Dynamics of Electron Transfers in Photosensitization Reactions of Zinc Porphyrin Derivatives

被引:0
作者
Kim, Soohwan [1 ]
Kim, Taesoo [1 ]
Choi, Sunghan [1 ]
Son, Ho-Jin [1 ]
Kang, Sang Ook [1 ]
Shin, Jae Yoon [1 ]
机构
[1] Korea Univ, Dept Adv Mat Chem, Sejong 30019, South Korea
来源
MOLECULES | 2023年 / 28卷 / 01期
基金
新加坡国家研究基金会;
关键词
Zn porphyrin; TiO2; electron transfer; photosensitizer; time-resolved spectroscopy; CHARGE-TRANSFER; DYE; FLUORESCENCE; REDUCTION; STATE; TIO2; PHTHALOCYANINE; PHOTOCATALYST; PERFORMANCE; SELECTIVITY;
D O I
10.3390/molecules28010327
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Photocatalytic systems for CO2 reduction operate via complicated multi-electron transfer (ET) processes. A complete understanding of these ET dynamics can be challenging but is key to improving the efficiency of CO2 conversion. Here, we report the ET dynamics of a series of zinc porphyrin derivatives (ZnPs) in the photosensitization reactions where sequential ET reactions of ZnPs occur with a sacrificial electron donor (SED) and then with TiO2. We employed picosecond time-resolved fluorescence spectroscopy and femtosecond transient absorption (TA) measurement to investigate the fast ET dynamics concealed in the steady-state or slow time-resolved measurements. As a result, Stern-Volmer analysis of fluorescence lifetimes evidenced that the reaction of photoexcited ZnPs with SED involves static and dynamic quenching. The global fits to the TA spectra identified much faster ET dynamics on a few nanosecond-time scales in the reactions of one-electron reduced species (ZnPs(center dot-)) with TiO2 compared to previously measured minute-scale quenching dynamics and even diffusion rates. We propose that these dynamics report the ET dynamics of ZnPs(center dot-) formed at adjacent TiO2 without involving diffusion. This study highlights the importance of ultrafast time-resolved spectroscopy for elucidating the detailed ET dynamics in photosensitization reactions.
引用
收藏
页数:10
相关论文
共 30 条
[1]   Molecular artificial photosynthesis [J].
Berardi, Serena ;
Drouet, Samuel ;
Francas, Laia ;
Gimbert-Surinach, Carolina ;
Guttentag, Miguel ;
Richmond, Craig ;
Stoll, Thibaut ;
Llobet, Antoni .
CHEMICAL SOCIETY REVIEWS, 2014, 43 (22) :7501-7519
[2]   Electron Injection Process of Porphyrin Dye into a Heterogeneous TiO2/Re(I) Photocatalyst [J].
Choi, Sunghan ;
Choe, Min Su ;
Lee, Daehan ;
Kim, So-Yoen ;
Shin, Jae Yoon ;
Kim, Chul Hoon ;
Son, Ho-Jin ;
Pac, Chyongjin ;
Kang, Sang Ook .
JOURNAL OF PHYSICAL CHEMISTRY C, 2021, 125 (14) :7625-7636
[3]   Collisional Electron Transfer Route between Homogeneous Porphyrin Dye and Catalytic TiO2/Re(I) Particles for CO2 Reduction [J].
Choi, Sunghan ;
Kim, Chul Hoon ;
Baeg, Jin-Ook ;
Son, Ho-Jin ;
Pac, Chyongjin ;
Kang, Sang Ook .
ACS APPLIED ENERGY MATERIALS, 2020, 3 (12) :11581-11596
[4]   Rapid Exciton Migration and Amplified Funneling Effects of Multi-Porphyrin Arrays in a Re(I)/Porphyrinic MOF Hybrid for Photocatalytic CO2 Reduction [J].
Choi, Sunghan ;
Jung, Won-Jo ;
Park, Kyutai ;
Kim, So-Yeon ;
Baeg, Jin-Ook ;
Kim, Chul Hoon ;
Son, Ho-Jin ;
Pac, Chyongjin ;
Kang, Sang Ook .
ACS APPLIED MATERIALS & INTERFACES, 2021, 13 (02) :2710-2722
[5]   ELECTRON-TRANSFER QUENCHING OF S-2 STATE FLUORESCENCE OF ZN-TETRAPHENYLPORPHYRIN [J].
CHOSROWJAN, H ;
TANIGICHI, S ;
OKADA, T ;
TAKAGI, S ;
ARAI, T ;
TOKUMARU, K .
CHEMICAL PHYSICS LETTERS, 1995, 242 (06) :644-649
[6]   Proton-Coupled Electron Transfer Cleavage of Heavy-Atom Bonds in Electrocatalytic Processes. Cleavage of a C-O Bond in the Catalyzed Electrochemical Reduction of CO2 [J].
Costentin, Cyrille ;
Drouet, Samuel ;
Passard, Guillaume ;
Robert, Marc ;
Saveant, Jean-Michel .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (24) :9023-9031
[7]   Theoretical studies of photoinduced electron transfer in dye-sensitized TiO2 [J].
Duncan, Walter R. ;
Prezhdo, Oleg V. .
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, 2007, 58 :143-184
[8]   Excited State and Injection Dynamics of Triphenylamine Sensitizers Containing a Benzothiazole Electron-Accepting Group on TiO2 and Al2O3 Thin Films [J].
Fakis, Mihalis ;
Hrobarik, Peter ;
Yushchenko, Oleksandr ;
Sigmundova, Ivica ;
Koch, Marius ;
Rosspeintner, Arnulf ;
Stathatos, Elias ;
Vauthey, Eric .
JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (49) :28509-28519
[9]   Interfacial electron transfer dynamics and photovoltaic performance of TiO2 and ZnO solar cells sensitized with Coumarin 343 [J].
Giannouli, Myrsini ;
Fakis, Mihalis .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 2011, 226 (01) :42-50
[10]   Time-resolved fluorescence spectroscopy of high-lying electronic states of Zn-tetraphenylporphyrin [J].
Gurzadyan, GG ;
Tran-Thi, TH ;
Gustavsson, T .
JOURNAL OF CHEMICAL PHYSICS, 1998, 108 (02) :385-388