The Molecular Design And Synthesis Of A Novel Triphenylamine Sensitized Dye

In recent years,with the rapid development of global industry,the demand for energy has been increasing,and the emission of large quantities of greenhouse gases lead to serious impact on the sustainable development of ecological balance.Development of renewable energy becomes an important way to solve the energy crisis and maintains the sustainable development of ecological balance.The solar energy as a renewable energy has the advantages of economy,environmental protection,sustainable development,so more and more attention have been foused on the research of solar energy.The high performance of sensitized dyes is crucial to improve photoelectric conversion efficiency.Triphenylamine,which could be used as electron donor in dye-sensitized solar cells,has been widely studied because of its unique spatial structure.With the development of quantum chemical calculation method and high performance computing platform,it is possible to study the molecular tructure and properties by computer.It can shorten development time and avoid waste of experimental resources.Two kinds of sensitizing dye molecules were designed in this paper.The first kind is D-A-?-A type sensitized dyes,obtained by introducing additional receptors in the dye B1;The second kind is the sensitized dye B1 with the benzene and oxadiazoles as additional receptor,bonding with the different groups on the triphenylamine branched chai.The density functional theory were used to study the structural optimization,charge distribution and energy calculation of the new dyes.Therefore,the impact of the different receptors and triphenylamine extra branched chain could be xplored.The calculation results show that all of the eleven dyes could maintain stable spatial structure,good absorption range of isible light and infrared light,and the narrow band gaps.The intramolecular charge transfer phenomenos were found in the calculation studys.All of the HOMO energy level are lower than the oxidation reduction potential of the electrolyte,at the same time,all of the LUMO energy level are haigher than the onduction band energy level of the TiO₂.As a result,the structures could ensure the electron transfer effectively and the regeneration of the dyes.Based on the comprehensive analysis,the theoretical performance ranking of the two kinds of dyes were revealed,shch as:DPP>BTD>BOD>PDP>Qu>BTZ>B1 and Dye E>DyeB>DyeC>DyeA>DyeD>B1–BOD.According to the calculation results,the B1-BOD and DyeE with good formance were determined.The formaldehyde,benzene and 1-4-three aniline boric acid,boric acid-4,4,4,-dimethoxy triphenylamine,cyano acetic acid were used as main raw materials.The B1-BOD and DyeE were synthesized by bromine generation reaction,Suzuki coupling reaction,the Knoevenagel condensation.The intermediates and target product were detected by 1 h NMR,13 c NMR,MS and IR.The results show that the target product B1-BOD and Dye E had been synthesized.The optical test,electrochemical test and photovoltaic performance test were carried out for B1-BOD and DyeE.The results showed that the two dyes both have the wide range absorption spectra,ranging from 200 to 652.5nm and 200-700 nm respectively.The HOMO and LUMO energy level of the two dyes could match the energy levels of TiO₂and electrolyte,which are in accordance with the sensitizer conditions.And quantum chemistry is used to calculate their electronic transition parameters,which theoretically indicates that the two dyes have good performance.