能源危機與環保問題為本世紀重要的挑戰，乾淨的氫能源成為取代石
化燃料的最佳替代能源，使得發展光觸媒來分解水產氫的研究變得很重要，
使用光觸媒有效利用太陽能分解水產氫，便是此研究的目標。
實驗中使用的ZIS (ZnmIn2S3+m)可見光光觸媒，隨著溫度的上升有助於
提升水分解效率，我們調整核殼結構(Coreshell)內部Nanoshell(Ag@Au)的
吸收波段至紅外光，將太陽能轉換為熱能，形成光觸媒侷部加熱的效應，
最高能有效提升光觸媒的產氫效率達74%。Nanoshell 是由銀與金奈米粒子
所組成，在太陽光照射下其具有表面電漿共振效應，使用吸收波長在700
nm 左右的Nanoshell 與光觸媒形成核殼結構後，表面電漿共振能量傳遞給
外層的光觸媒，利於電子電洞的分離，提升產氫效率最高可達1.62 倍。
我們也改變Nanoshell 上不同SiO2 厚度，觀察光觸媒與Nanoshell 之
間的交互作用對於產氫效率的影響，當無SiO2 在兩者之間時，電子會在兩
者之間傳遞，而過厚的SiO2 會阻礙表面電漿效應的能量傳遞，而使得光觸
媒產氫效率提升幅度下降。
將光觸媒與Nanoshell 直接合成核殼結構，可能會有光觸媒過厚或是
部分Nanoshell 裸露的情形產生，所以我們嘗試先在ZIS 表面改質，再與
Nanoshell 合成核殼結構，反之，也可以在Nanoshell 表面改質，再與ZIS
合成核殼結構，使得每個Nanoshell 的表面都有均勻分布的ZIS，得到最佳的核殼結構。

Energy crisis and environmental protection are big challenges of this century. Hydrogen is the most promising replacement for fossil fuels. Therefore, the development of visible-light-driven photocatalysts for water splitting is critical. The purpose of this study is to effectively use photocatalysts to change solar energy into hydrogen energy.
We used ZIS (ZnmIn2S3+m) as visible-light-driven photocatalyst. Its water splitting reaction rate increased with the temperature. The absorption of the nanoshells in the coreshell nanoparticles can be adjusted systematically from visible light to IR range making the solar energy into heat and resulted in local thermal effect which can effectively enhance hydrogen evolution to 74%. Because the nanoshell was formed by silver and gold nanoparticles, it had the surface plasmon resonance. Using nanoshells absorbing at 700 nm can transfer enengy to photocatalysts and separated the combination of electrons and holes in photocatalysts making the enhancement of hydrogen evolution to 1.62 times.
We also changed the thickness of SiO2 on the nanoshells to observe the interaction between nanoshells and coreshells which might influence the enhancement of hydrogen evolution. When there was no SiO2, electron would transfer between nanoshells and photocatalysts. Thicker thickness of SiO2 might hinder the translation of energy from nanoshells decreasing the enhancement of hydrogen evolution.
Making photocatalysts directly into coreshell structures might cause thicker shell or uncovered nanoshells. So we try to mdify the surface of ZIS or mdify the surface of nanoshells and formed coreshell, making uniform distribution of ZIS on nanoshells.

1. Bull, S. R., Renewable energy today and tomorrow. Proceedings of the
IEEE, 2001. 89(8): p. 1216-1226.
2. Crabtree, G. W., M. S. Dresselhaus, and M. V. Buchanan, The hydrogen
economy. Physics Today, 2004. 57(12): p. 39-44.
3. Turner, J. A., A realizable renewable energy future. Science, 1999.
285(5428): p. 687-689.
4. Fujishima, A. and K. Honda, Electrochemical Photolysis of Water at a
Semiconductor Electrode. Nature, 1972. 286( 5772): p. 474-476.
5. Maeda, K. and K. Domen, New non-oxide photocatalysts designed for
overall water splitting under visible light. The Journal of Physical
Chemistry C, 2007. 111(22): p. 7851-7861.
6. Lewis, N. S., Light work with water. Nature, 2001. 414(6864): p.
589-590.
7. Kudo, A., Recent progress in the development of visible light-driven
powdered photocatalysts for water splitting. International journal of
hydrogen energy, 2007. 32(14): p. 2673-2678.
8. Kawai, T. and T. Sakata, Conversion of carbohydrate into hydrogen fuel
by a photocatalytic process. 1980.
9. Tsuji, I., H. Kato, H. Kobayashi, and A. Kudo, Photocatalytic H2
Evolution Reaction from Aqueous Solutions over Band
Structure-Controlled (AgIn) x Zn2 (1-x) S2 Solid Solution Photocatalysts
with Visible-Light Response and Their Surface Nanostructures. Journal of
the American Chemical Society, 2004. 126(41): p. 13406-13413.
10. Kudo, A., H. Kato, and I. Tsuji, Strategies for the development of visible-light-driven photocatalysts for water splitting. Chemistry Letters,
2004. 33(12): p. 1534-1539.
11. Steele, B. C. and A. Heinzel, Materials for fuel-cell technologies. Nature,
2001. 414(6861): p. 345-352.
12. Wu, C.-C., H.-F. Cho, W.-S. Chang, and T.-C. Lee, A simple and
environmentally friendly method of preparing sulfide photocatalyst.
Chemical Engineering Science, 2010. 65(1): p. 141-147.
13. Chen, Y., S. Hu, W. Liu, X. Chen, L. Wu, X. Wang, P. Liu, and Z. Li,
Controlled syntheses of cubic and hexagonal ZnIn2S4 nanostructures with
different visible-light photocatalytic performance. Dalton Transactions,
2011. 40(11): p. 2607-2613.
14. Chen, Y., S. Hu, W. Liu, X. Chen, L. Wu, X. Wang, P. Liu, and Z. Li,
Controlled syntheses of cubic and hexagonal ZnIn 2S4 nanostructures with
different visible-light photocatalytic performance. Dalton Transactions,
2011. 40(11): p. 2607-2613.
15. Wang, T. X., S. H. Xu, and F. X. Yang, ZnIn2S4 nanopowder as an
efficient visible light-driven photocatalyst in the reduction of aqueous Cr
(VI). Materials Letters, 2012. 83: p. 46-48.
16. Shen, S., J. Chen, X. Wang, L. Zhao, and L. Guo, Microwave-assisted
hydrothermal synthesis of transition-metal doped ZnIn2S4 and its
photocatalytic activity for hydrogen evolution under visible light. Journal
of Power Sources, 2011. 196(23): p. 10112-10119.
17. Hu, X., J. C. Yu, J. Gong, and Q. Li, Rapid mass production of
hierarchically porous ZnIn2S4 submicrospheres via a
microwave-solvothermal process. Crystal Growth and Design, 2007.
7(12): p. 2444-2448.
18. Shen, S., J. Chen, X. Wang, L. Zhao, and L. Guo, Microwave-assisted
hydrothermal synthesis of transition-metal doped ZnIn 2S4and its
photocatalytic activity for hydrogen evolution under visible light. Journal
of Power Sources, 2011. 196(23): p. 10112-10119.
19. Shen, S., L. Zhao, and L. Guo, Cetyltrimethylammoniumbromide
(CTAB)-assisted hydrothermal synthesis of ZnIn2S4 as an efficient
visible-light-driven photocatalyst for hydrogen production. International
journal of hydrogen energy, 2008. 33(17): p. 4501-4510.
20. Shen, J., J. Zai, Y. Yuan, and X. Qian, 3D hierarchical ZnIn2S4: The
preparation and photocatalytic properties on water splitting. International
journal of hydrogen energy, 2012. 37(22): p. 16986-16993.
21. Shen, S., L. Zhao, and L. Guo, ZnmIn 2S3+ m (m= 1–5, integer): A new
series of visible-light-driven photocatalysts for splitting water to hydrogen.
International journal of hydrogen energy, 2010. 35(19): p. 10148-10154.
22. Olekseyuk, I., V. Halka, O. Parasyuk, and S. Voronyuk, Phase equilibria in
the AgGaS2–ZnS and AgInS2–ZnS systems. Journal of alloys and
compounds, 2001. 325(1): p. 204-209.
23. Torimoto, T., T. Adachi, K.-i. Okazaki, M. Sakuraoka, T. Shibayama, B.
Ohtani, A. Kudo, and S. Kuwabata, Facile synthesis of ZnS-AgInS2 solid
solution nanoparticles for a color-adjustable luminophore. Journal of the
American Chemical Society, 2007. 129(41): p. 12388-12389.
24. Kudo, A., I. Tsuji, and H. Kato, AgInZn7S9 solid solution photocatalyst for
H2 evolution from aqueous solutions under visible light irradiation.
Chemical communications, 2002(17): p. 1958-1959.
25. Serrano, D., M. Uguina, R. Sanz, E. Castillo, A. Rodrıguez, and P.
Sanchez, Synthesis and crystallization mechanism of zeolite TS-2 by microwave and conventional heating. Microporous and mesoporous
materials, 2004. 69(3): p. 197-208.
26. Shahid, R., M. S. Toprak, and M. Muhammed, Microwave-assisted low
temperature synthesis of wurtzite ZnS quantum dots. Journal of Solid
State Chemistry, 2012. 187: p. 130-133.
27. Ge, S. X., Z. Y. Shui, Z. Zheng, and L. Z. Zhang, A general
microwave-assisted nonaqueous approach to nanocrystalline ternary metal
chalcogenide and the photoluminescence study of CoIn2S4. Optical
Materials, 2011. 33(8): p. 1174-1178.
28. Link, S., Z. L. Wang, and M. El-Sayed, Alloy formation of gold-silver
nanoparticles and the dependence of the plasmon absorption on their
composition. The Journal of Physical Chemistry B, 1999. 103(18): p.
3529-3533.
29. Link, S. and M. A. El-Sayed, Spectral properties and relaxation dynamics
of surface plasmon electronic oscillations in gold and silver nanodots and
nanorods. The Journal of Physical Chemistry B, 1999. 103(40): p.
8410-8426.
30. Raether, H., Springer tracts in modern physics. Vol. 111. 1988.
31. Zayats, A. V., I. I. Smolyaninov, and A. A. Maradudin, Nano-optics of
surface plasmon polaritons. Physics reports, 2005. 408(3): p. 131-314.
32. Barnes, W. L., A. Dereux, and T. W. Ebbesen, Surface plasmon
subwavelength optics. Nature, 2003. 424(6950): p. 824-830.
33. Mafuné, F., J.-y. Kohno, Y. Takeda, T. Kondow, and H. Sawabe,
Formation and Size Control of Silver Nanoparticles by Laser Ablation in
Aqueous Solution. The Journal of Physical Chemistry B, 2000. 104(39): p.
9111-9117.
34. Link, S. and M. A. El-Sayed, Size and Temperature Dependence of the
Plasmon Absorption of Colloidal Gold Nanoparticles. The Journal of
Physical Chemistry B, 1999. 103(21): p. 4212-4217.
35. Kelly, K. L., E. Coronado, L. L. Zhao, and G. C. Schatz, The optical
properties of metal nanoparticles: the influence of size, shape, and
dielectric environment. The Journal of Physical Chemistry B, 2003.
107(3): p. 668-677.
36. Mock, J., M. Barbic, D. Smith, D. Schultz, and S. Schultz, Shape effects
in plasmon resonance of individual colloidal silver nanoparticles. The
Journal of chemical physics, 2002. 116(15): p. 6755-6759.
37. Kottmann, J. P., O. J. Martin, D. R. Smith, and S. Schultz, Plasmon
resonances of silver nanowires with a nonregular cross section. Physical
Review B, 2001. 64(23): p. 235402.
38. Lee, T. R., Metal Nanoshells for Plasmonically Enhanced Solar-to-Fuel
Photocatalytic Conversion ppt.
39. Maier, S. A. and H. A. Atwater, Plasmonics: Localization and guiding of
electromagnetic energy in metal/dielectric structures. Journal of Applied
Physics, 2005. 98(1): p. 011101.
40. Wei, A., Plasmonic nanomaterials, in Nanoparticles2004, Springer. p.
173-200.
41. Cushing, S. K., J. Li, F. Meng, T. R. Senty, S. Suri, M. Zhi, M. Li, A. D.
Bristow, and N. Wu, Photocatalytic activity enhanced by plasmonic
resonant energy transfer from metal to semiconductor. Journal of the
American Chemical Society, 2012. 134(36): p. 15033-15041.
42. Kochuveedu, S. T., D.-P. Kim, and D. H. Kim, Surface-plasmon-induced
visible light photocatalytic activity of TiO2 nanospheres decorated by Aunanoparticles with controlled configuration. The Journal of Physical
Chemistry C, 2012. 116(3): p. 2500-2506.
43. Ingram, D. B. and S. Linic, Water splitting on composite
plasmonic-metal/semiconductor photoelectrodes: evidence for selective
plasmon-induced formation of charge carriers near the semiconductor
surface. Journal of the American Chemical Society, 2011. 133(14): p.
5202-5205.
44. Zhang, Z., Z. Wang, S.-W. Cao, and C. Xue, Au/Pt
Nanoparticle-Decorated TiO2 Nanofibers with Plasmon-Enhanced
Photocatalytic Activities for Solar-to-Fuel Conversion. The Journal of
Physical Chemistry C, 2013. 117(49): p. 25939-25947.
45. Torimoto, T., H. Horibe, T. Kameyama, K.-i. Okazaki, S. Ikeda, M.
Matsumura, A. Ishikawa, and H. Ishihara, Plasmon-enhanced
photocatalytic activity of cadmium sulfide nanoparticle immobilized on
silica-coated gold particles. The Journal of Physical Chemistry Letters,
2011. 2(16): p. 2057-2062.
46. Takahashi, T., A. Kudo, S. Kuwabata, A. Ishikawa, H. Ishihara, Y. Tsuboi,
and T. Torimoto, Plasmon-Enhanced Photoluminescence and
Photocatalytic Activities of Visible-Light-Responsive ZnS-AgInS2 Solid
Solution Nanoparticles. The Journal of Physical Chemistry C, 2012.
117(6): p. 2511-2520.
47. Duan, H. and Y. Xuan, Enhancement of light absorption of cadmium
sulfide nanoparticle at specific wave band by plasmon resonance shifts.
Physica E: Low-dimensional Systems and Nanostructures, 2011. 43(8): p.
1475-1480.
48. Li, J., S. K. Cushing, J. Bright, F. Meng, T. R. Senty, P. Zheng, A. D. Bristow, and N. Wu, Ag@ Cu2O core-shell nanoparticles as visible-light
plasmonic photocatalysts. ACS Catalysis, 2012. 3(1): p. 47-51.
49. Daneshvar, N., M. Rabbani, N. Modirshahla, and M. A. Behnajady,
Kinetic modeling of photocatalytic degradation of Acid Red 27 in
UV/TiO2 process. Journal of photochemistry and photobiology A:
Chemistry, 2004. 168(1–2): p. 39-45.
50. Landry, C. C., J. Lockwood, and A. R. Barron, Synthesis of chalcopyrite
semiconductors and their solid solutions by microwave irradiation.
Chemistry of materials, 1995. 7(4): p. 699-706.