CN113600165A - Tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and preparation method thereof - Google Patents

Tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and preparation method thereof Download PDF

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CN113600165A
CN113600165A CN202110935008.7A CN202110935008A CN113600165A CN 113600165 A CN113600165 A CN 113600165A CN 202110935008 A CN202110935008 A CN 202110935008A CN 113600165 A CN113600165 A CN 113600165A
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李忠玉
仇苏红
梁倩
周满
徐松
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Abstract

The invention belongs to the field of nano material preparation, and particularly relates to a preparation method of a tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst, which comprises the steps of preparing the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine, pretreating a multi-walled carbon nanotube and preparing the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst. The invention has the beneficial effects that: the method synthesizes the metal phthalocyanine by the liquid phase method of the phthalodinitrile, has mild reaction conditions, less impurities and lower purification difficulty, and the composite catalyst has simpler preparation method and high yield, thereby effectively improving the problem that the catalytic activity of the phthalocyanine is reduced due to easy aggregation; the composite catalyst prepared by the invention has wide application range, has excellent catalytic effect, can catalyze various benzyl alcohols under mild reaction conditions, and has good application prospect.

Description

Tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and preparation method thereof
Technical Field
The invention particularly relates to a tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and a preparation method thereof, belonging to the field of nano material preparation.
Background
Phthalocyanines and their derivatives have a unique conjugated macrocyclic system and are chemically stable. Its central macrocyclic cavity contains 2 hydrogen atoms which can be substituted by other elements, and can be formed into metal phthalocyanine complex with several metal elements. The phthalocyanine compound has an electron conjugated structure of 18 pi, and the electron density of the phthalocyanine is very uniform. Catalytic reactions can take place in planar axial positions, and aromatic rings can act as electron acceptors and electron donors and are therefore widely used as catalysts. However, due to the super-conjugated plane macromolecular structure of phthalocyanine molecules, the molecules have strong pi-pi conjugation, so that the phthalocyanine molecules are insoluble in common organic solvents and poor in solubility, and the phthalocyanine molecules are easy to aggregate in a reaction medium to form inactive dimers or even polymers due to the structural characteristics of the phthalocyanine molecules, so that the specific surface area of the catalyst is greatly reduced, and the catalytic efficiency of the catalyst is reduced. Therefore, it is important to develop a metal phthalocyanine composite material which can effectively prevent the phthalocyanine from aggregating and enhance the catalytic activity thereof.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and a preparation method thereof.
In order to realize the purpose of the invention, the adopted technical scheme is as follows: the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube catalyst is used for catalytic oxidation of various benzyl alcohols, and is formed by compounding tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine and multi-walled carbon nanotubes, wherein the structural formula of the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine is as follows:
Figure BDA0003212543180000021
the preparation method of the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-wall carbon nanotube composite catalyst comprises the following steps:
adding 50-70 wt% of concentrated nitric acid into a multi-walled carbon nanotube, heating and stirring at 80-100 ℃ for 12-24 h, cooling after the reaction is finished, washing with water to be neutral, drying to obtain a pretreated multi-walled carbon nanotube, immersing the treated multi-walled carbon nanotube and tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine into a petroleum ether solution, carrying out ultrasonic treatment, and drying to obtain the tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst. The carbon nano tube is acidized in order to increase the activity of the carbon nano tube and remove impurities, so that carboxyl is carried on the surface of the carbon nano tube, the dispersibility of the carbon nano tube in a solvent can be increased, meanwhile, the end opening of the carbon nano tube is opened after the carbon nano tube is acidized, the surface area of the carbon nano tube is obviously increased, and the loading of metal phthalocyanine is facilitated. If the concentration of the concentrated nitric acid is out of the defined range, the reaction is very violent, and a large amount of NO is generated2Gas, lack of safety in experiment and production, and also cause the weight loss rate of the carbon nano tube to be too large, resulting in serious loss of the carbon nano tube. The acidification time of the carbon nano tube is prolonged, the temperature is increased, the reaction speed is increased, and the weight loss rate of the carbon nano tube purification is also improved.
Preferably, the heating and stirring temperature of the multi-wall carbon nano-tube in concentrated nitric acid is 80 ℃, and the heating and stirring time is 24 h.
Preferably, the mass ratio of the tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt to the multi-walled carbon nanotube is 2:1-4:1, and more preferably 3: 1.
Preferably, the ultrasonic load time is 4 h.
Preferably, the preparation method of the tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt comprises the following steps:
(1) preparation of 3- (4-formyl) phenoxy phthalodinitrile: fully dissolving 3-nitrophthalonitrile and p-hydroxybenzaldehyde in a solvent to obtain a mixture, adding a catalyst (the catalyst is preferably any one of potassium carbonate, potassium bicarbonate and sodium carbonate) into the mixture in batches under the protection of nitrogen at a reaction temperature with stirring, cooling to room temperature after the reaction is finished, dropwise adding a reaction solution into a 0.5mol/l NaOH solution, filtering, washing with deionized water and a saturated NaCl aqueous solution, and drying a filter cake to obtain a pure light yellow product, namely 3- (4-formyl) phenoxy phthalic nitrile;
(2) preparation of 3- (4-hydroxymethyl) phenoxy phthalodinitrile: 3- (4-formyl) phenoxy phthalic nitrile obtained in the step (1) and NaBH4Dissolving in an anhydrous methanol solvent, stirring at room temperature for reaction, dropwise adding 20 wt% hydrochloric acid into the reaction solution for quenching until no bubbling, centrifuging, taking the supernatant, concentrating in vacuum to obtain light yellow powder, namely a crude product of 3- (4-hydroxymethyl) phenoxy phthalonitrile, and purifying by column chromatography by taking a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain a white pure product, namely 3- (4-hydroxymethyl) phenoxy phthalonitrile;
(3) preparation of tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt: adding 3- (4-hydroxymethyl) phenoxy phthalic nitrile, cobalt chloride hexahydrate, a catalyst 1, 8-diazabicyclo [5,4,0] undec-7-ene and an n-amyl alcohol solvent into a reaction container, heating and stirring under the protection of nitrogen, refluxing, condensing, reacting, cooling after the reaction is finished, pouring into petroleum ether, separating a solid product by suction filtration, washing with ethyl acetate and ethanol for several times, drying (the drying temperature is preferably 60 ℃) to obtain a crude product, and purifying by column chromatography by using a mixed solvent of the petroleum ether and the ethyl acetate as an eluent to obtain the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine.
Further, the molar ratio of the 3-nitrophthalonitrile to the p-hydroxybenzoic acid in the step (1) is 1: 1.5;
further, the solvent in step (1) is DMF (N-N dimethylformamide), and experiments show that the solvent can be DMSO (the yield of the 3- (4-formyl) phenoxy phthalic nitrile can reach 75.6 percent), acetonitrile (the yield of the 3- (4-formyl) phenoxy phthalic nitrile can reach 65.1 percent), DMF is used for realizing the best solubility, and the yield of the obtained 3- (4-formyl) phenoxy phthalic nitrile (the yield is 84.3 percent) is the highest.
Further, in the step (1), the reaction temperature is 70 ℃, and the stirring reaction time is 4.5 h.
Further, the stirring reaction time of the step (2) is 2 hours.
Further, the volume ratio of the eluent, the petroleum ether and the ethyl acetate in the step (2) is 2: 1.
Further, in the step (3), the reflux condensation reaction temperature is 130 ℃, and the reaction time is 10 hours.
Further, the eluent in the step (3) is petroleum ether and ethyl acetate in a volume ratio of 3: 1.
The metal phthalocyanine-based composite material is connected with a high molecular carrier, so that the phthalocyanine metal catalyst is immobilized, the loss of active components of the catalyst is reduced, and the performance of the catalyst is improved. Carbon nanotubes have unique physical and chemical properties, high levels of electron mobility and conductivity, and large specific surface area, which not only makes them useful as supports for macrocyclic organic catalysts, but also the introduction of multi-walled carbon nanotubes (MWCNTs) can increase catalytically active sites and improve catalytic activity. The method adopts an ultrasonic impregnation method to fix the tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine on the surface of the MWCNTs, so that the aggregation of the tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine is effectively prevented, and the catalytic activity to benzyl alcohol is effectively improved.
Compared with the prior art, the invention has the beneficial effects that: the method synthesizes the metal phthalocyanine by the liquid phase method of the phthalodinitrile, has mild reaction conditions, less impurities and lower purification difficulty, and the composite catalyst has simpler preparation method and high yield, thereby effectively improving the problem that the catalytic activity of the phthalocyanine is reduced due to easy aggregation; the composite catalyst prepared by the invention has wide application range, has excellent catalytic effect, can catalyze various benzyl alcohols under mild reaction conditions, and has good application prospect.
Drawings
FIG. 1 is an X-ray diffraction diagram of the tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multi-walled carbon nanotube composite catalyst prepared in example 1 of the invention.
FIG. 2 is a transmission electron micrograph of tetra-substituted cobalt 3- (4-formyl) phenoxyphthalocyanine and tetra-substituted cobalt 3- (4-formyl) phenoxyphthalocyanine/multi-walled carbon nanotube composite catalyst used in comparative example 1 and example 3 according to the present invention; wherein 2a is tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine, and 2b is the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalytic material.
Fig. 3 is a graph showing the effect of the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst with the mass ratio of 3:1 in catalyzing different benzyl alcohols in application examples 1-5 of the present invention.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in other embodiments according to the disclosure of the present invention, or make simple changes or modifications on the design structure and idea of the present invention, and fall into the protection scope of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention is described in more detail below with reference to the following examples:
example 1
The invention relates to a preparation method of a tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube catalyst, which specifically comprises the following steps:
(1) preparation of 3- (4-formyl) phenoxy phthalodinitrile: 0.75g of 3-nitrophthalonitrile (4.33mmol) and 0.795g of p-hydroxybenzoic acid (6.50mmol) are dissolved in 15ml of DMF (N-dimethylformamide) solvent, the mixture is stirred at 70 ℃ for 4.5h under nitrogen protection, and the catalyst (1.195 g of potassium carbonate (8.665mmol) is added in portions, and experiments prove that the catalyst can be potassium carbonate (the yield of 3- (4-formyl) phenoxy phthalic nitrile can reach 84.3%), potassium bicarbonate (the yield of 3- (4-formyl) phenoxy phthalic nitrile can reach 66.8%), sodium carbonate (the yield of 3- (4-formyl) phenoxy phthalic nitrile can reach 78.3%), when the catalyst is potassium bicarbonate or sodium carbonate, the yield of 3- (4-formyl) phenoxy phthalic nitrile can be reduced), after the mixture is cooled to room temperature, dropwise adding the reaction solution into 0.5mol/l dilute NaOH solution, filtering, washing with deionized water and saturated NaCl aqueous solution, and drying a filter cake to obtain a pure light yellow product;
(2) preparation of 3- (4-hydroxymethyl) phenoxy phthalodinitrile: 3- (4-hydroxymethyl) phenoxy phthalonitrile (0.50g, 2.015mmol) obtained in step (1) and NaBH4(0.0835g, 2.215mmol) is dissolved in 20ml of absolute methanol solvent, the mixture is stirred for 2h at room temperature, after the reaction is finished, 20% diluted hydrochloric acid is dropwise added into the reaction liquid for quenching until no bubbling occurs, centrifugation is carried out, the supernatant is taken and concentrated in vacuum to obtain light yellow powder, namely a crude product of the 3- (4-hydroxymethyl) phenoxy phthalic dinitrile, and the mixture is purified by column chromatography by taking a mixed solvent (volume ratio is 2: 1) of petroleum ether and ethyl acetate as an eluent to obtain a white pure product;
(3) preparation of tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt: adding 3- (4-hydroxymethyl) phenoxy phthalic nitrile (0.50g, 2.00mmol), cobalt chloride hexahydrate (0.229g, 1.250mmol), 1, 8-diazabicyclo [5,4,0] undec-7-ene (1mL) as a catalyst and n-amyl alcohol (25mL) as a solvent into a reaction vessel, heating and stirring under the protection of nitrogen, refluxing and condensing, reacting at 130 ℃ for 10 hours, cooling after the reaction is finished, pouring into petroleum ether, separating a solid product by suction filtration, washing with ethyl acetate and ethanol for several times, then drying at 60 ℃ overnight to obtain a crude product, and purifying by column chromatography with a mixed solvent of petroleum ether and ethyl acetate (volume ratio of 3: 1);
(4) pretreatment of the multi-wall carbon nano tube: weighing 1g of multi-walled carbon nanotube, putting the multi-walled carbon nanotube into a three-neck flask, adding 150ml (50-70 wt%) of concentrated nitric acid, heating and stirring at 80-100 ℃ for 12-24 h, cooling after the reaction is finished, washing with water to be neutral, and drying to obtain the treated multi-walled carbon nanotube;
(5) preparing a tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube catalyst: 0.3g of tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine and 0.1g of multi-walled carbon nanotubes (corresponding to the mass ratio of cobalt phthalocyanine to carbon nanotubes being 3: 1; or 0.15g of carbon nanotubes being 0.075g and corresponding to the mass ratio of cobalt phthalocyanine to carbon nanotubes being 2:1 and 4: 1), respectively, are added into 40ml of petroleum ether solution, ultrasonically loaded for 4h, and dried to obtain the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst with different mass ratios, and the catalyst is marked as C (x), wherein x is the mass ratio of cobalt phthalocyanine to carbon nanotubes (the preparation method of C (x) in the following examples and application examples is the same except that the mass ratio of cobalt phthalocyanine to carbon nanotubes is changed). The yield of composite catalyst C (3: 1) was 90%.
The crystal phase structure of the composite catalyst C (3: 1) prepared in example 1 was analyzed by a rotational X-ray diffractometer in Japan science D/max2500PC, wherein the X-ray is a Cu target K.alpha.
Figure BDA0003212543180000071
The voltage is 40kV, the current is 100mA, the step length is 0.02 degrees, and the scanning range is 10-80 degrees. The X-ray diffraction pattern is shown in fig. 1, the 3- (4-formyl) phenoxyphthalocyanine cobalt has three distinct diffraction peaks, and after the multi-wall carbon nanotube is loaded, compared with the characteristic diffraction peak of the 3- (4-formyl) phenoxyphthalocyanine cobalt, the 3- (4-formyl) phenoxyphthalocyanine cobalt/multi-wall carbon nanotube contains the characteristic peaks of the two, which indicates that the tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt is successfully fixed on the multi-wall carbon nanotube.
Example 2
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (2: 1), 0.3g of benzyl alcohol, 3.0ml of TBHP, and 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and the conversion of benzyl alcohol was 32.78% and the selectivity of benzaldehyde was 45.18% by gas chromatography GC analysis.
Example 3
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of benzyl alcohol, 3.0ml of TBHP, and 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and the conversion of benzyl alcohol was 50.02% and the selectivity of benzaldehyde was 88.98% by gas chromatography GC analysis.
Example 4
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (4: 1), 0.3g of benzyl alcohol, 3.0ml of TBHP, and 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and the conversion of benzyl alcohol was 43.36% and the selectivity of benzaldehyde was 58.89% by gas chromatography GC analysis.
Comparative example 1
The tetrasubstituted 3- (4-formyl) phenoxy cobalt phthalocyanine prepared by the method is used as a catalyst to catalyze the selective oxidation of the benzyl alcohol to prepare the benzaldehyde, and the experimental conditions are the same as those in example 3. The conversion of benzyl alcohol was 29.43% and the selectivity of benzaldehyde was 99% by GC analysis.
The morphology of the catalysts in example 3 and comparative example 1 was observed using a transmission electron microscope, model JSM-6360A, japan, and the results are shown in fig. 2a and 2b, respectively. As can be seen from FIG. 2, the aggregated tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt is attached to the multi-walled carbon nanotube as a clearly visible small particle, which shows that the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt is effectively dispersed on the multi-walled carbon nanotube, so that the defect that the metal phthalocyanine is easy to aggregate, thereby reducing the catalytic efficiency can be overcome. Through gas chromatography analysis, the yield of benzaldehyde in comparative example 1 is far less than that in example 3, and the mass ratio is further proved to be 3: the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-wall carbon nanotube composite catalyst of 1 has higher activity.
Application example 1
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of 4-methylbenzyl alcohol, 3.0ml of TBHP, 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and analyzed by gas chromatography GC.
Application example 2
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of p-bromobenzyl alcohol, 3.0ml of TBHP, 5ml of toluene were added and reacted for 6 hours in an oil bath at 80 ℃ and analyzed by gas chromatography GC.
Application example 3
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of p-nitrobenzyl alcohol, 3.0ml of TBHP, 5ml of toluene were added and reacted for 6 hours in an oil bath at 80 ℃ and analyzed by gas chromatography GC.
Application example 4
To a 25ml pressure resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of 2-naphthalenemethanol, 3.0ml of TBHP, 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and analyzed by gas chromatography GC.
Application example 5
To a 25ml pressure-resistant reaction tube, 20mg of catalyst C (3: 1), 0.3g of thiophene-2-methanol, 3.0ml of TBHP, and 5ml of toluene were added and reacted in an oil bath at 80 ℃ for 6 hours, and analyzed by gas chromatography GC.
The tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalytic material prepared by the invention has higher catalytic activity than that of the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine, successfully improves the agglomeration problem of the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine, has simple preparation process and high yield, and is a good catalyst composite material.
The tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalytic material prepared by the invention has good catalytic effect on various benzyl alcohols under normal pressure, has wide application range and mild reaction conditions, and can be applied to catalysis of various benzyl alcohols in industry.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (9)

1. A tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-wall carbon nanotube catalyst is used for catalytic oxidation of benzyl alcohol, and is characterized in that: the composite material is compounded by tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine and a multi-wall carbon nano tube, wherein the structural formula of the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine is as follows:
Figure FDA0003212543170000011
2. the method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 1, wherein: the method comprises the following steps: adding 50-70 wt% of concentrated nitric acid into a multi-walled carbon nanotube, heating and stirring at 80-100 ℃ for 12-24 h, cooling after the reaction is finished, washing with water to be neutral, drying to obtain a pretreated multi-walled carbon nanotube, immersing the treated multi-walled carbon nanotube and tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine into a petroleum ether solution, carrying out ultrasonic treatment, and drying to obtain the tetrasubstituted 3- (4-formyl) phenoxyl cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst.
3. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 2, characterized in that: the mass ratio of the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine to the multi-wall carbon nano tube is 2:1-4: 1.
4. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 3, characterized in that: the mass ratio of the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine to the multi-wall carbon nano tube is 3: 1.
5. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 2, characterized in that: the ultrasonic load time is 4 h.
6. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 2, characterized in that: the preparation method of the tetra-substituted 3- (4-formyl) phenoxyl cobalt phthalocyanine comprises the following steps:
(1) preparation of 3- (4-formyl) phenoxy phthalodinitrile: fully dissolving 3-nitrophthalonitrile and p-hydroxybenzaldehyde in a solvent to obtain a mixture, adding the mixture into a catalyst in batches under the protection of nitrogen at a reaction temperature with stirring, cooling to room temperature after the reaction is finished, dropwise adding the reaction solution into 0.5mol/l NaOH solution, filtering, washing with deionized water and saturated NaCl aqueous solution, drying a filter cake, and obtaining a pure light yellow product, namely 3- (4-formyl) phenoxy phthalonitrile;
(2) preparation of 3- (4-hydroxymethyl) phenoxy phthalodinitrile: 3- (4-formyl) phenoxy phthalic nitrile obtained in the step (1) and NaBH4Dissolving in an anhydrous methanol solvent, stirring at room temperature for reaction, dropwise adding 20 wt% hydrochloric acid into the reaction solution for quenching until no bubbling, centrifuging, taking the supernatant, concentrating in vacuum to obtain light yellow powder, and purifying by column chromatography with a mixed solvent of petroleum ether and ethyl acetate as an eluent to obtain a white pure product, namely 3- (4-hydroxymethyl) phenoxy phthalonitrile;
(3) preparation of tetra-substituted 3- (4-formyl) phenoxyphthalocyanine cobalt: adding 3- (4-hydroxymethyl) phenoxy phthalic nitrile, cobalt chloride hexahydrate, a catalyst 1, 8-diazabicyclo [5,4,0] undec-7-ene and a solvent n-amyl alcohol into a reaction container, heating and stirring under the protection of nitrogen, refluxing, condensing, reacting, cooling after the reaction is finished, pouring into petroleum ether, separating a solid product by suction filtration, washing with ethyl acetate and ethanol for several times, drying to obtain a crude product, and purifying by column chromatography by using a mixed solvent of the petroleum ether and the ethyl acetate as an eluent to obtain the tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine.
7. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 6, wherein: the reaction temperature in the step (1) is 70 ℃, and the stirring reaction time is 4.5 h;
and/or the volume ratio of the petroleum ether to the ethyl acetate in the eluent in the step (2) is 2: 1;
and/or, the stirring reaction time in the step (2) is 2 hours;
and/or the volume ratio of the petroleum ether to the ethyl acetate in the eluent in the step (3) is 3: 1;
and/or the reflux condensation reaction temperature in the step (3) is 130 ℃, and the reaction time is 10 h.
8. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 6, wherein: in the step (1), the molar ratio of the 3-nitrophthalonitrile to the p-hydroxybenzaldehyde is 1: 1.5;
and/or, the catalyst in the step (1) is any one of potassium carbonate, potassium bicarbonate and sodium carbonate.
9. The method for preparing the tetrasubstituted 3- (4-formyl) phenoxyphthalocyanine cobalt/multiwalled carbon nanotube composite catalyst according to claim 6, wherein: in the step (1), the solvent is any one of DMF (N-N dimethylformamide), DMSO and acetonitrile.
CN202110935008.7A 2021-08-16 2021-08-16 Tetra-substituted 3- (4-formyl) phenoxy cobalt phthalocyanine/multi-walled carbon nanotube composite catalyst and preparation method thereof Pending CN113600165A (en)

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