Preparation Of Porphyrin-based Organic And Inorganic Supramolecular Materials And Study On Their Nonlinear Optical Properties And Photocatalytic Degradation Of 2-chloroethyl Ethyl Sulfide

Tetraphenyl porphyrin containing metal center highly delocalizedπconjugated system,not only has good nonlinear optical response,but also under the condition of visible light irradiation to produce singlet oxygen,can selectively mustard gas simulation agent CEES sulfoxide form of oxidation for non-toxic,is a kind of excellent organic nonlinear optical material and photosensitizer,It has excellent research value in nonlinear laser protection and photocatalytic degradation of mustard gas.This article embarks from the metal porphyrin,the design of the two different types of organic-inorganic subject system,extend the conjugate system of hybrid material,reduces the accumulation of porphyrin,thus enhance the nonlinear optical response of porphyrins and the yield of singlet oxygen,is a kind of laser protection and light catalytic degradation of mustard gas has double functions of supramolecular materials.The main conclusions are as follows:1.3,4’,4’’,4’’’-copper phthalocyanine（CuPcTS）and tetrahydroxy phenyl zinc porphyrin（ZnTHPP）or tetracarboxyl phenyl zinc porphyrin（ZnTCPP）containing different groups on benzene ring were co-intercalated to magnesium aluminum hydrotalcitine（Mg₂Al-LDH）laminate at different concentration ratios.LDH-（ZnTHPP）_x（CuPcTS）_y and LDH-（ZnTCPP）_x（CuPcTS）_y complexes were synthesized with the concentration ratios of porphyrin/phthalocyanine at 3:1,2:1,1:1,1:2 and1:3 respectively,and they were characterized by ¹H NMR,elemental analysis,UV-vis,XRD and SEM.The photocatalytic degradation of porphyrin-phthalocyanine hydrotalcite co-intercalated complexes on mustard gas simulator（2-chloroethyl ethyl sulfide,CEES）was studied.The results showed that the degradation rates of LDH-（ZnTHPP）₁（CuPcTS）₂ and LDH-（ZnTHPP）₁（CuPcTS）₃ were 90.5%after180 min of visible light catalytic reaction.The degradation rates of other LDH-（ZnTHPP）_x（CuPcTS）_y and LDH-（ZnTCPP）_x（CuPcTS）_y hybrids were above 99%,and could still reach 99%after five repetitions.The half-life of LDH-（ZnTHPP）_x（CuPcTS）_y is shorter than that of LDH-（ZnTCPP）_x（CuPcTS）_y with the same concentration ratio.LDH-（ZnTHPP）₃（CuPcTS）₁ has the shortest half-life of 19.61 min.GC-MS analysis showed that CEES were degraded by oxidation and hydrolysis.In addition,the third-order nonlinear properties of hybrid materials were also studied.LDH-（ZnTHPP）₃（CuPcTS）₁ had the highestχ^（3）value(13.31×10^-11（esu）)andγ(6.88×10^-28（esu）)in LDH-（ZnTHPP）_x（CuPcTS）_y.LDH-（ZnTCPP）₁（CuPcTS）₁ had the highestχ^（3）value(13.12×10^-11（esu）)andγ(6.79×10^-28（esu）)in LDH-（ZnTCPP）_x（CuPcTS）_y.They are much larger than their corresponding single intercalated hybrid materials.The porphyrin-phthalocyanine hydrotalcite co-intercalated material synthesized in this paper not only has excellent third-order nonlinear optical response,but also can degrade CEES rapidly and efficiently,which has great potential application value in nonlinear laser protection and mustard agent degradation fields.2.Molybdenum wheel type more acid Na₁₆[（MoO₃）₁₇₆（H₂O）₆₃（CH₃OH）₁₇H₁₆]·ca.100H₂O({Mo₁₇₆})were choosed to reaction with three tetraphenyl zinc porphyrin（tetracarboxyl phenyl zinc porphyrin ZnTCPP,tetrahydroxy phenyl zinc porphyrin ZnTHPP,tetraminophenyl zinc porphyrin ZnTAPP）which benzene rings contain different substituent（-COOH,-OH,NH₂）respectively.Three porphyrin-polyacid complexes(ZnTCPP-{Mo₁₇₆},ZnTHPP-{Mo₁₇₆}and ZnTAPP-{Mo₁₇₆})were prepared by hydrogen bonding（denoted as hybrid1-3）.Hybrid 1-3 were characterized by ¹H NMR,IR,UV-vis,fluorescence,thermogravimetric analysis and elemental analysis.The degradation of hybrid 1-3 to mustard gas simulant CEES was studied.The results showed that the degradation rate of hybrid 1 and hybrid 2 to CEES was 99%and that of hybrid 3 was 97.22%after 180 min reaction.The degradation rate of CEES was in the order of hybrid 2>hybrid 1>hybrid 3.Product analysis by GC-MS showed that the degradation of CEES by hybrid 1-3was mainly through oxidation process.The degradation process of CEES by hybrid 1-3 was a homogeneous catalytic first-order kinetic reaction,with good reuse performance.The half-lives of hybrid 1-3 were 13.04,9.73and 24.60 min,respectively.In addition,the nonlinear optical properties of three porphyrin-polyacid complexes were also studied.The results showed that the order ofχ^（3）andγvalues was as follows:hybrid 1>hybrid 2>hybrid 3.The nonlinear optical response parameters of hybrid 1-3 were all larger than their corresponding porphyrins.Both hybrid 1 and hybrid 2 had large nonlinear attenuation factors（5.65 and 3.69,respectively）and low limiting thresholds(0.3 and 0.32(J/cm^-1),respectively).So in this paper,the synthesis of such clusters-molybdenum wheel porphyrin hybrid materials not only have excellent third-order nonlinear optical response,and can quickly efficient degradation CEES,degradation and mustard gas agents in the field of nonlinear laser protection field has a great potential application value,is expected to be developed as a new type of promising nonlinear optical limiting and mustard gas degradation of dual functional materials.