Properties of Gold Nanorods: From Noninvasive Monitoring of Growth Kinetics to Tailoring Internal Mirror Charges. J Phys Chem C Nanomater Interfaces 2015, 119 (17), 9513-9523.
31. Zhu, X. Z. X.; Li, Q.; Yang, Z.; Wang, J., Gold Nanobipyramid-Directed Growth of Length-Variable Silver Nanorods with Multipolar Plasmon Resonances.
ACS Nano 2015, 9, 7523-7535.
32. Jiang, R.; Chen, H.; Shao, L.; Li, Q.; Wang, J., Unraveling the evolution and nature of the plasmons in (Au core)-(Ag shell) nanorods. Adv Mater 2012, 24 (35), OP200-207.
33. Hsia, C.-F.; Madasu, M.; Huang, M. H., Aqueous Phase Synthesis of Au–Cu Core–Shell Nanocubes and Octahedra with Tunable Sizes and Noncentrally Located Cores. Chemistry of Materials 2016, 28 (9), 3073-3079.
34. Lyu, Z.; Xie, M.; Aldama, E.; Zhao, M.; Qiu, J.; Zhou, S.; Xia, Y., Au@Cu Core–Shell Nanocubes with Controllable Sizes in the Range of 20–30 nm for Applications in Catalysis and Plasmonics. ACS Applied Nano Materials 2019, 2 (3), 1533-1540.
35. Su, G.; Jiang, H.; Zhu, H.; Lv, J. J.; Yang, G.; Yan, B.; Zhu, J. J., Controlled deposition of palladium nanodendrites on the tips of gold nanorods and their enhanced catalytic activity. Nanoscale 2017, 9 (34), 12494-12502.
36. Ye, R.; Zhang, Y.; Chen, Y.; Tang, L.; Wang, Q.; Wang, Q.; Li, B.;
Zhou, X.; Liu, J.; Hu, J., Controlling Shape and Plasmon Resonance of Pt-Etched Au@Ag Nanorods. Langmuir 2018, 34 (20), 5719-5727.
37. González, E.; Arbiol, J.; Puntes, V. F., Carving at the Nanoscale Sequential Galvanic Exchange and Kirkendall Growth at Room Temperature. SCIENCE 2011.
51
38. Yen, H.-C.; Su, M.-N.; Liu, Y.-C.; Lee, M.-W.; Sheu, Y.-L.; Hsu, L.-Y.;
Chen, C.-C., Design of Plasmon Resonance Shifts by the Galvanic Replacement Degree of Au–Ag Nanozappers. The Journal of Physical Chemistry C 2019, 123 (48), 29298-29305.
39. Yang, X.; Roling, L. T.; Vara, M.; Elnabawy, A. O.; Zhao, M.; Hood, Z.
D.; Bao, S.; Mavrikakis, M.; Xia, Y., Synthesis and Characterization of Pt-Ag Alloy Nanocages with Enhanced Activity and Durability toward Oxygen Reduction.
Nano Lett 2016, 16 (10), 6644-6649.
40. Hajfathalian, M.; Gilroy, K. D.; Golze, S. D.; Yaghoubzade, A.;
Menumerov, E.; Hughes, R. A.; Neretina, S., A Wulff in a Cage: The Confinement of Substrate-Based Structures in Plasmonic Nanoshells, Nanocages, and Nanoframes Using Galvanic Replacement. ACS Nano 2016, 10 (6), 6354-6362.
41. Li, H.; Wu, H.; Zhai, Y.; Xu, X.; Jin, Y., Synthesis of Monodisperse Plasmonic Au Core–Pt Shell Concave Nanocubes with Superior Catalytic and Electrocatalytic Activity. ACS Catalysis 2013, 3 (9), 2045-2051.
42. Xiong, W.; Mazid, R.; Yap, L. W.; Li, X.; Cheng, W., Plasmonic caged gold nanorods for near-infrared light controlled drug delivery. Nanoscale 2014, 6 (23), 14388-14393.
43. Hydrogen for Large-scale Electricity Generation in USA.
44. Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; Norskov, J.
K.; Jaramillo, T. F., Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355 (6321).
45. Scarabelli, L.; Sánchez-Iglesias, A.; Pérez-Juste, J.; Liz-Marzán, L. M., A
“Tips and Tricks” Practical Guide to the Synthesis of Gold Nanorods. The Journal of Physical Chemistry Letters 2015, 6 (21), 4270-4279.