CN102887541A - Preparation method of phthalocyanine sensitized TiO2 nano-particle by microwave-hydrothermal method - Google Patents

Preparation method of phthalocyanine sensitized TiO2 nano-particle by microwave-hydrothermal method Download PDF

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CN102887541A
CN102887541A CN2011102056370A CN201110205637A CN102887541A CN 102887541 A CN102887541 A CN 102887541A CN 2011102056370 A CN2011102056370 A CN 2011102056370A CN 201110205637 A CN201110205637 A CN 201110205637A CN 102887541 A CN102887541 A CN 102887541A
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phthalocyanine
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tio
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CN102887541B (en
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毋伟
王倩
陈建峰
马凯
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Beijing University of Chemical Technology
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Abstract

The invention discloses a preparation method of phthalocyanine sensitized TiO2 nano-particle by a microwave-hydrothermal method, which belongs to the application of microwave methods in the field of nano-particle preparation. Firstly, a variety of phthalocyanine complexes are synthesized by the microwave irradiation method. Then, with ethanol solution of titanate and phthalocyanine as a raw material, phthalocyanine/ TiO2 nano-photocatalyst provided by the invention is obtained by microwave irradiation and hydrothermal treatment under the combined actions of surfactant and catalyst. The phthalocyanine/ TiO2 nano-photocatalyst has good utilization efficiency for visible light and has good catalytic efficiency for the conversion of CO2 to a methanol test under irradiation of visible light. The method provided by the invention provides a concise and pratical preparation of phthalocyanine sensitized TiO2 with visible light response, and also provides a catalyst preparing scheme with good prospect for photocatalysis.

Description

A kind of microwave-hydrothermal method synthetic phthalocyanine sensitization TiO 2the preparation method of nanoparticle
Technical field
The present invention relates to a kind of microwave-hydrothermal method synthetic dyestuff doped Ti O 2the preparation method of nanoparticle, belong to the application of microwave method in the preparation field of nanoparticles.
Background technology
The Nano semiconductor photocatalyst material can utilize nearly all organism in luminous energy catalyzed degradation water and air, and photocatalyst material is at photocatalytic degradation CO 2broad research is also arranged in technology, is to reduce discharging CO 2one of the technology with applications well prospect.TiO 2show the advantages such as unreactiveness, light stability, cheap and easy to get, nontoxic and catalytic capability be stronger in light-catalyzed reaction, thereby become light-catalyzed reaction material the most commonly used.But TiO 2due to energy gap wider (3.2eV), only can utilize the UV-light in sunlight, for by TiO 2absorption be extended to visible region, the TiO such as that people have studied is metal-doped, doped metallic oxide, dye sensitization 2mixture.Wherein phthalocyanine pigment is doped in to TiO 2in be a kind of not only simply but also effective means.Phthalocyanine is the plane macrocycle molecule with π-electron system of height conjugation, and its special structure makes it have good stability and photoelectric characteristic, at catalyzer, and photocell, dyestuff, optical recording material, there is excellent characteristic the aspects such as biomedical material.The Q band of phthalocyanine is excited after the 600-800nm visible region absorbs photon, by electronic injection TiO 2conduction band, conduction band electron and TiO 2surface adsorbed oxygen is had an effect and is generated O 2 -with .thereby OH etc. have the active group performance TiO of extremely strong oxygenizement 2photocatalysis.
In preparing the method for phthalocyanine, solid phase method and solvent method are two kinds of preparation technologies that are widely used.But these two kinds of methods can produce more waste liquid, waste gas, and long reaction time, output and productive rate are all lower.Microwave chemical is subject to extensive concern in recent years, and microwave heating promotes chemical reaction can realize the stirring on molecular level, has that speed of response is fast, yield is high, system temperature is even, pollute the advantages such as little or pollution-free.Microwave method prepares phthalocyanine and also is divided into solid phase method and solvent method preparation, solid phase method is about to acid anhydrides, urea, and metal-salt mixes and adds the molybdenum compound to make catalyzer, microwave exposure generates the phthalocyanine crude product, as Chinese patent " a kind of method for preparing phthalocyanine blue " (patent No. CN01139219.3).Chinese patent " method and apparatus for preparing metal or nonmetal phthalocyanine " (patent No.: 200480020240) disclose a kind of under the existence of solvent microwave method prepare the method for phthalocyanine, but their materials are numerous and diverse, long reaction time.
Current phthalocyanine-sensitized TiO 2the preparation method of photocatalyst has sol-gel method, hydrothermal method, original position self-assembly, preparation method in place etc.Sol-gel method is by metal-salt, phthalic nitrile, tetrabutyl titanate adds catalyzer to obtain xerogel by processing, as Chinese patent " a kind of sol-gel original position and self assembling process of synthesizing of the composite photocatalyst material " (patent No.: CN200310122931.0) after mixing.Chinese patent " hydro-thermal of phthalocyanine-sensitized nano TiO 2 powder the preparation method in place " (patent No.: 200510049257) utilize the method for preparing nano-powder under the hydro-thermal super critical condition, synchronously add as the Phthalocyanine with sensitizing agent, make it participate in nano-titania particle forming process compound with it, and then make phthalocyanine-sensitized nano TiO 2 powder.Composite material granular irregularity prepared by these two kinds of methods, phthalocyanine defect pockety, all have much room for improvement to visible ray utilization ratio and catalytic efficiency.
Microwave method is in recent years at preparation TiO 2field obtains broad research.200910198043) and " a kind of method that adopts microwave exposure to prepare anatase type nano titanium dioxide sol " (patent No.: 200710144382) reported with different material and prepared TiO through microwave method respectively current Chinese patent " a kind of method of the synthesizing nano titanium dioxide through microwaves " (patent No.: 2nano particle, the TiO prepared through microwave treatment 2the product prepared with immersion method under the same terms is compared, and its degree of crystallinity is high, photocatalytic activity good, and its particle diameter is less, it is narrower to distribute, and therefore has better stability.Also have with microwave method and prepare sensitization TiO in addition 2report, as Chinese patent, " a kind of microwave prepares foamed nickel supported modification TiO 2method and application " (patent No. 200610085775), but adopt microwave technology to be applied to prepare dye sensitization TiO 2photocatalyst also rarely has report, and prepares phthalocyanine-sensitized TiO with microwave-hydro-thermal 2the preparation of composite nanoparticle there is not yet report.
Summary of the invention
The object of the invention is to for improving TiO 2photocatalysis efficiency, provide a kind of stable, reliably, the new preparation technology of phthalocyanine-sensitized nano TiO 2 powder cheaply, concrete is at first to adopt microwave method synthetic phthalocyanine title complex, then with microwave-hydrothermal method, prepares phthalocyanine-sensitized TiO 2nanoparticle.Another object of the present invention is to provide the preparation method of the high efficiency phthalocyanine complex of a kind of high yield.The present invention uses phthalic nitrile, and metal-salt is raw material, under solvent exists, adds catalyzer, and microwave number minute both obtained the higher product of productive rate, and its synthetic method is as follows, and this preparation method there is not yet report.
Figure BDA0000077519400000031
The phthalocyanine-sensitized TiO of microwave-Hydrothermal Synthesis provided by the invention 2the preparation method of nanoparticle, is characterized in that at first with microwave exposure, preparing phthalocyanine complex, then phthalocyanine is doped in to TiO with microwave-hydrothermal method 2in nanoparticle, form phthalocyanine-sensitized TiO 2composite nanoparticle.
A kind of microwave of the present invention-hydrothermal method synthetic phthalocyanine sensitization TiO 2the preparation method of nanoparticle comprises the following steps:
(1) preparation of phthalocyanine complex
Phthalic nitrile, metal-salt be take to mol ratio and as 4: 1, be dissolved in solvent, after adding diazabicylo (DBU) to mix, in microwave reactor, with 2450MHz microwave exposure 2-30min, cooled and filtered is purified and is obtained corresponding phthalocyanine complex.
(2) phthalocyanine-sensitized TiO 2the preparation of composite nanoparticle
Step (1) phthalocyanine complex, tensio-active agent and titanium source are scattered in ethanolic soln, after stirring, splash into catalyzer, after continuing to stir 0.5h, mixed solution is placed in to microwave reactor with 2450MHz microwave exposure 2min～30min; Cooled and filtered with the deionized water supersound washing, then by powder with 150-200 ℃ of hydrothermal treatment consists 3h～10h; Finally by washing, to filter, drying obtains phthalocyanine-sensitized TiO 2composite nanoparticle.
The metal-salt that above-mentioned steps (1) is used can be one or more in the muriate of zinc, cobalt, copper, iron, nickel, acetate, vitriol, and metal ion as the masterplate agent, is more conducive to phthalic nitrile and aggregates into phthalocyanine structure around it in reaction.
The described solvent of step (1) can be N-N dimethyl formamide (DMF), thanomin, and dimethyl sulfoxide (DMSO), primary isoamyl alcohol, one or more in Pentyl alcohol, wherein 1g phthalic nitrile solvent for use is that 2-30ml, DBU used are 0.2-5ml.
Step (1) irradiation power is 300-1000W, and irradiation time is 2-30min.
Wherein the phthalocyanine of step (1) gained can be Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc, FePC, one or more in Nickel Phthalocyanine.
Step of the present invention (2) is dispersed preferably for guaranteeing that phthalocyanine has in ethanol, reaches higher photocatalysis efficiency simultaneously, and the consumption of phthalocyanine can be TiO 20.2%～5% of massfraction, preferred phthalocyanine consumption is TiO 2massfraction 0.5%～2%.
The present invention's titanium used source is tetrabutyl titanate, a kind of in titanium isopropylate.Tensio-active agent is a kind of in cetyl trimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP).Its concentration is controlled at 0.005M～0.2M.Tensio-active agent can standard TiO in this system 2pattern, and at TiO 2occupy certain space in building-up process, remove after tensio-active agent the TiO that just obtains vesicular structure 2.
The catalyzer used in the present invention has the ability that promotes the hydrolysis of titanium source, can be in water, hydrazine hydrate, ammoniacal liquor a kind of.The volume ratio of catalyzer and ethanol is 1: 120 to 1: 6, preferably 1: 60.
Step of the present invention (2) adds after catalyzer after stirring 0.5h and adds microwave reactor, and microwave exposure power is 300W～1000W, and irradiation time is 5min～30min, preferred 800W, 10min.
The present invention, after mixed solution is carried out to microwave exposure, with the deionized water supersound washing for several times, then is scattered in composite particles in water the hydrothermal reaction kettle that adds the tetrafluoroethylene cover, and hydrothermal temperature is 150 ℃～200 ℃, and the time is 3h～10h, and preferably the time is 5h.This hydrothermal treatment consists process can be by TiO 2transformation of crystal be Detitanium-ore-type, have the activation phthalocyanine effect the time phthalocyanine can not decomposed.The hydrothermal treatment consists time, too short crystallization was incomplete.
The postprocessing working procedures such as separation of the present invention, filtration, washing and drying are conventional treatment process.
Phthalocyanine-sensitized TiO prepared by the present invention 2composite nanoparticle is nano spherical particle.
The present invention be take the 500W xenon lamp as light source, with CO 2producing methyl alcohol in photocatalytic process is that evaluation index has been carried out certain evaluation to this catalyzer.
Another object of the present invention: a kind of preparation method of phthalocyanine complex, step (1) comprises the following steps: as take metal-salt, phthalic nitrile mol ratio as 1 or is dissolved in solvent at 0: 4, after adding DBU to mix, in microwave reactor, with 2450MHz microwave exposure 2-30min, cooled and filtered is purified and is obtained corresponding phthalocyanine complex.
The metal-salt used can be in muriate, acetate, vitriol a kind of.Hollow phthalocyanine is and does not add masterplate agent metal-salt, directly catalysis phthalic nitrile synthetic phthalocyanine.Solvent for use can be N-N dimethyl formamide (DMF), thanomin, dimethyl sulfoxide (DMSO), primary isoamyl alcohol, one or more in Pentyl alcohol.Wherein 1g phthalic nitrile solvent for use consumption is that 2-30ml, DBU consumption used are 0.2-5ml.Can prepare Phthalocyanine Zinc, Cobalt Phthalocyanine, CuPc, FePC, Nickel Phthalocyanine, hollow phthalocyanine and other metal phthalocyanines.
Beneficial effect of the present invention: the present invention is applied to prepare phthalocyanine and Phthalocyanine of Doping TiO to microwave technology 2composite nanoparticle.Traditional phthalocyanine technology for preparing is generally the chemical heat method, and required time 7h～20h consumes greatly, and pollution is many.The present invention can complete in several minutes for the preparation of the method for phthalocyanine, has greatly saved cost and has improved efficiency.The present invention by Phthalocyanine of Doping in TiO 2in crystal, combine phthalocyanine and TiO 2advantage, improved TiO 2in the responding ability of visible region, it is a kind of method that effectively prepares visible light catalyst.Method simple process of the present invention, efficiency is high, and productive rate is high, and the scale that is easy to is amplified.
Adopt the standby phthalocyanine/TiO of this legal system 2photocatalyst has utilising efficiency preferably to visible ray, for visible ray, shines lower CO 2be converted into Methanol catalytic efficiency is preferably arranged.This method provides a kind of preparation of succinct practicality to have visible light-responded phthalocyanine-sensitized TiO 2, for photochemical catalysis provides a kind of catalyzer with good prospect, prepare scheme.
The accompanying drawing explanation
Fig. 1 is that institute's Phthalocyanine Zinc content of Comparative Examples 1 and embodiment 6 is respectively (a) 0%; (b) 0.6%; (c) 1.3%; (d) 2% ZnPc/TiO 2the scanning electron microscope (SEM) photograph of nanoparticle.
Fig. 2 is the prepared Phthalocyanine Zinc of the present invention, TiO 2and different content Phthalocyanine Zinc sensitization TiO 2the uv-absorbing spectrogram of composite nanoparticle.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Embodiment
Below that the present invention prepares phthalocyanine and phthalocyanine-sensitized TiO 2the non-limiting example of composite nanoparticle.The present invention also should comprise, the various changes that those of ordinary skills can carry out under the condition that does not deviate from the scope of the invention.
Embodiment 1:
By phthalic nitrile (0.008mol), ZnCl 2(0.002mol) be dissolved in 2mlDMF, add 0.2mlDBU, be placed in microwave reactor with 2450MHz microwave 300W microwave 30min, cooled and filtered, with deionized water dilution filtrate, cross the leaching filter cake extremely colourless with deionized water wash, dry product and obtain Phthalocyanine Zinc, productive rate is 78%.
Embodiment 2:
By phthalic nitrile (0.008mol), CoCl 26H 2o (0.002mol) is dissolved in 5mlDMAE, adds 0.6mlDBU, is placed in microwave reactor with 2450MHz microwave 1000W microwave 2min, cooled and filtered, with deionized water dilution filtrate, cross the leaching filter cake extremely colourless with deionized water wash, dry product and obtain Cobalt Phthalocyanine, productive rate is 63%.
Embodiment 3:
By phthalic nitrile (0.008mol), CuCl 22H 2o (0.002mol) is dissolved in the 20ml Pentyl alcohol, adds 3mlDBU, is placed in microwave reactor with 2450MHz microwave 600W microwave 8min, cooled and filtered, with deionized water dilution filtrate, cross the leaching filter cake extremely colourless with deionized water wash, dry product and obtain CuPc, productive rate is 52%.
Embodiment 4:
By phthalic nitrile (0.008mol), NiCl 26H 2o (0.002mol) is dissolved in the 30ml dimethyl sulfoxide (DMSO), add 5mlDBU, be placed in microwave reactor with 2450MHz microwave 450W microwave 15min, cooled and filtered, with deionized water dilution filtrate, cross the leaching filter cake extremely colourless with deionized water wash, dry product and obtain Nickel Phthalocyanine, productive rate is 60%.
Embodiment 5:
Phthalic nitrile (0.008mol) is dissolved in 3mlDMAE, add 1mlDBU, be placed in microwave reactor with 2450MHz microwave 800W microwave 10min, cooled and filtered, with deionized water dilution filtrate, cross the leaching filter cake extremely colourless with deionized water wash, dry product and obtain hollow phthalocyanine, productive rate is 32%.
Embodiment 6:
Product 0.003g Phthalocyanine Zinc in embodiment 1 is scattered in the 30ml ethanolic soln, add wherein CTAB (0.2M) and 2ml tetrabutyl titanate, add the 5ml hydrazine hydrate after stirring, continue to stir after 0.5h in microwave reactor with 2450MHz microwave 1000W irradiation 3min, cooling and with deionized water supersound washing filtration product repeatedly, then it is dispersed in deionized water to 180 ℃ of crystallization 5h in water heating kettle.Final product after filtration, make the ZnPc/TiO that the ZnPc mass content is 6% after washing, drying 2composite nanoparticle.The add-on of controlling phthalocyanine can make different content as 0.6%, 1.3%, 2% ZnPc/TiO 2, the scanning electron microscope of its nanoparticle is as Fig. 1 (b, c, d), and the uv-absorbing spectrogram is as Fig. 2.
Select the ZnPc/TiO of 0.6%, 1.3%, 2% 3 content 2for photochemical catalysis CO 2methyl alcohol experiment processed, its productive rate is respectively 2700 μ mol/g-cat., 3890 μ mol/g-cat., 1480 μ mol/g-cat..
Embodiment 7:
Getting CuPc in embodiment 3 (0.006g) is scattered in the 30ml ethanolic soln, add wherein PVP (0.3g) and 2ml titanium isopropylate, add the 1ml deionized water after stirring, continue to stir after 0.5h 300W irradiation 30min in microwave reactor, cooling and with deionized water supersound washing filtration product repeatedly, then it is dispersed in deionized water to 150 ℃ of crystallization 10h in water heating kettle.Final product after filtration, make CuPc/TiO after washing, drying 2composite nanoparticle.
Embodiment 8:
Except following variation, all the other are with embodiment 8.Get embodiment 2 Cobalt Phthalocyanines (0.036g) and be scattered in 30ml ethanol, 800W microwave 10min, in 200 ℃ of crystallization 5h.Products therefrom is CoPc/TiO 2composite nanoparticle.
Embodiment 9:
Except following variation, all the other are with embodiment 8.Get embodiment 4 Nickel Phthalocyanines (0.048g) and be scattered in 30ml ethanol, 800W microwave 10min, in 200 ℃ of crystallization 5h.Products therefrom is NiPc/TiO 2composite nanoparticle.
Comparative Examples 1:
Add CTAB (0.005M) and 2ml tetrabutyl titanate in 30ml ethanol, stir in backward mixed solution and add the 0.5ml hydrazine hydrate, after continuing to stir 0.5h, mixed solution is placed in to microwave oven 800W irradiation 10min, cooling and with deionized water supersound washing filtration product repeatedly, then it is dispersed in deionized water to 200 ℃ of high temperature crystallization 3h in water heating kettle.Final product after filtration, make TiO after washing, drying 2nanoparticle, Phthalocyanine Zinc content is 0%.The scanning electron microscope of this nanoparticle is as Fig. 1 (a), and the uv-absorbing spectrogram is as Fig. 2.This catalyzer is at photochemical catalysis CO 2in methyl alcohol experiment processed, methanol yield is 320 μ mol/g-cat..

Claims (10)

1. microwave-hydrothermal method synthetic phthalocyanine sensitization TiO 2the preparation method of nanoparticle, is characterized in that, comprises the following steps:
(1) preparation of phthalocyanine complex
Phthalic nitrile, metal-salt be take to mol ratio and as 4: 1, be dissolved in solvent, after adding diazabicylo (DBU) to mix, in microwave reactor, with 2450MHz microwave exposure 2-30min, cooled and filtered is purified and is obtained corresponding phthalocyanine complex;
(2) phthalocyanine-sensitized TiO 2the preparation of composite nanoparticle
Step (1) phthalocyanine complex, tensio-active agent and titanium source are scattered in ethanolic soln, after stirring, splash into catalyzer, after continuing to stir 0.5h, mixed solution is placed in to microwave reactor with 2450MHz microwave exposure 2min～30min; Cooled and filtered with the deionized water supersound washing, then by powder with 150-200 ℃ of hydrothermal treatment consists 3h～10h; Finally by washing, to filter, drying obtains phthalocyanine-sensitized TiO 2composite nanoparticle.
2. according to the method for claim 1, it is characterized in that one or more in the muriate that the metal-salt that step (1) is used is zinc, cobalt, copper, iron, nickel, acetate, vitriol.
3. according to the method for claim 1, it is characterized in that, the described solvent of step (1) is N-N dimethyl formamide (DMF), thanomin, dimethyl sulfoxide (DMSO), primary isoamyl alcohol, one or more in Pentyl alcohol.
4. according to the method for claim 1, it is characterized in that, 1g phthalic nitrile solvent for use is that 2-30ml, DBU used are 0.2-5ml.
5. according to the method for claim 1, it is characterized in that, step (1) irradiation power is 300-1000W, and irradiation time is 2-30min.
6. according to the method for claim 1, it is characterized in that, the consumption of step (2) phthalocyanine is TiO 20.2%～5% of massfraction.
7. according to the method for claim 1, it is characterized in that, step (2) titanium source is tetrabutyl titanate, a kind of in titanium isopropylate.
8. according to the method for claim 1, it is characterized in that, tensio-active agent is a kind of in cetyl trimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), and its concentration is controlled at 0.005M～0.2M.
9. according to the method for claim 1, it is characterized in that, catalyzer is a kind of in water, hydrazine hydrate, ammoniacal liquor, and the volume ratio of catalyzer and ethanol is 1: 120 to 1: 6.
10. the preparation method of a phthalocyanine complex, it is characterized in that comprising the following steps: metal-salt, phthalic nitrile be take to mol ratio as 1 or be dissolved in solvent at 0: 4, after adding DBU to mix, in microwave reactor, with 2450MHz microwave exposure 2-30min, cooled and filtered is purified and is obtained corresponding phthalocyanine complex;
Metal-salt is a kind of in muriate, acetate, vitriol; Solvent is N-N dimethyl formamide (DMF), thanomin, dimethyl sulfoxide (DMSO), primary isoamyl alcohol, one or more in Pentyl alcohol; Wherein 1g phthalic nitrile solvent for use consumption is that 2-30ml, DBU consumption used are 0.2-5ml.
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CN107601558A (en) * 2017-10-25 2018-01-19 广西科技大学 A kind of method that microwave heating prepares nano titanium oxide
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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN104690295A (en) * 2013-12-05 2015-06-10 南通建陵纳米科技有限公司 Method for preparing monodispersed ultrafine particles
CN104690295B (en) * 2013-12-05 2017-06-30 南通建陵纳米科技有限公司 The method for preparing monodisperse superfine particle
CN105131002A (en) * 2015-08-25 2015-12-09 辽宁大学 Synthetic method of unsubstituted cobalt phthalocyanine
CN105536876A (en) * 2016-02-05 2016-05-04 常州大学 Preparation method of nitro-cobalt phthalocyanine/attapulgite composite photo-catalyst
CN107601558A (en) * 2017-10-25 2018-01-19 广西科技大学 A kind of method that microwave heating prepares nano titanium oxide
CN109400614A (en) * 2018-12-07 2019-03-01 浙江工业大学上虞研究院有限公司 A kind of preparation method of Phthalocyanine Zinc
CN110559949A (en) * 2019-08-13 2019-12-13 中北大学 Phthalocyanine derivative modified surfactant and polyoxometallate self-assembly nano material and preparation method thereof
CN114405548A (en) * 2021-12-30 2022-04-29 福州大学 Composite photocatalyst metal phthalocyanine/lanthanum titanate and preparation method and application thereof
CN114405548B (en) * 2021-12-30 2023-02-14 福州大学 Composite photocatalyst metal phthalocyanine/lanthanum titanate and preparation method and application thereof

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