7
摘要
五種本實驗室裡合成出來的聯砒啶釕錯合物，被成功的做成光敏
性太陽能電池。光電流的產生率可用來探討此類釕錯合物在激發態
時，電子在配位基上的分佈情形，是否會影響電子由激發態注入到
TiO2 傳導帶上的效率。實驗結果顯示，當釕錯合物在激發態時，電子
密度分佈在含羧酸基的bpy 上的比例較多時，的確可以造成較好的光
電流值。同時我們也使用循環伏特安培計(CV)，來偵測此光電系統
中I3
－離子的產生速率，雖然在測量上受到了干擾而無法準確的估計
I3
－生成速率，但我們確定了可以利用逆反應來觀察電解液中I3
－離子
的生成速率。
利用TiO2 nano-particles 的特性，可以使Hemin 照光激發後，將
電子由激發態注入至TiO2 的傳導帶上，本身則被氧化成FeIII(P•＋)。當
有受質Guaiacol 存在時，會得到單電子的氧化物，再偶合得到雙聚物
3,3΄-dimethoxy-4,4΄-dihydroxy-biphenyl。此產物的生成更確定了ferric
cation-radical porphyrin (FeIII(P•＋)) 的形成。光激發活化血基質，是除
了以氧化劑、電化學方式之外，另一條活化血基質蛋白酵素的路徑。

8
Five ruthenium bipyridine type complexes have been incorporated
into the dye-sensitized solar cell system. The results show the
distribution of the electron density of the ruthenium complexes in the
excited state will slightly alter the photo-to-current efficiency. When the
carboxyl containing bipyridine has more electron density in the excited
state, the photo-to-current values will increase. The Cyclic Voltammetry
has been used to detect the production of the I3
－ ion.
Although Hemin has a very short-lived excited-state, it has
photochemistry while absorbed onto nano-sized TiO2 particles. Upon
excitation, Hemin injects one electron into the conduction band of
titanium dioxide and oxidizes to FeIII(P•+). In the presence of substrate,
Guaiacol, the major photoproduct is radical coupled dimer,
3,3΄-dimethoxy-4,4΄-dihydroxy-biphenyl. This result further supports
the formation of ferric cation-radical porphyrin (FeIII(P•+)) upon excition.
Photoinduced FeIII(P•+) formation is a new route to initiate iron-porphyrin
catalysis.

9
【Reference 】
1. Grätzel, M. Natrue 2001, 414, 338.
2. Honda, K.; Fujishima, A. Nature 1972, 238, 37.
3. Tufts, B. J. Nature 1987, 326, 681.
4. Heller, A. Acc. Chem. Res. 1981, 14, 154.
5. Tributsch, H.; Bennet, J. C. J. Electroanal. Chem. 1977, 81, 97.
6. Bard, A. J. Science 1980, 207, 139.
7. O’Regan, B.; Grätzel, M. Natrue (Landon) 1991, 353, 737.
8. Nazeeruddin, Md. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.; Müller,
E.; Liska, P.; Vlachopoulos, N.; Grätzel, M. J. Am. Chem. Soc. 1993,
115, 6382.
9. (a) Argazzi, R.; Bignozzi, C. A.; Heimer, T. A.; Castellano, F. N.;
Meyer, G. J. J. Phys. Chem. B 1997, 101, 2591. (b) Kelly, C. A.; Farzad,
F.; Thompson, D. W.; Meyer, G. J. Langmuir 1999, 15, 971. (c)
Gholamkhass, B.; Koike, K.; Negishi, N.; Hori, H.; Takeuchi, K. Inorg.
Chem. 2001, 40, 756. (d) Renouard, T.; Grätzel, M. Tetrahedron 2001,
57, 8145. (e) Hara, K.; Sugihara, H.; Tachibana, Y.; Islam, A.; Yanagida,
M.; Sayama, K.; Arakawa, H. Langmuir 2001, 17, 5992.
10. Hara, K.; Sato, T.; Katoh, R.; Furube, A.; Ohga, Y.; Shinpo, A.; Suga,
S.; Sayama, K.; Sugihara, H.; Arakawa, H. J. Phys. Chem. B 2003, 107,
597.
11. Huber, R.; Spörlein, S.; Moser, J. E.; Grätzel, M.; Wachtveitl, J. J.
Phys. Chem. B 2000, 104, 8995.
12. Ehret, A.; Stuhl, L.; Spitler, M. T. J. Phys. Chem. B 2001, 105, 9960.