CN104959166A - In-situ preparation method of zinc phthalocyanine/carbon nanotube composite catalyst based on solvothermal method - Google Patents
In-situ preparation method of zinc phthalocyanine/carbon nanotube composite catalyst based on solvothermal method Download PDFInfo
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Abstract
The invention relates to an in-situ preparation method of a zinc phthalocyanine/carbon nanotube composite catalyst based on a solvothermal method. The in-situ preparation method comprises the steps of pretreating a carbon nanotube: adding concentrated nitric acid to the carbon nanotube, flowing back, heating, mixing, cooling, washing with water to be neutral, performing suction filtration, and drying; preparing the zinc phthalocyanine/carbon nanotube composite catalyst: adding the carbon nanotube, phthalonitrile, octan zinecnaty, 1,8-diazabicyclo [5,4,0] hendecane-7-alkene and the carbon nanotube to a beaker, adding a solvent, mixing for 30 minutes, and then pouring into a reaction still for solvothermal reaction. The in-situ preparation method has the beneficial effects that the used solvent is low in price and is easy to obtain, and no environmental pollution is generated; the preparation method of the zinc phthalocyanine/carbon nanotube is simple, the reaction time is short, the aftertreatment is easy, and industrial production is facilitated; effective degradation of pollutants malachite green is realized, and the photocatalytic activity is obviously better than that of pure zinc phthalocyanine particles.
Description
Technical field
The invention belongs to material chemistry technical field, relate to a kind of method preparing ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position.
Background technology
Phthalocyanine, particularly metal phthalocyanine generally all have good catalytic performance, this is because phthalocyanine there is the macrocyclic ligand of elevation plane characteristic, make catalytic reaction can occur in the axial location of plane.The simultaneously character of macrocyclic ligand not only electronq donor, and there is the characteristic of electron acceptor, thus the connecing nucleophobic ability and can be regulated by the replacement changed around the metallic element of its frame center and its ring on phenyl ring of phthalocyanine, and the chemical property of metal phthalocyanine is highly stable.At present, comprise ammonia synthesis reaction, hydrogenation reaction, dehydrogenation reaction, the reduction reaction of nitrogen oxide and acetylene, the carboxylation reaction of aromatic hydrocarbons, decarboxylic reaction, dehalogenation reaction, many reactions such as decomposition reaction and oxidation reaction can with phthalocyanine as catalyst.The visible catalytic oxidation technologies of metal phthalocyanine is also in exploratory development and starting stage, and catalytic efficiency is not very high, and the reaction time is long, and these are all affect it to become the difficult problem that excellent catalyst needs to capture.So the reason of analyzing influence metal phthalocyanine catalytic efficiency, finds out the method improving catalytic efficiency and has important practical significance and huge applications value.
CNT (CNTs) is a kind of novel material with carbon element, because the machinery of its uniqueness, electricity, chemical stability and the excellent properties such as heat endurance, high-specific surface area cause the very big concern of people.CNT has unique hollow tube cavity configuration and excellent electronic property, and absorption property, mechanics and Thermodynamically stable performance etc., be therefore very suitable as catalyst carrier.Active constituent loads on CNT by people usually, thus obtains carbon nanotube loaded catalyst.In prior art, report about carbon nanotube loaded method is adopt infusion process substantially, and as well known to those skilled in the art, and the course of reaction time of the carbon nano tube composite catalyst adopting the technical scheme of this infusion process to obtain is longer, to consume raw material more, post processing comparatively bothers.Therefore, provide a kind of whole reaction time short, pollution-free, the preparation method of the simple metal phthalocyanine/carbon nano tube composite catalyst of post processing is problem in urgent need to solve.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides a kind of solvent-thermal method and react the method that a step preparation has the ZnPc/carbon nano tube compound material of photocatalytic activity, utilize the carboxyl of carbon nano tube surface and the electrostatic interaction of Phthalocyanine Zinc, make Phthalocyanine Zinc original position be adsorbed in carbon nano tube surface, and then form the composite that Phthalocyanine Zinc original position is covered in CNT.
It is a kind of method preparing ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position that the present invention solves a kind of technical scheme that its technical problem adopts, and comprises the following steps:
(1) pretreatment of CNT: add nitric acid in CNT, 115 ~ 125 DEG C of reflux heatings stir 8.5 ~ 9.5h, and cooling, is washed to neutrality, and suction filtration is dried;
(2) preparation of ZnPc/carbon nano tube composite catalyst: by pretreated CNT, phthalonitrile, two acetate hydrate zinc, 1 in step (1), 8-diazabicylo [5,4,0] 11 carbon-7-alkene and CNT join in beaker, add solvent, stir 30 minutes, pour in reactor, after being sealed by reactor, carry out the solvent thermal reaction of 2 ~ 4 hours in 190 DEG C; Room temperature is naturally cooled to after reaction terminates; The sample prepared is taken out, repeatedly rinses the residual reactant of removal ZnPc/carbon nano tube surface absorption successively with purified water and absolute ethyl alcohol, put into oven drying and can obtain ZnPc/carbon nano tube compound material.
Further, in step (1), CNT is multi-walled carbon nano-tubes, and the concentration of nitric acid is 50 ~ 70wt%.
Further, in step (2), the mol ratio of phthalonitrile and two acetate hydrate zinc is 4:1, phthalonitrile and 1,8-diazabicylo [5,4,0] mass ratio of 11 carbon-7-alkene is 1.5 ~ 4:1, and the mass ratio of phthalonitrile and CNT is 2.7 ~ 7.7:1.
Further, in step (2), solvent is ethanol or methyl alcohol.
The invention has the beneficial effects as follows: the etoh solvent that (1) uses is cheap and easy to get, and environmentally safe; (2) ZnPc/preparation method of carbon nano-tube is simple, and the reaction time is short, and post processing is easy, is conducive to suitability for industrialized production; (3) achieve the effective degraded to pollutant malachite green, its photocatalytic activity will significantly better than pure ZnPc particle.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described.
Fig. 1 is preparation flow figure of the present invention;
Fig. 2 is the transmission electron microscope picture of ZnPc/carbon nano tube composite catalyst synthesized by the embodiment of the present invention 1 and CNT, and a is ZnPc/carbon nano tube composite catalyst, and b is CNT;
Fig. 3 is the XRD figure of ZnPc/carbon nano tube composite catalyst synthesized by the embodiment of the present invention 1 and ZnPc;
Fig. 4 is the DRS figure of the ZnPc/carbon nano tube composite catalyst ZnPc synthesized by the embodiment of the present invention 1;
Fig. 5 is under xenon lamp irradiates after 50min, ZnPc/carbon nano tube composite catalyst synthesized by ZnPc, embodiment 1 and CNT are to the degradation rate comparison diagram of malachite green, a is ZnPc, and b is ZnPc/carbon nano tube composite catalyst, and c is CNT.
Detailed description of the invention
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
(1) pretreatment of CNT
Take the multi-walled carbon nano-tubes of 0.3029g, add the red fuming nitric acid (RFNA) of 150mL 65%, 120 DEG C add thermal agitation 9h, and reaction terminates rear cooling, washes with water to neutrality, obtain the CNT of purifying after drying.
(2) preparation of ZnPc/carbon nano tube compound material
Take 1.5mmol bis-acetate hydrate zinc, 6mmol phthalonitrile, CNT 0.25g with 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene (DBU) 0.2mL, add 50ml absolute ethyl alcohol as solvent, stir and pour in reactor after 30 minutes, after reactor sealing, carry out the solvent thermal reaction of 2 hours in 190 DEG C, reaction terminates rear stopping heating, naturally cools to room temperature.The above-mentioned sample prepared is taken out, uses purified water and absolute ethyl alcohol repeatedly to rinse the residual reactant of ZnPc/carbon nano tube surface absorption, then put into oven drying and can obtain ZnPc/carbon nano tube composite catalyst.
Embodiment 2
(1) pretreatment of CNT
Take the multi-walled carbon nano-tubes of 0.5010g, add the red fuming nitric acid (RFNA) of 150mL 65%, 120 DEG C add thermal agitation 9h, and reaction terminates rear cooling, washes with water to neutrality, obtain the CNT of purifying after drying.
(2) preparation of ZnPc/carbon nano tube compound material
Take 1.5mmol bis-acetate hydrate zinc, 6mmol phthalonitrile, CNT 0.4g and 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene (DBU) 0.5mL, add 50ml absolute ethyl alcohol as solvent, stir and pour in reactor after 30 minutes, after reactor sealing, carry out the solvent thermal reaction of 4 hours in 190 DEG C, reaction terminates rear stopping heating, naturally cools to room temperature.The above-mentioned sample prepared is taken out, uses purified water and absolute ethyl alcohol repeatedly to rinse the residual reactant of ZnPc/carbon nano tube surface absorption, then put into oven drying and can obtain ZnPc/carbon nano tube composite catalyst.
As shown in Figure 2, ZnPc granular absorption is on CNT tube wall, dispersed better for the transmission electron microscope picture of the ZnPc/carbon nano tube composite catalyst prepared by embodiment 1.Metal phthalocyanine can be overcome so easily occur to assemble clustering phenomena thus the shortcoming reducing catalytic efficiency.
As shown in Figure 3, the ZnPc characteristic peak of fabricated in situ is obvious for the XRD figure of the ZnPc/carbon nano tube composite catalyst prepared by embodiment 1, illustrates to have good crystal formation by the ZnPc of solvent structure.After carbon nanotube loaded, the specific diffraction maximum ining contrast to the specific diffraction maximum ZnPc/CNT (ZnPc-MWCNTs) of ZnPc (ZnPc) obviously dies down, this also illustrates the performance that CNT have impact on ZnPc, it is good that the load of CNT has made the dispersiveness of ZnPc become, and effectively prevents the clustering phenomena of ZnPc.
Fig. 4 is the uv drs curve map of ZnPc/carbon nano tube composite catalyst prepared by embodiment 1 situ, and ZnPc/carbon nano tube composite catalyst synthesized as seen from the figure has good absorption in visible region.
The light-catalyzed reaction of ZnPc/carbon nano tube composite catalyst prepared by embodiment 1 situ is carried out in photo catalysis reactor.Reactor is three layers of concentric circles tubular glass container, and middle hanging has 1000w xenon lamp, and logical recirculated cooling water in inner sleeve, respond in the middle of inner-outer sleeve device.Under magnetic stirring ZnPc/the carbon nano tube composite catalyst of preparation in 40mg embodiment 1 is joined 50ml initial concentration C
0in the malachite green of=15mg/L, powerful magnetic agitation is adopted to keep Granular composite even, by malachite green concentration C after assaying reaction and initial concentration C
0ratio weigh the photocatalytic activity of ZnPc/CNT.Concrete grammar for get 2ml solution after 10min, so that the concentration of test malachite green, centrifugal filtration dezincify phthalocyanine/carbon nanotube particulate, at ultraviolet-visible spectrometer in its UV absorption intensity of 617nm place test, thus analyzes the photocatalytic activity of malachite green solution.
Result as shown in Figure 5, shows that prepared ZnPc/carbon nano tube compound material demonstrates and has better photocatalytic activity than pure ZnPc.
ZnPc/carbon nano tube composite catalyst that the method prepares, decentralized photo is good on the carbon nanotubes for ZnPc well-regulated crystal outward appearance and ZnPc, effectively prevent the gathering of phthalocyanine, whole preparation process is simple to operate, with low cost, the reaction time is short, does not produce harmful substance, course of reaction is easy to control, and meets production actual needs.
The composite of prepared ZnPc/CNT is carried out photocatalysis experiment, to test its photocatalytic activity.Experimental result shows that ZnPc/carbon nano tube compound material that this method is synthesized has the photocatalytic activity being better than pure ZnPc, can be applicable to the process of pollutant in environment.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must determine its technical scope according to right.
Claims (4)
1. prepare a method for ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position, it is characterized in that: comprise the following steps:
(1) pretreatment of CNT: add nitric acid in CNT, 115 ~ 125 DEG C of reflux heatings stir 8.5 ~ 9.5h, and cooling, is washed to neutrality, and suction filtration is dried;
(2) preparation of ZnPc/carbon nano tube composite catalyst: by pretreated CNT, phthalonitrile, two acetate hydrate zinc, 1 in step (1), 8-diazabicylo [5,4,0] 11 carbon-7-alkene and CNT join in beaker, add solvent, stir 30 minutes, pour in reactor, after being sealed by reactor, carry out the solvent thermal reaction of 2 ~ 4 hours in 190 DEG C; Room temperature is naturally cooled to after reaction terminates; The sample prepared is taken out, repeatedly rinses the residual reactant of removal ZnPc/carbon nano tube surface absorption successively with purified water and absolute ethyl alcohol, put into oven drying and can obtain ZnPc/carbon nano tube compound material.
2. a kind of method preparing ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position according to claim 1, is characterized in that: in described step (1), CNT is multi-walled carbon nano-tubes, and the concentration of nitric acid is 50 ~ 70wt%.
3. a kind of method preparing ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position according to claim 1, it is characterized in that: in described step (2), the mol ratio of phthalonitrile and two acetate hydrate zinc is 4:1, phthalonitrile and 1,8-diazabicylo [5,4,0] mass ratio of 11 carbon-7-alkene is 1.5 ~ 4:1, and the mass ratio of phthalonitrile and CNT is 2.7 ~ 7.7:1.
4. a kind of method preparing ZnPc/carbon nano tube composite catalyst based on solvent-thermal method original position according to claim 1, is characterized in that: in described step (2), solvent is ethanol or methyl alcohol.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732814A (en) * | 2016-12-02 | 2017-05-31 | 东华大学 | A kind of fiber/CNT/ZnPc three-dimensional recyclable efficient catalytic material and its preparation and application |
| CN108855221A (en) * | 2018-05-07 | 2018-11-23 | 常州大学 | A kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation method |
| CN108878906A (en) * | 2018-06-20 | 2018-11-23 | 重庆大学 | The method that solvent-thermal method prepares Fe-N-C type carbonaceous oxygen reduction catalyst |
| CN109675603A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-supported catalysts and its preparation method and application of silica protection |
| CN110479373A (en) * | 2019-06-12 | 2019-11-22 | 常州大学 | The preparation method of one kind 3 α-(to tert-butyl benzene oxygroup)-α-(nitro)-Phthalocyanine Zinc/multi-walled carbon nanotube catalyst |
| CN111229325A (en) * | 2020-02-29 | 2020-06-05 | 杭州师范大学钱江学院 | BC/CNT/MPc ternary composite catalyst and synthetic method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006291088A (en) * | 2005-04-13 | 2006-10-26 | Dainippon Ink & Chem Inc | Phthalocyanine compound and colored composition containing the same |
| CN101507930A (en) * | 2009-03-27 | 2009-08-19 | 华南师范大学 | Metal phthalocyanine/carbon nano tube composite catalyst and its preparation method and lithium/thinly chloride battery using the catalyst |
| CN103787302A (en) * | 2014-01-23 | 2014-05-14 | 黑龙江大学 | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
-
2015
- 2015-07-06 CN CN201510392137.0A patent/CN104959166A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006291088A (en) * | 2005-04-13 | 2006-10-26 | Dainippon Ink & Chem Inc | Phthalocyanine compound and colored composition containing the same |
| CN101507930A (en) * | 2009-03-27 | 2009-08-19 | 华南师范大学 | Metal phthalocyanine/carbon nano tube composite catalyst and its preparation method and lithium/thinly chloride battery using the catalyst |
| CN103787302A (en) * | 2014-01-23 | 2014-05-14 | 黑龙江大学 | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
Non-Patent Citations (2)
| Title |
|---|
| YI WAN ET AL.: "Significant improvement of styrene oxidation over zinc phthalocyanine supported on multi-walled carbon nanotubes", 《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》 * |
| 张克立等: "《无机合成化学》", 31 October 2004, 武汉大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732814A (en) * | 2016-12-02 | 2017-05-31 | 东华大学 | A kind of fiber/CNT/ZnPc three-dimensional recyclable efficient catalytic material and its preparation and application |
| CN108855221A (en) * | 2018-05-07 | 2018-11-23 | 常州大学 | A kind of [3-2- (N- ethyl phenylamino) ethyoxyl] ZnPc/attapulgite composite photo-catalyst preparation method |
| CN108878906A (en) * | 2018-06-20 | 2018-11-23 | 重庆大学 | The method that solvent-thermal method prepares Fe-N-C type carbonaceous oxygen reduction catalyst |
| CN109675603A (en) * | 2018-12-28 | 2019-04-26 | 西安交通大学 | A kind of carbon-supported catalysts and its preparation method and application of silica protection |
| CN110479373A (en) * | 2019-06-12 | 2019-11-22 | 常州大学 | The preparation method of one kind 3 α-(to tert-butyl benzene oxygroup)-α-(nitro)-Phthalocyanine Zinc/multi-walled carbon nanotube catalyst |
| CN111229325A (en) * | 2020-02-29 | 2020-06-05 | 杭州师范大学钱江学院 | BC/CNT/MPc ternary composite catalyst and synthetic method thereof |
| CN111229325B (en) * | 2020-02-29 | 2023-05-30 | 杭州师范大学钱江学院 | BC/CNT/MPc ternary composite catalyst and synthetic method thereof |
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