Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers...Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.展开更多
Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the...Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O.The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration.The obvious quenching of visible emission from IrⅢ complex in the IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes indicates that energy transfer occurred from IrⅢ center to lanthanides.NIR emissions from NdⅢ,YbⅢ,and ErⅢ were obtained under the excitation of visible light by selective excitation of the IrⅢ-based chromophore.It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdⅢ,YbⅢ,and ErⅢ.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21776207 and 21576195)。
文摘Molecular engineering is a crucial strategy for improving the photovoltaic performance of dye-sensitized solar cells(DSSCs). Despite the common use of the donor-π bridge-acceptor architecture in designing sensitizers, the underlying structure-performance relationship remains not fully understood. In this study, we synthesized and characterized three sensitizers: MOTP-Pyc, MOS_(2)P-Pyc, and MOTS_(2)P-Pyc, all featuring a bipyrimidine acceptor. Absorption spectra, cyclic voltammetry, and transient photoluminescence spectra reveal a photo-induced electron transfer(PET) process in the excited sensitizers. Electron spin resonance spectroscopy confirmed the presence of charge-separated states. The varying donor and π-bridge structures among the three sensitizers led to differences in their conjugation effect, influencing light absorption abilities and PET processes and ultimately impacting the photovoltaic performance. Among the synthesized sensitizers, MOTP-Pyc demonstrated a DSSC efficiency of 3.04%. Introducing an additional thienothiophene block into the π-bridge improved the DSSC efficiency to 4.47% for MOTS_(2)P-Pyc. Conversely, replacing the phenyl group with a thienothiophene block reduced DSSC efficiency to 2.14% for MOS_(2)P-Pyc. Given the proton-accepting ability of the bipyrimidine module, we treated the dye-sensitized TiO_(2) photoanodes with hydroiodic acid(HI), significantly broadening the light absorption range. This treatment greatly enhanced the short-circuit current density of DSSCs owing to the enhanced electron-withdrawing ability of the acceptor. Consequently, the HI-treated MOTS_(2)P-Pyc-based DSSCs achieved the highest power conversion efficiency of 7.12%, comparable to that of the N719 dye at 7.09%. This work reveals the positive role of bipyrimidine in the design of organic sensitizers for DSSC applications.
基金Supported by the National Basic Research Program of China (Grant No. 2006CB601103)the National Natural Science Foundation of China (Grant Nos. 20221101, 50772003, 20671006, 20971006, and 90922004)
文摘Bipyrimidines have been chosen as(N^N)(N^N) bridging ligands for connecting metal centers.IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes [Ir(dfppy)2(μ-bpm)Ln(TTA)3]Cl were synthesized by using Ir(dfppy)2(bpm)Cl as the ligand coordinating to lanthanide complexes Ln(TTA)3·2H2O.The stability constants between Ir(dfppy)2(bpm)Cl and lanthanide ions were measured by fluorescence titration.The obvious quenching of visible emission from IrⅢ complex in the IrⅢ-LnⅢ(Ln = Nd,Yb,Er) bimetallic complexes indicates that energy transfer occurred from IrⅢ center to lanthanides.NIR emissions from NdⅢ,YbⅢ,and ErⅢ were obtained under the excitation of visible light by selective excitation of the IrⅢ-based chromophore.It was proven that Ir(dfppy)2(bpm)Cl as the ligand could effectively sensitize NIR emission from NdⅢ,YbⅢ,and ErⅢ.