| With the rapid development of society,the demand for functional materials is increasing.It is a hot topic to seek new or improve traditional materials.According to the shortage of energy and ecological environment,it is urgent to explore the catalyst for hydrogen production from water with high efficiency and stability.In the field of high-speed communication and frequency conversion,it is necessary to explore new optical materials with better performance in the field of high-speed communication and frequency conversion.On this basis,according to the characteristics of porphyrin due to its stable large?conjugate structure and strong modification of the outer ring,the catalytic performance of transition metal porphyrins for hydrogen production is studied by introducing different metals which have great influence on the properties of the porphyrin,which is characterized by its stable large?conjugate structure and strong modification of the outer ring.The optical properties of picrate quaternary phosphonium salt were investigated by fine-tuning the structure of benzyltriphenylphosphonium ion and its derivative cations.Twelve metal cobalt complexes with different substituents in the phenyl rings were synthesized based on 3-substituted complexs Co[T(3-R)PP],where R=F(1),Cl(2),Br(3),and CN(4);bisubstituent owes Co[T(3,5-bi Br)PP](5)and Co TPP,3-substituted-4-sulfonic porphyrins Co[T(3-R)PPS],R=F(6),Cl(7),and Br(8);4-imidazolyl porphyrin Co[T(4-R)PP],R=thidia(9),tria(10),tetra(11),and benzimida(12).The performance of catalytic hydrogen production was investigated and the influence of structure on the performance was preliminarily analyzed.A nonlinear optical crystal material,[2Cl4Cl Bz TPP][PIC](13)was synthesized,and its crystal structure analysis and optical properties were investigated.1.Four kinds of non-water soluble 3-substituted metal cobalt porphyrins 1,2,3,and 4,were synthesized,and their properties of electrocatalytic hydrogen production was studied.When the overpotential of acetic acid as proton in organic solution is 941.6 m V,the TOF values are 42.24 h-1(3)>37.16 h-1(1)>26.95 h-1(2)>26.06 h-1(4),respectively.In neutral phosphate buffer solution,the TOF with overpotential of 837.6 m V is 228.39 h-1(3)>203.66h-1(2)>165.65 h-1(1)>126.08 h-1(4),respectively.2.3,5-bisubstituted metal cobalt porphyrin was synthesized and compared with unsubstituted cobalt porphyrin 6 by electrocatalysis and photocatalysis.The TOF in organic phase was 126.2 h-1(5)>41.8 h-1(Co TPP),and the TOF in neutral buffer solution was 844.2h-1(5)>352.5 h-1(6).The yield of hydrogen produced by photocatalysis for 9 h is 3.64 mmol(Co TPP)>2.31 mmol(5),respectively.3.Three sulfonic-based water-soluble metal cobalt porphyrins 6,7 and 8 were synthesized,and the catalytic hydrogen production was studied in homogeneous system.In neutral phosphate solution,when the applied potential is 1100 m V,the TOF value is 1616.4h-1(6)>1326.4 h-1(7)>1252.3 h-1(8).The order of hydrogen obtained after further electrolysis for 1 h was 58.09 m L(6)>51.87 m L(7)>40.99 m L(8).4.The electrocatalytic hydrogen production was carried out by the synthesis of 4 kinds of detomidine 9,10,11,and 12.The TOF value obtained in the organic phase is 119.5 h-1(9)>103.03 h-1(11)>96.5 h-1(12)>75.7 h-1(10),and the value in the neutral phosphate solution is 1475.02 h-1(9)>963.7 h-1(11)>885.1 h-1(12)>713.3 h-1(10).5.A bisubstituted benzylquaternary phosphonium salt 13 was synthesized and compared with[Bz TPP][PIC]to explore their nonlinear optical properties.The two quaternary phosphonium salts are monoclinic,P2(1)/c space group.Their thermal stability and fluorescence properties are tested,and the results show that they have good thermal resistance.The phosphonium salt 13 shows the main emission peaks at 377 nm and 509nm under 250nm wavelength excitation,which indicates that the phosphonium salt 13 has purple and green fluorescence emission.[Bz TPP][PIC]has a strong emission peak at 295 nm and 388 nm under 240 nm excitation,indicating that it has purple fluorescence emission.The IR,Raman and nonlinear optical effects of the complexes were calculated by density functional theory(DFT).The results show that the calculated values are in good agreement with the experimental values.The first hyperpolarizability?tot of complex 13 is 10.2 times higher than that of the reference crystal KDP.The first hyperpolarizability(?tot)of the complex 13 and[Bz TPP][PIC]is 10.2 and 16 times,respectively,of the reference crystal KDP. |
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