Wang Qing, Campbell Wayne M, Bonfantani Edia E, Jolley Kenneth W, Officer David L, Walsh Penny J, Gordon Keith, Humphry-Baker Robin, Nazeeruddin Mohammad K, Grätzel Michael
Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss Federal Institute of Technology, CH-1015 Lausanne, Switzerland.
J Phys Chem B. 2005 Aug 18;109(32):15397-409. doi: 10.1021/jp052877w.
A series of novel zinc metalloporphyrins, cyano-3-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-3), 3-(trans-2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-acrylic acid (Zn-5), 2-cyano-5-(2'-(5',10',15',20'-tetraphenylporphyrinato zinc(II))yl)-penta-2,4-dienoic acid (Zn-8), 4-(trans-2'-(2' '-(5' ',10' ',15' ',20' '-tetraphenylporphyrinato zinc(II))yl)ethen-1'-yl))-1,2-benzenedicarboxylic acid (Zn-11), and 2-cyano-3-[4'-(trans-2' '-(2' ''-(5' '',10' '',15' '',20' ''-tetraphenylporphyrinato zinc(II))yl) ethen-1' '-yl)-phenyl]-acrylic acid (Zn-13) were synthesized and characterized by using various spectroscopic techniques. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations show that key molecular orbitals (MOs) of porphyrins Zn-5 and Zn-3 are stabilized and extended out onto the substituent by pi-conjugation, causing enhancement and red shifts of visible transitions and increasing the possibility of electron transfer from the substituent. The porphyrins were investigated for conversion of sunlight into electricity by constructing dye-sensitized TiO(2) solar cells using an I(-)/I(3)(-) electrolyte. The cells yield close to 85% incident photon-to-current efficiencies (IPCEs), and under standard AM 1.5 sunlight, the Zn-3-sensitized solar cell demonstrates a short circuit photocurrent density of 13.0 +/- 0.5 mA/cm(2), an open-circuit voltage of 610 +/- 50 mV, and a fill factor of 0.70 +/- 0.03. This corresponds to an overall conversion efficiency of 5.6%, making it the most efficient porphyrin-sensitized solar cell reported to date.
合成了一系列新型锌金属卟啉，即氰基-3-(2'-(5',10',15',20'-四苯基卟啉锌(II))基)-丙烯酸(Zn-3)、3-(反式-2'-(5',10',15',20'-四苯基卟啉锌(II))基)-丙烯酸(Zn-5)、2-氰基-5-(2'-(5',10',15',20'-四苯基卟啉锌(II))基)-戊-2,4-二烯酸(Zn-8)、4-(反式-2'-(2''-(5'',10'',15'',20''-四苯基卟啉锌(II))基)乙烯-1'-基))-1,2-苯二甲酸(Zn-11)和2-氰基-3-[4'-(反式-2''-(2'''-(5''',10''',15''',20'''-四苯基卟啉锌(II))基)乙烯-1''-基)-苯基]-丙烯酸(Zn-13)，并使用各种光谱技术对其进行了表征。密度泛函理论(DFT)和含时密度泛函理论(TDDFT)计算表明，卟啉Zn-5和Zn-3的关键分子轨道(MOs)通过π共轭得到稳定并延伸到取代基上，导致可见跃迁增强和红移，并增加了电子从取代基转移的可能性。通过使用I(-)/I(3)(-)电解质构建染料敏化TiO(2)太阳能电池，研究了这些卟啉将太阳光转化为电能的性能。这些电池的入射光子到电流效率(IPCEs)接近85%，在标准AM 1.5太阳光下，Zn-3敏化太阳能电池的短路光电流密度为13.0±0.5 mA/cm(2)，开路电压为610±50 mV，填充因子为0.70±0.03。这对应于5.6%的总转换效率，使其成为迄今为止报道的最有效的卟啉敏化太阳能电池。
