Phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and preparation method thereof
阅读说明：本技术 酞菁衍生物修饰表面活性剂与多金属氧酸盐自组装纳米材料及其制备方法 (Phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and preparation method thereof ) 是由 王蕊欣 王飞 刘叶峰 陈南 左鹏 焦纬洲 赵文英 于 2019-08-13 设计创作，主要内容包括：本发明属功能材料制备技术领域,针对多金属氧酸盐作催化剂易溶于水、难分离回收,作光催化剂时光响应范围窄等缺陷,提供一种酞菁衍生物修饰表面活性剂与多金属氧酸盐复合物的自组装纳米材料及其制备方法。由酞菁衍生物与双链阳离子表面活性剂共价键合制得酞菁衍生物修饰表面活性剂,然后与多金属氧酸盐静电相结合形成复合物,该复合物在溶液中自组装形成具有一定形貌结构的纳米材料。使表面活性剂有了酞菁的光谱学性质。不仅提高酞菁在溶液中的分散性,增强酞菁的光催化活性,还能够使酞菁的光催化活性与POM的光催化功能发挥协同作用。在溶液中自组装得到了不同形貌的纳米材料,将在光电材料、光催化等领域具有重要意义。(The invention belongs to the technical field of functional material preparation, and provides a self-assembly nano material of a phthalocyanine derivative modified surfactant and polyoxometallate compound and a preparation method thereof, aiming at the defects that polyoxometallate is easy to dissolve in water and difficult to separate and recycle as a catalyst, and the photoresponse range is narrow when the polyoxometallate is used as a photocatalyst. The phthalocyanine derivative modified surfactant is prepared by covalent bonding of a phthalocyanine derivative and a double-chain cationic surfactant, and then is combined with polyoxometallate in an electrostatic manner to form a compound, and the compound is self-assembled in a solution to form a nano material with a certain morphology structure. The surfactant is made to have the spectroscopic properties of phthalocyanine. Not only improves the dispersibility of the phthalocyanine in the solution and enhances the photocatalytic activity of the phthalocyanine, but also enables the photocatalytic activity of the phthalocyanine and the photocatalytic function of the POM to play a synergistic role. The nano materials with different morphologies are obtained by self-assembly in the solution, and the method has important significance in the fields of photoelectric materials, photocatalysis and the like.)
1. A phthalocyanine derivative-modified surfactant characterized by: the phthalocyanine derivative modified surfactant is a double-chain cationic surfactant modified by a phthalocyanine derivative, and the phthalocyanine derivative is: a tetra-beta- (4-nitro) metal phthalocyanine MNPc, wherein NPc is tetra-beta- (4-nitro) phthalocyanine; m = any one of Fe, Co, Mn, Zn, Ni, or Cu; the double-chain cationic surfactant is 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol).
2. A method of preparing a phthalocyanine derivative-modified surfactant according to claim 1, comprising: the method comprises the following steps: dissolving 0.5-1.00 g of MNPc in 30-55 mL of DMSO, adding 20-45 mL of DMSO solution containing DDAB-11-ol, and introducing N2Heating for 20-30 min to 45-55Reacting at 0.5-1.5 hr under magnetic stirring, and mixing at 0.36-0.41 g K deg.C2CO3Adding the raw materials into the reaction system in four batches within two hours, monitoring the reaction process by a point plate, finishing the reaction after DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 400-500 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product by using ethanol, filtering to remove unreacted phthalocyanine derivatives, performing rotary evaporation on the filtrate, and drying to obtain the phthalocyanine derivative modified double-chain cationic surfactant MNPc-O-DDAB.
3. The method for producing a phthalocyanine derivative-modified surfactant according to claim 2, wherein: the molar ratio of MNPc to DDAB-11-ol is 1:2-3: 1.
4. A phthalocyanine derivative-modified surfactant-bound polyoxometalate complex, the phthalocyanine derivative-modified surfactant being MNPc-O-DDAB prepared according to claim 2, characterized in that: the polyoxometallate POM is Keggin type phosphotungstic acid H3PW12O40·xH2O, Dawson type phosphotungstate K6 [α-P2W18O62]·14H2O, Dawson type phosphotungstate K10[α-P2W17O61]·20H2O or Waugh type phosphotungstate Na3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O。
5. A method of preparing a phthalocyanine derivative-modified surfactant-bound polyoxometalate complex as claimed in claim 4, wherein: the method comprises the following specific steps: dissolving 0.05-0.1 g of MNPc-O-DDAB in 50-70 mL of absolute ethyl alcohol, dropwise adding 40-50mL of aqueous solution containing POM under magnetic stirring, reacting for 8-12 h, centrifuging the reaction solution, successively washing for 3-5 times by using the absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the compound MNPc-O-DDAB/POM of the phthalocyanine derivative modified double-chain cationic surfactant combined with polyoxometallate.
6. The method of preparing a phthalocyanine derivative-modified surfactant-bound polyoxometalate complex as claimed in claim 5, wherein: the molar ratio of the MNPc-O-DDAB to the POM is 1:6-3: 1.
7. The method for preparing a self-assembly material in solution from a phthalocyanine derivative modified surfactant-bound polyoxometalate complex prepared in claim 5, characterized in that: the specific method comprises the following steps: fully dissolving 0.004 g of MNPc-O-DDAB/POM in 4-10 mL of good solvent, adding 1-8mL of poor solvent under the condition of ultrasound/oscillation, and standing for 30 min after 10-15 min of ultrasound/oscillation to obtain a self-assembly solution;
Centrifuging the self-assembly solution at 25 deg.C and 8000rpm for 10-15 min, dispersing the precipitate in 10-20 ml deionized water, standing for 60-120 min, and centrifuging at 25 deg.C and 8000rpm to obtain spindle-shaped or spherical MNPc-O-DDAB/POM self-assembly material; or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160-200 ℃ for 10-12 h to obtain the stable shuttle-shaped or spherical MNPc-O-DDAB/POM self-assembly material.
8. The method for preparing the self-assembly material of the phthalocyanine derivative modified surfactant-bound polyoxometalate complex in solution according to claim 7, wherein: the good solvent is dimethyl sulfoxide DMSO and N, N-dimethylformamide DMF processed by anhydrous magnesium sulfate; the poor solvent is water or carbon tetrachloride.
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and a preparation method thereof. The material is formed by self-assembling a compound of a phthalocyanine derivative modified surfactant and polyoxometallate in a solution; the phthalocyanine derivative modified surfactant is prepared by covalently bonding a phthalocyanine derivative and a surfactant, and the phthalocyanine derivative modified surfactant and a polyoxometallate compound are combined through electrostatic interaction.
Background
Polyoxometalates (abbreviated as POM) are inorganic metal oxygen cluster compounds formed by connecting high-valence early transition metals (V, Nb, Ta, Mo, W, etc.) and oxygen atoms through oxygen coordination bridges. The polyoxometalate cluster consists of two parts, namely an oxygen-enriched anion cluster and a counter cation. Polyoxometallate is a compound with a structure smaller than that of virus molecules, the size is about 0.5-5 nm, and the polyoxometallate can be dissolved in polar solvents such as water and the like. It possesses excellent chemical properties such as redox, electron transfer, ion exchange, etc. due to its unique and steric framework. Other characteristics such as exhibiting a stronger acidity than conventional inorganic oxyacids are considered to be solid superacids which have a higher acid strength than concentrated sulfuric acid in non-polar organic solvents and a very high thermal stability. The polyoxometallate also has strong oxidizability and reducibility, has good storage capacity for electrons and protons, can absorb ultraviolet light and the like, and is an ideal raw material for preparing functional materials. However, the use of polyacids is limited by the disadvantages of small specific surface area, high solubility in polar solvents such as water, difficulty in separation and recovery, etc.
Researches find that the controllable self-assembly of the POM is beneficial to the materialization use of the POM.self-assembly of polyoxometalate clusters in solution was first discovered by A.M ü ller and T.B. Liu et al, who discovered a wheel in 2003 { Mo154The anion cluster can self-assemble in aqueous solution to form an assembly body with a hollow monolayer vesicular blackberry structure, and the polymetallic oxygen cluster with larger size can basically form the assembly body spontaneously in aqueous solution, but the assembled form and structure are relatively single. Therefore, in order to obtain a functionally-rich and structurally-diverse assembly, researchers have organically modified POM and induced its self-assembly. Functional organic groups are modified on polyoxometallate through a physical or chemical method to obtain functional organic-inorganic hybrid composite molecules, and the composite molecules can be self-assembled to generate aggregates with various structures and rich functions. The organic cationic surfactant is utilized to carry out electrostatic modification on the POM, so that the amphipathy of the compound is improved, the controllable aggregation of the compound is facilitated, the flexibility of self-assembly of the organic-inorganic hybrid compound in a solution is greatly improved, and the organic cationic surfactant is a research hotspot in the field of current material science.
The phthalocyanine compound is a highly conjugated system with 18 pi electrons, aromatic pi electrons of the phthalocyanine compound are conjugated on the whole porphyrazine ring, the phthalocyanine compound is a conjugated macromolecule with high planarity, and the phthalocyanine compound has the characteristics of electron supply and electron donor, and the whole chemical property is very stable; the p-type semiconductor is a p-type semiconductor, has strong absorption and fluorescence emission of a B band (300-400 nm) and a Q band (600-800 nm), can perform energy transfer with a triplet state oxygen molecule under a certain excitation wavelength to generate singlet state oxygen molecules with high activity, can be effectively used as a photosensitizer or a catalyst, and is widely applied to optical materials, semiconductor materials and the like.
Disclosure of Invention
The invention provides the following defects that Polyoxometallate (POM) is easy to dissolve in water and difficult to separate and recycle as a catalyst, and has narrow photoresponse range when being used as a photocatalyst and the like: (1) a phthalocyanine derivative modified surfactant and a preparation method thereof; (2) a phthalocyanine derivative modified surfactant combined polyoxometallate compound and a preparation method thereof; (3) the prepared phthalocyanine derivative modified surfactant and polyoxometallate compound self-assembly nano material and a preparation method thereof.
Dawson type phosphotungstate K used in the present invention6 [α-P2W18O62]·14H2O according to The reference [ Graham C R, Finke R G, The classic Wells-Dawson polyoxometalate, K6[alpha-P2W18O62].14H2O. Answering an 88 year-old question: what is its preferred, optimum synthesis[J]. Inorganic Chemistry, 2008, 47(9): 3679-3686]Preparing; k used10[α-P2W17O61]·20H2O (abbreviated as P)2W17) According to the literature [ cyanine, preparation of covalently bonded polyacid/naphthalene and porphyrin hybrid materials and research on photoelectric properties [ D]Hubei: 2014: 23-24 of Hubei university]Preparing; the Waugh type phosphotungstate Na is used3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O according to the reference [ Lv H, Gao Y, Guo W, et al. Cu-based Polyoxometalate Catalyst for Efficient Catalytic Hydrogen Evolution [ J]. Inorganic Chemistry, 2016, 55(13): 6750.]Preparing; the phthalocyanine derivatives (MNPc) used are based on the simple synthesis and characterization of two tetraamino zinc phthalocyanine isomers according to the reference [ Congress, Du-tin-light, Zhao-Bao, et al. ] [ J]The higher school journal of chemistry 2002,23(12): 2221-2225.]Preparing; the 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol) is used according to the reference [ Zhang jiao. Anthracene modified surfactant/polymetallic oxygen cluster compound light-controlled self-assembly [ D]Jilin: jilin university, 2015: 19-21.]And (4) preparation.
The invention is realized by adopting the following technical scheme: a phthalocyanine derivative-modified surfactant which is a phthalocyanine derivative-modified double-stranded cationic surfactant, the phthalocyanine derivative being: a tetra-beta- (4-nitro) metal phthalocyanine MNPc, wherein NPc is tetra-beta- (4-nitro) phthalocyanine; m = any one of Fe, Co, Mn, Zn, Ni, or Cu; the double-chain cationic surfactant is 11-alcohol-didodecyldimethylammonium bromide (DDAB-11-ol).
The method for preparing the phthalocyanine derivative modified surfactant comprises the following specific steps: dissolving 0.5-1.00 g of phthalocyanine derivative MNPc in 30-55 mL of DMSO, adding 20-45 mL of DMSO solution in which a certain amount of DDAB-11-ol is dissolved, and introducing N2Heating to 45-55 deg.C for 20-30 min, reacting for 0.5-1.5 hr under magnetic stirring, and mixing with 0.36-0.41 g K2CO3Adding the raw materials into the reaction system in four batches within two hours, monitoring the reaction process by a point plate, finishing the reaction after DDAB-11-ol in the system is completely reacted, pouring the reaction solution into 400-500 mL of ice water, performing suction filtration to obtain a crude product, re-dissolving the crude product by using ethanol, filtering to remove unreacted phthalocyanine derivatives, performing rotary evaporation on the filtrate, and drying to obtain the phthalocyanine derivative modified double-chain cationic surfactant MNPc-O-DDAB. Wherein the molar ratio of MNPc to DDAB-11-ol is 1:2-3: 1.
The phthalocyanine derivative modified surfactant is MNPc-O-DDAB prepared by the method, and the polyoxometallate POM is Keggin type phosphotungstic acid H3PW12O40·xH2O, Dawson type phosphotungstate K6 [α-P2W18O62]·14H2O, Dawson type phosphotungstate K10[α-P2W17O61]·20H2O or Waugh type phosphotungstate Na3K7[Cu4(H2O)2(B-α-PW9O34)2]·30H2O。
The preparation method of the phthalocyanine derivative modified surfactant combined polyoxometallate compound comprises the following specific steps: dissolving 0.05-0.1 g of MNPc-O-DDAB in 50-70 mL of absolute ethyl alcohol, dropwise adding 40-50mL of aqueous solution containing POM under magnetic stirring, reacting for 8-12 h, centrifuging the reaction solution, successively washing for 3-5 times by using the absolute ethyl alcohol and deionized water, and drying in vacuum to obtain the compound MNPc-O-DDAB/POM of the phthalocyanine derivative modified double-chain cationic surfactant combined with polyoxometallate. Wherein the molar ratio of MNPc-O-DDAB to POM is 1:6-3: 1.
The preparation method of the self-assembly nano material in the solution by combining the phthalocyanine derivative modified surfactant and the polyoxometallate compound comprises the following specific steps: fully dissolving 0.004 g of MNPc-O-DDAB/POM in 4-10 mL of good solvent, adding 1-8mL of poor solvent under the condition of ultrasound/oscillation, and standing for 30 min after 10-15 min of ultrasound/oscillation to obtain a self-assembly solution;
Centrifuging the self-assembly solution at 25 deg.C and 8000rpm for 10-15 min, dispersing the precipitate in 10-20 ml deionized water, standing for 60-120 min, and centrifuging at 25 deg.C and 8000rpm to obtain spindle-shaped or spherical MNPc-O-DDAB/POM self-assembly material; or carrying out hydrothermal reaction on the precipitate re-dispersed in water at 160-200 ℃ for 10-12 h to obtain the stable shuttle-shaped or spherical MNPc-O-DDAB/POM self-assembly material. Wherein the good solvent is dimethyl sulfoxide DMSO and N, N-dimethylformamide DMF treated by anhydrous magnesium sulfate; the poor solvent is water or carbon tetrachloride.
Compared with the prior art, the invention has the following remarkable advantages: (1) the invention adopts the phthalocyanine derivative to modify the double-chain cationic surfactant, and the modified surfactant keeps the spectroscopic property of the phthalocyanine; (2) the phthalocyanine derivative modified double-chain cationic surfactant is combined with polyoxometallate to form a compound, so that the aggregation of phthalocyanine in a solution can be avoided, and the dispersibility of the phthalocyanine in the solution is improved; in addition, in ZnTNPc-O-DDAB/PW12In the compound, ZnTNPc and PW12Remain unchanged and retain the respective light absorption due to ZnTNPc and PW12The compound has better photocatalytic activity, so the compound is supposed to integrate the photocatalytic activity of phthalocyanine and the photocatalytic function of POM; (3) the phthalocyanine derivative modified double-chain cationic surfactant and polyoxometallate compound are self-assembled in solution to obtain nano materials with different morphologies, and the nano materials have important significance for application as photocatalytic materials and the like.
In order to illustrate the chemical structures of the phthalocyanine derivative modified double-stranded cationic surfactant (MNPc-O-DDAB) and the phthalocyanine derivative modified double-stranded cationic surfactant and polyoxometallate complex (MNPc-O-DDAB/POM), the present invention is further illustrated with reference to the attached drawings.
Drawings
FIG. 1 is an infrared spectrum of ZnNPc, ZnNPc-O-DDAB, DDAB-11-ol. As can be seen from the spectrogram of ZnNPc, it is 1083 cm-1、837 cm-1、744 cm-1Is located at 1522 cm of the vibration peak of the skeleton of phthalocyanine-1、1337 cm-1Is a symmetric telescopic absorption peak of nitro on phthalocyanine ring, 1609 cm-1Is the stretching vibration peak of benzene ring, 1489 cm-1Is C-N stretching vibration peak. From the spectrogram of DDAB-11-ol, at 2919 cm-1And 2850 cm-11466 cm from symmetric and asymmetric absorption peak of stretching vibration due to methylene-1Shear mode vibration absorption peak at 724 cm of methylene-1And an in-plane bending vibration absorption peak of methylene. 1609 cm in the infrared spectrogram of ZnNPc-O-DDAB-1、1486 cm-1、746 cm-1Respectively shows an absorption peak on a phthalocyanine ring, 2924 cm-1、2852 cm-1An absorption peak of DDAB-11-ol appeared, indicating that ZnNPc has been bonded to DDAB-11-ol to form ZnNPc-O-DDAB.
FIG. 2 is a view of ZnNPc-O-DDAB1H-NMR spectrum, shift of hydrogen protons on the methyl group at the end of ZnNPc-O-DDAB chain at δ =0.86 (b), on the two methyl groups on the nitrogen atom of the quaternary amine at δ =2.96 (c), δ =3.36 (d) on the methylene group adjacent to O, δ =1.63 (e) on the two methylene groups adjacent to the methylene group connected to the end O, δ =3.19 (f) on the two methylene groups on the nitrogen atom of the quaternary amine. g. h and i are chemical shifts on a long alkyl chain, which are attributed to the shift of hydrogen protons on DDAB-11-ol, and besides, the shift of hydrogen protons j-u on a phthalocyanine ring appears in a range of delta =6.0-8.5, thereby also indicating that ZnNPc-O-DDAB has been successfully synthesized.
FIG. 3 shows ZnNPc-O-DDAB, PW12、ZnNPc-O-DDAB/PW12Infra-red spectrograms, PW12At 1080, 982, 889 and 805 cm-1The absorption at four positions is P-Oa (tetrahedral oxygen) stretching vibration, W = Od (terminal oxygen)The antisymmetric stretching vibration peak of W-Ob-W (oxygen shared by the tops of different trimetal clusters) and W-Oc-W (oxygen shared by the same trimetal cluster). At 1609, 1487, 745cm-1Is the absorption peak of the phthalocyanine ring. When PW is generated12After forming a complex with ZnNPc-O-DDAB, due to PW12Electrostatic interaction exists between the outer negatively charged O atom and the N atom of the positively charged quaternary ammonium salt of ZnNPc-O-DDAB, which causes PW12The characteristic absorption peak of (A) slightly shifts to 1089 cm respectively-1、978 cm-1、894 cm-1And 817 cm-1。ZnNPc-O-DDAB/PW12In the compound, both PW and beta-cyclodextrin are retained12The basic framework structure of the ZnNPc-O-DDAB is not damaged at the same time, which shows that the ZnNPc-O-DDAB/PW is formed12And (c) a complex.
FIG. 4 shows that different concentrations of PW are added into ZnTNPc-O-DDAB solution12Fluorescence emission spectrum of (a). As can be seen from the fluorescence spectrum of ZnTNPc-O-DDAB in FIG. 4, the fluorescence emission intensity of ZnTNPc-O-DDAB at 700 nm varies with PW12The increase in concentration is substantially in an increasing trend. The increase in fluorescence intensity is probably due to the fact that when PW is used12When the concentration is increased, the nano-particles and ZnTNPc-O-DDAB have electrostatic interaction, thus reducing aggregation caused by accumulation of the ZnTNPc-O-DDAB pi-pi, improving the dispersibility of the nano-particles in a solution and increasing the fluorescence emission of the ZnTNPc.
FIG. 5 shows ZnTNPc, ZnTNPc-O-DDAB, PW12、ZnTNPc-O-DDAB/PW12In DMSO and H2O mixed solvent (V)DMSO : VH2OElectron absorption spectrum in =4: 1). From PW12Can be seen in the spectrogram, PW12O in (1)dThe → W characteristic charge shift is caused by its absorption peak transition at 266 nm, which has no absorption in the visible range; the absorption peaks of ZnTNPc at 256 nm and 347 nm are a1uTo egThe characteristic absorption peak of B band caused by (pi) low-energy transition is a2uTo eg(π) characteristic absorption peak of Q band due to high energy transition. While the electron absorption spectrum of ZnTNPc-O-DDAB is almost the same as that of ZnTNPc, and characteristic absorption peaks of the B band and the Q band of ZnTNPc appear at 347 nm and 693 nm.ZnTNPc-O-DDAB/PW12The absorption spectrum of the compound shows both the absorption peak of ZnTNPc and PW12absorption peak of, i.e. broadening PW12Absorption into the visible region.
In order to illustrate the self-assembly behavior of the phthalocyanine derivative modified double-chain cationic surfactant and the polyoxometalate complex in the solution, the invention is further illustrated with reference to the attached drawings.
FIG. 6 shows ZnNPc-O-DDAB/PW12Field emission Scanning Electron Microscopy (SEM) of self-assemblies of the composites. In the figure: a, b are ZnNPc-O-DDAB/PW12Complex in DMSO/H2Structure of assembly in O (V: V =4: 1); c, d is a secondary assembly structure of the centrifugal precipitation of the primary self-assembly liquid and 10ml of water; e and f are assembly structures of the secondary assembly through hydrothermal reaction for 10 hours at 180 ℃.
From fig. 6 (a, b) it is seen that the composite assembled in mixed solvent forms a multi-layer densely packed network 100 nm wide. FIG. 6 (c, d) is an SEM image of a self-assembly liquid centrifugally precipitated solid dispersed in an aqueous solution, and the aggregates formed small spheres and fusiform aggregates in the aqueous solution. Fig. 6 (e, f) is an SEM image of the self-assembled pellet and spindle shaped aggregate after hydrothermal treatment, still pellet and spindle shaped aggregate.
Detailed Description
The preparation method of the phthalocyanine derivative modified surfactant combined polyoxometallate composite is illustrated by the following example.
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