CN105126916B - A kind of recyclable tetranitro copper phthalocyanine composite catalyst of magnetic and the application in phenolic comp ' ds pollution develops the color identification reaction - Google Patents
A kind of recyclable tetranitro copper phthalocyanine composite catalyst of magnetic and the application in phenolic comp ' ds pollution develops the color identification reaction Download PDFInfo
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Abstract
Application the present invention relates to a kind of recyclable tetranitro copper phthalocyanine composite catalyst of magnetic and in phenolic comp ' ds pollution develops the color identification reaction, it is coated with the ferroferric oxide magnetic carrier of amorphous c film layer, and is supported on carrier surface, tetranitro copper (II) phthalocyanine with " island shape " nanostructured.The catalyst of the present invention is with low cost and nontoxic, not only with stable physical property, and integrates chemical catalysis and the function of magnetic recovery two, repeated multiple times can use.It is used as a variety of phenol (phenol, 2 chlorophenols, 4 chlorophenols and 2 in the catalyst aqueous solution, 4 chlorophenols) with the chromogenic reactions of 4 amino-antipyrines, colour developing is quick, with low cost, easily operated, and catalytic reaction is without illumination and heating, only can quickly it be reacted at room temperature by the contact between catalyst, oxidant and substrate, it is catalytic reaction process green safety, easily controllable.
Description
Technical field
The present invention relates to a kind of preparation of the composite with chemical catalysis and magnetic recovery function, and in particular to one
Recyclable tetranitro copper (II) the phthalocyanine composite catalyst of magnetic is planted, it can accelerate 4-AA and phenol as catalyst
The chromogenic reaction of class compound such as phenol (or chlorophenol), improves 4-AA chromogenic assay identification phenolic compound,
Colour developing identification for phenolic comp ' ds pollution in water environment.
Background technology
Phenol and chlorinated phenols are a class high toxicity environmental contaminants, and this kind of compound derives from pharmacy, printing and dyeing, papermaking
And Insecticides (tech) ＆ Herbicides (tech) and bactericide in the chemical industry such as plastic products, and agricultural and wood working industry.Phenolic compound
It is difficult to by Institute of Micro-biology's degraded of nature, and with the property such as soluble in water, volatile, the water source by its pollution can be with certainly
Expand pollution range in the presence of right boundary water circulation, easily cause animals and plants and human infection and produce various serious diseases.Cause
This, using simply, easily method detects that the phenolic comp ' ds pollution in environment has great importance.
The phenol pollutant in solution can be accurately detected using high performance liquid chromatography (HPLC) and gas-chromatography (GC) technology,
But this kind of large-scale instrument is costly, maintenance cost is high, operating personnel need to could be competent at the detection work typically required through professional training
Make.At present, detection industry often makees oxidant using the potassium ferricyanide, in the basic conditions pacifies the 4- amino coexisted in the aqueous solution
For than woods (developer) and phenolic compound oxidation, the quinoneimine dye of generation pink is allowed to, can be tested by its shade
Demonstrate,prove phenol content and its contaminated degree, i.e. 4-AA chromogenic assay in solution.This method has chromogenic reaction fast
Speed, the accurate advantage of measure, it has also become the standard method of phenolic compound detection accreditation in industry.But this method actually makes
During, the influence factor for causing its testing result inaccurate is still suffered from.The potassium ferricyanide oxidant such as used is in illumination bar
Its bad stability under part, the hydrogen cyanide gas for reaction generation severe toxicity of decomposing in acid condition.In addition, potassium ferricyanide sheet
Body belongs to low toxicity compounds, and the aqueous solution is dissolved in chromogenic reaction and is used, it is difficult to recycling, thus is easily caused environmental pollution.
Metal phthalocyanine is a kind of inexpensive, avirulent metal organic complex, and some metal phthalocyanines have active oxidation dosage form into urging
Change the ability that extremely strong " metal-oxygen " active specy of oxidability accelerates substrate stoichiometric reaction, therefore with metal phthalocyanine and oxidation
The oxidized catalyst precursor of agent composition, which ties up to advanced catalytic oxidation technical field, important application.
2007, India scholar Santhanalakshmi reported a variety of water-soluble tetrasulfonic acid metal phthalocyanines and peroxide
Change hydrogen (H2O2) as catalyst and oxidant, accelerate the chromogenic reaction [1] of phenol and 4-AA.The application first
Inventor has found that tetranitro iron (II) phthalocyanine can make catalyst during Wuhan University of Technology completes doctoral candidate's work, plus
Fast four kinds of phenolic compounds of dioxygen oxidation (phenol, 2- chlorophenols, 4- chlorophenols and 2,4- chlorophenols) and 4-AA
Chromogenic reaction [2].Seminar of Xuchang College where then successively reports water-soluble eight carboxyls iron (III) phthalocyanine activation uncle again
Butylhydroperoxide (BuOOH), accelerates the chromogenic reaction [3] of phenol (2- chlorophenols, 1- naphthols) and 4-AA, and
Two kinds of water-soluble iron (III) phthalocyanines containing high steric-hindrance amino substituent structure are catalyzed five kinds of phenolic compounds with TBHP
(phenol, 2- chlorophenols, 4- chlorophenols, 2,4- chlorophenols and 1- naphthols) oxidation reaction, the research for recognizing phenolic comp ' ds pollution
Work [4].In addition, it has been found that manganese phthalocyanine can accelerate 2- phenol (4- chlorophenols or 2,4- chlorine under sunshine illumination effect
Phenol) with the chromogenic reaction [5] of 4-AA.Research illustrates that metal phthalocyanine can be normal with some as catalyst above
With oxidant (such as：H2O2, BuOOH, persulfate etc.) realize the chromogenic reaction of phenolic comp ' ds pollution.Our seminar are sent out in the near future
Existing, tetranitro copper (II) phthalocyanine (TNCuPc) can constitute catalytic oxidation system with TBHP, accelerate phenol (2- chlorine
Phenol, 4- chlorophenols, 2,4- chlorophenols or 1- naphthols) chromogenic reaction between 4-AA.
At present, about tetranitro copper (II) phthalocyanine the existing many document reports of synthesis and performance study, but existing literature
In terms of the photocatalysis research for being only limitted to tetranitro copper (II) phthalocyanine, such as Northeast Normal University Shao Chang roads seminar successively reports molten
The hot method of agent prepares the hollow form micron ball works of tetranitro copper (II) phthalocyanine, as the photochemical catalyst of rhodamine B degradation
[6]；Solvent thermal reaction prepares the TiO that surface has tetranitro copper (II) phthalocyanine to modify2Bundles of nanofibers, is used for as photochemical catalyst
The degraded [7] of rhodamine B；Solvent thermal reaction prepares the Fe of class dandelion structure3O4@CuTNPc photochemical catalysts, for rhodamine B
[8] are reacted in light degradation with methyl blue.In addition, Heilongjiang University SmithKline English professor reports sol-gel process synthesis tetranitro
Copper phthalocyanine/meso-porous titanium dioxide silicon composite and its structural analysis and the research work [9] characterized.However, in non-illuminated conditions
Under (without using sunshine and artificial light source), tetranitro copper (II) phthalocyanine can be catalyzed phenol colour developing research work there is no be seen in it is all kinds of
Document.Except this, although consumption of the metal phthalocyanine of detection in a chromogenic reaction is completed is less, if can be by simplicity side
Method is reclaimed, and cost can have not only been saved with Reusability, can also reduce the metal phthalocyanine caused by misoperation be lost in
Environment.
Bibliography
[1]N.Rajendiran,J.Santhanalakshmi,J.Mol.Catal.A:Chem.245(2006)185–
191.
[2]D.P.Li,Y.L.Tong,J.Huang,L.Y.Ding,Y.M.Zhong,D.Zeng,P.Yan,
J.Mol.Catal.A:Chem.345(2011)108–116.
[3]D.P.Li,S.X.Ge,J.Huang,J.J.Gong,P.Yan,W.Y.Lu,G.Z.Tian,L.Y.Ding,
Catal.Commun.45(2014)95–99.
[4]J.J.Gong,D.P.Li,J.Huang,L.Y.Ding,Y.L.Tong,K.Li,C.Zhang,
Catal.Lett.144(2014)487–497.
[5]D.P.Li,S.X.Ge,J.Huang,J.J.Gong,T.X.Wang,P.Yan,G.B.Li,L.Y.Ding,
Sep.Purif.Technol.125(2014)216–222.
[6]M.Y.Zhang,C.L.Shao,Z.C.Guo,Z.Y.Zhang,J.B.Mu,P.Zhang,T.P.Cao,
Y.C.Liu,ACS Appl.Mater.Interfaces 3(2011)2573–2578.
[7]M.Y.Zhang,C.L.Shao,Z.C.Guo,Z.Y.Zhang,J.B.Mu,T.P.Cao,Y.C.Liu,ACS
Appl.Mater.Interfaces 3(2011)369–377.
[8]Z.C.Guo,C.L.Shao,M.Y.Zhang,J.B.Mu,Z.Y.Zhang,P.Zhang,B.Chen,
Y.C.Liu,J.Mater.Chem.21(2011)12083–12088.
[9] Jin Xiaoqi, Shao Shizhuan, Wang Haiyan, Zhang Hengbin, SmithKline English tetranitro substituted phthalocyanine copper/mesoporous silicon oxide are multiple
The synthesis of condensation material and sign Heilongjiang University's natural science journal 25 (2) (2008) 246-250.
The content of the invention
One of goal of the invention of the present invention is to provide a kind of magnetic recyclable tetranitro copper (II) phthalocyanine composite catalyzing
Agent.
The two of the goal of the invention of the present invention are that providing a kind of recyclable tetranitro copper (II) phthalocyanine of above-mentioned magnetic is combined
The preparation method of catalyst.
The three of the goal of the invention of the present invention are that providing a kind of recyclable tetranitro copper (II) phthalocyanine of above-mentioned magnetic is combined
Application of the catalyst in (chlorine) phenolic comp ' ds pollution develops the color identification reaction.
A kind of recyclable tetranitro copper (II) phthalocyanine composite catalyst (Fe of magnetic3O4@C@TNCuPc), including be coated with
The ferroferric oxide magnetic carrier of amorphous c film layer, and it is supported on carrier surface, four with " island shape " nanostructured
Nitro copper (II) phthalocyanine, is designated as Fe3O4@C@TNCuPc。
By such scheme, the load capacity of tetranitro copper (II) phthalocyanine is to contain 2 to 3mg tetra- nitre per 15mg composite catalysts
Base copper (II) phthalocyanine.
By such scheme, the magnetic ferroferric oxide is micro-sphere structure of the diameter 700 to 900nm.
The preparation method of the recyclable tetranitro copper phthalocyanine composite catalyst of magnetic, it uses solvent-thermal method to prepare, including
Following steps：
Step (1)：Fe3O4The preparation of magnetic carrier：
By FeCl3·6H2O is added in the ethylene glycol solution containing neopelex and sodium acetate and fully stirred
Mixing dissolves it, 170-190 DEG C of 8-16h of reaction, obtains Fe3O4Magnetic carrier；
Step (2)：Fe3O4@C preparation：
Fe prepared by step (1)3O4Magnetic carrier is added in D/W, and ultrasonic disperse is uniform, and 170-190
DEG C reaction 2-6h, obtain be coated with amorphous c film layer ferroferric oxide magnetic carrier Fe3O4@C；
Step (3)：Fe3O4@C@TNCuPc preparation：
Phthalonitrile, copper acetate and ammonium molybdate are added in the glass beaker for filling ethylene glycol, stirring makes its abundant
Dissolving, is subsequently added the Fe of step (2) preparation3O4@C powder simultaneously makes its ultrasonic disperse, and liquid mixed above is transferred into reactor
Interior, 160 to 180 DEG C are reacted 10-12 hours.
By such scheme, in described step (1), FeCl3·6H2O：Neopelex：Sodium acetate：Ethylene glycol
For 1.35-2.5g：0.4-0.8g：3-4.5g：60-75mL.
By such scheme, in described step (2), glucose：Fe3O4：The consumption of water is 6.5-9.0g：0.4-0.8g：
60-75mL。
By such scheme, in described step (3), phthalonitrile：Copper acetate：Ammonium molybdate：Fe3O4@C are 17.3-
34.6mg：5.5-11mg：10-20mg：100-250mg.
By such scheme, question response kettle naturally cools to room temperature, product deionization after the completion of described step (1) reaction
Water, absolute ethyl alcohol are washed three times respectively, and gained sample collects stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers.
By such scheme, the product after the completion of step (2) reaction is washed respectively with a small amount of deionized water and absolute ethyl alcohol
Wash three times, collect stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers.
By such scheme, after completion of the reaction, reactor naturally cools to room temperature to the step (3), and black powder product is used
A small amount of deionized water and absolute ethyl alcohol are washed three times respectively, are collected after being dried 12 hours in 60 DEG C of vacuum drying chambers.
Recyclable tetranitro copper (II) the phthalocyanine composite catalyst of above-mentioned magnetic is anti-in the colour developing identification of (chlorine) phenolic comp ' ds pollution
Should in application, accelerate (chlorine) phenolic comp ' ds pollution to pacify with 4- amino itself and TBHP composition catalytic oxidation system and replace
Than the chromogenic reaction of woods, with (chlorine) phenolic comp ' ds pollution in the quinone imines pink colour dyestuff discriminance analysis system of generation.
By such scheme, described (chlorine) phenolic comp ' ds pollution is phenol, 2- chlorophenols, 4- chlorophenols or 2,4- chlorophenol.
By such scheme, above-mentioned application process is concretely comprised the following steps：By Fe3O4@C@TNCuPc catalyst is added to be detected
In the aqueous solution of (chlorine) phenol pollutant aqueous solution and 4-AA, ultrasonic disperse is subsequently added TBHP
And stir, reaction starts timing, at regular intervals, using magnet separating catalyst and collects reaction solution, using purple
Outer visible absorption spectra instrument carries out absorbance detection：Using deionized water as reference, detection reaction solution is in the range of 200-800nm
Absorbance, record 510nm at absorption values.
By such scheme, the Fe3O4The consumption of@C@TNCuPc catalyst is 4- amino peace in 10-20mg, the system
For than the concentration of woods be 2.0 × 10-4Mol/L, the concentration of TBHP is about 3 × 10-4mol/L。
By such scheme, the Fe3O4@C@TNCuPc catalyst is recovered to be reused after purification, and method is as follows：Use
Magnet is by Fe3O4@C@TNCuPc are adsorbed to beaker inwall, and the remaining pink aqueous solution is carefully poured out, then into empty beaker
Add deionized water, ultrasonic disperse Fe3O4Adsorbed again and pouring soln using magnet after@C@TNCuPc, so repeatedly until water
Solution is finally carried out after elution action again in colourless using more than 60 DEG C of deionized water, is dried in 60 DEG C of vacuum drying chambers
Collect stand-by after 12 hours.
The effect and advantage of the present invention：
1. the catalyst of the present invention uses solvothermal preparation method, obtained through three-step reaction thin to be coated with agraphitic carbon
Tetranitro copper (II) phthalocyanine of the ferroferric oxide magnetic carrier of layer.Preparation technology is simply controllable.Wherein, the carbon-coating of cladding is not only
Make material that there is resistance to acids and bases, be effectively protected ferroferric oxide magnetic carrier, and the hydrophobicity of carbon-coating makes its surface easy
With tetranitro copper (II) phthalocyanine catalyst strong bonded of hydrophobic property, the stability of catalyst is enhanced.The catalyst is through even
It is active without substantially decay after continuous four-wheel catalytic reaction, then has carbon coating layer to prepare simply, and raw materials of glucose is cheap, nontoxic
It is harmless, it is very suitable for making the interlayer between catalyst and magnetic carrier and uses.
2. the Fe of the present invention3O4@C@TNCuPc can be used as a variety of phenol (phenol, the 2- chlorobenzenes in the catalyst aqueous solution
Phenol, 4- chlorophenols and 2,4- chlorophenol) with the chromogenic reaction of 4-AA, the quinone imines pink colour dyestuff based on generation is used
Recognized in the colour developing of phenolic comp ' ds pollution.With following reaction advantage：Catalyst is with low cost and nontoxic, can be reclaimed through magnet
And be used for multiple times, its activity is without substantially decay after continuous four-wheel catalytic reaction；Catalytic reaction is without illumination and heating, only
Can quickly it be reacted at room temperature by the contact between catalyst, oxidant and substrate；Avoid in traditional detection method
The use of the harmful substance potassium ferricyanide, it is catalytic reaction process green safety, easily controllable.
Brief description of the drawings
Fig. 1 is (a) TNCuPc, (b) Fe3O4、(c)Fe3O4@C、(d)Fe3O4@C TNCuPc XRD diffraction spectral lines.
Fig. 2 is (a) TNCuPc, (b) Fe3O4、(c)Fe3O4@C、(d)Fe3O4@C@TNCuPc fourier-transform infrared light
Spectrogram.
Fig. 3 is the electron micrograph image of series of samples.Low multiplication factor (a) and the Fe of high-amplification-factor (b, c)3O4Microballoon
SEM figure；Low multiplication factor (d) and the Fe of high-amplification-factor (e)3O4The SEM figures of@C microballoons；Low multiplication factor (f) and high amplification
The Fe of multiple (g)3O4The SEM figures of@C@TNCuPc catalyst；Fe3O4The transmission electron microscope (h) of@C@TNCuPc catalyst and
High resolution transmission electron microscopy (i) figure.
Fig. 4 is (a) Fe3O4@C@TNCuPc XPS is composed and (b) Cu, (c) Fe, the high-resolution XPS collection of illustrative plates of (d) N element entirely.
Fig. 5 is through Fe3O4The UV-visible absorption spectrum of the 2- chlorophenol chromogenic reactions of@C@TNCuPc catalysis.
Fig. 6 is through Fe3O4The UV-visible absorption spectrum of the 2,4 dichloro phenol chromogenic reaction of@C@TNCuPc catalysis.
Fig. 7 is through Fe3O4The UV-visible absorption spectrum of the 4- chlorophenol chromogenic reactions of@C@TNCuPc catalysis.
Fig. 8 is through Fe3O4The UV-visible absorption spectrum of the phenol chromogenic reaction of@C@TNCuPc catalysis.
Fig. 9 is through Fe3O4Liquid chromatogram of the 2- chlorophenols color development system of@C@TNCuPc catalysis in the differential responses time.
Figure 10 is Fe3O4The uv-visible absorption spectra comparison diagram of the continuous four-wheel catalytic reactions of@C@TNCuPc, with 2- chlorobenzenes
Exemplified by phenol system.(absorbance of system is the absorbance of reaction solution at wavelength 510nm).
Figure 11 is the catalytic efficiency contrast of four kinds of catalytic oxidation systems.Wherein ■ represents Fe3O4@C@TNCuPc and BuOOH groups
Into catalytic oxidation system, ● represent the catalytic oxidation system that TNCuPc and BuOOH are constituted, ▲ represent TNFePc and BuOOH groups
Into catalytic oxidation system, ▼ represents TNCuPc and O2The catalytic oxidation system of composition.(a) 2-CP chromogenic reactions；(b) DCP shows
Colour response；(c) 4-CP chromogenic reactions；(d) Phenol chromogenic reactions.
Embodiment
Below in conjunction with drawings and examples, further the present invention will be described.
Embodiment 1
Step (1) Fe3O4The preparation of magnetic carrier：
0.64g neopelexes (SDBS) and 3.72g sodium acetates are dissolved in 65mL ethylene glycol, ultrasonic disperse
15min and being aided with stirring is completely dissolved it, adds 2.16g FeCl3·6H2O is after magnetic agitation 30min, by mixed liquor
It is transferred in 100mL hydrothermal reaction kettles, 12h is reacted at a temperature of 180 DEG C.Question response kettle naturally cools to room temperature, and product is spent
Ionized water, absolute ethyl alcohol are washed three times respectively, and gained sample collects stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers.
Step (2) Fe3O4@C preparation：
7.90g glucose is added in 70mL deionized waters, it is agitated after it is completely dissolved, take 0.46g steps (1) to make
Standby Fe3O4Powder adds ultrasonic disperse 5min in D/W, and then reaction solution is transferred in 100mL reactors, passes through
180 DEG C of reaction 4h.Product is washed three times respectively with a small amount of deionized water and absolute ethyl alcohol, and 12 are dried in 60 DEG C of vacuum drying chambers
Collect stand-by after hour.
Step (3) Fe3O4@C@TNCuPc preparation：
By 20.5mg phthalonitriles, 8.7mg Cu (Ac)2·H2O and 12mg ammonium molybdates are added sequentially to fill 75mL second
In the beaker of glycol, stirring is completely dissolved it, adds 0.2g Fe prepared by step (2)3O4@C powder and ultrasonic disperse 5min
Mixed solution is transferred in 100mL reactors afterwards, reaction temperature is set in 160 DEG C of maintenance 10h.After question response is finished, reactor
Room temperature is naturally cooled to, black powder product is washed three times respectively with a small amount of deionized water and absolute ethyl alcohol, it is dry in 60 DEG C of vacuum
Collected after being dried 12 hours in dry case.
(a) TNCuPc, (b) Fe of above-mentioned preparation3O4、(c)Fe3O4@C、(d)Fe3O4@C@TNCuPc XRD diffraction spectrograms
See Fig. 1.As seen from Figure 1：Fe3O4@C@TNCuPc diffraction maximum curve (d) and magnetic Fe3O4The diffraction maximum curve (b) of carrier
It is very close, the amorphous peak of carbon in curve (c) is not observed, this explanation Fe3O4Surface coated carbon-coating is relatively thin, additionally by song
The load capacity that TNCuPc also can be explained in line (a) and (d) contrast is seldom.FFIR figure is shown in Fig. 2, infrared spectrum
Test uses KBr pressed disc methods.As shown in Figure 2：Carbon-coating and TNCuPc are in Fe3O4Content is relatively low in@C@TNCuPc composite catalysts.
Electron micrograph image is shown in Fig. 3, as seen from Figure 3：Fe3O4@C@TNCuPc composite catalysts are by including being coated with amorphous c film
The ferroferric oxide magnetic carrier of layer, and it is supported on carrier surface, tetranitro copper (II) phthalein with " island shape " nanostructured
Cyanines are constituted, and are designated as Fe3O4@C@TNCuPc。(a)Fe3O4@C@TNCuPc XPS is composed and (b) Cu, (c) Fe, the height of (d) N element entirely
Differentiate XPS collection of illustrative plates and see Fig. 4.The high-resolution x-ray photoelectron spectroscopy (b) of element Cu illustrates that TNCuPc successfully loads to catalysis
Agent surface.
Using pipettor by 5mL 1.0 × 10-3Mol/L (chlorine) the phenol aqueous solution and 10mL 1.0 × 10-3Mol/L 4- amino
The antipyrine aqueous solution is moved in 50mL glass beakers, and adding 35mL deionized waters makes overall solution volume be 50mL.To above-mentioned
15mg Fe are added in solution3O4@C@TNCuPc catalyst, is then placed in supersonic wave cleaning machine by the glass beaker for filling reaction solution
Interior ultrasonic 10 seconds, disperse catalyst.Then, 15 μ L TBHPs are pipetted using pipettor and adds it to reaction
Stirred in solution and using glass bar, catalytic reaction is from this timing.Using magnet separating catalyst and use at regular intervals
Suction pipe collects 3mL reaction solutions, and absorbance detection is carried out using ultraviolet-visible absorption spectroscopy instrument.
Fe3O4The UV-visible absorption spectrum of@C@TNCuPc catalysis 2- chlorophenol chromogenic reactions is shown in Fig. 5.
Fe3O4The uv-visible absorption spectra of@C@TNCuPc catalysis 2,4 dichloro phenol chromogenic reactions is shown in Fig. 6.
Fe3O4The UV-visible absorption spectrum of@C@TNCuPc catalysis 4- chlorophenol chromogenic reactions is shown in Fig. 7.
Fe3O4The UV-visible absorption spectrum of@C@TNCuPc catalysis of phenol chromogenic reactions is shown in Fig. 8.
Fig. 9 is, by liquid chromatography technology, 2- chlorophenols coloring reaction system have been carried out into the chromatogram that separation is obtained, from
It can be found in the figure with the extension of chromogenic reaction time, as reactant, its chromatographic peak area constantly reduces 4-AAP and 2-CP,
Product dyes chromatographic peak area is continuously increased, and illustrates that the output of dyestuff is more and more, oxidant BuOOH chromatographic peak area
Without significant change.
Figure 10 is that selection 2- chlorophenol color development systems are test object, by Fe after the completion of every secondary response3O4@C@TNCuPc are urged
Agent is recovered to be reused after purification, and method is as follows：Using magnet by Fe3O4@C@TNCuPc are adsorbed to beaker inwall, will be surplus
The remaining pink aqueous solution is carefully poured out, then adds into empty beaker deionized water, ultrasonic disperse Fe3O4Make after@C@TNCuPc
Adsorbed again with magnet and pouring soln, so repeatedly until the aqueous solution is in colourless, finally using more than 60 DEG C of deionized water
Carry out after elution action, collected after being dried 12 hours in 60 DEG C of vacuum drying chambers again, carry out next round chromogenic reaction test, knot
Fruit shows：Fe3O4@C@TNCuPc are through continuous four-wheel catalytic reaction, the dyestuff generation process of each round chromogenic reaction, it is possible to find phase
Absorbance with the reaction time is closer to, and illustrates the activity of catalyst without substantially decay.
(a) 2-CP is catalyzed using four kinds of catalytic oxidation systems；(b)DCP；(c)4-CP；(d) Phenol chromogenic reaction, enters
Row catalytic efficiency is contrasted.Wherein four kinds catalyst amounts are 15mg, and BuOOH consumptions are 15 μ L.TNFePc and O2What is constituted urges
Change in oxidation system, O2For dissolved oxygen in solution.TNFePc is tetranitro (II) iron-phthalocyanine.■ represents Fe3O4@C@TNCuPc with
The catalytic oxidation system of BuOOH compositions, ● represent the catalytic oxidation system that TNCuPc and BuOOH are constituted, ▲ represent TNFePc with
The catalytic oxidation system of BuOOH compositions, ▼ represents TNCuPc and O2The catalytic oxidation system of composition.From these four phenol different
From the point of view of the result of chromogenic reaction process complex chart 11a-d under " metal phthalocyanine-oxidant " effect, Fe3O4@C@TNCuPc's urges
Change performance best；Non-loaded TNCuPc and TNFePc catalytic performances are worse than Fe3O4@C@TNCuPc；It is being oxidant using oxygen
Under conditions of, TNFePc catalytic activity is most weak.In general, Fe is selected3O4@C@TNCuPc catalyst, in current experiment condition
Under phenolic compound can be converted into quinoneimine dye to greatest extent, it is ensured that the accuracy of analysis.And stability is good, it can weigh
It is used for multiple times again.
Embodiment 2
0.80g neopelexes (SDBS) and 4.50g sodium acetates are dissolved in 75mL ethylene glycol, ultrasonic disperse
20min and being aided with stirring is completely dissolved it, adds 2.50g FeCl3·6H2O is after magnetic agitation 30min, by mixed liquor
It is transferred in 100mL hydrothermal reaction kettles, 8h is reacted at a temperature of 190 DEG C.Question response kettle naturally cools to room temperature, product spend from
Sub- water, absolute ethyl alcohol are washed three times respectively, and gained sample collects stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers.
Step (2) Fe3O4@C preparation：
9.0g glucose is added in 70mL deionized waters, it is agitated after it is completely dissolved, take 0.60g steps (1) to make
Standby Fe3O4Powder adds ultrasonic disperse 5min in D/W, and then reaction solution is transferred in 100mL reactors, passes through
190 DEG C of reaction 3h.Product is washed three times respectively with a small amount of deionized water and absolute ethyl alcohol, and 12 are dried in 60 DEG C of vacuum drying chambers
Collect stand-by after hour.
Step (3) Fe3O4@C@TNCuPc preparation：
By such scheme, in described step (3), by 25mg phthalonitriles, 10.5mg Cu (Ac)2·H2O and 15mg
Ammonium molybdate is added sequentially to fill in the beaker of 75mL ethylene glycol, and stirring is completely dissolved it, adds prepared by step (2)
0.25g Fe3O4Mixed solution is transferred in 100mL reactors after@C powder and ultrasonic disperse 5min, reaction temperature is set in 180
DEG C maintain 6h.After question response is finished, reactor naturally cools to room temperature, black powder product a small amount of deionized water and anhydrous second
Alcohol is washed three times respectively, is collected after being dried 12 hours in 60 DEG C of vacuum drying chambers and is obtained Fe3O4@C@TNCuPc。
Through characterizing：Fe3O4@C@TNCuPc composite catalysts by be coated with amorphous c film layer Fe 3 O 4 magnetic
Carrier, and carrier surface, tetranitro copper (II) phthalocyanine composition with " island shape " nanostructured are supported on, it is designated as Fe3O4@C@
TNCuPc。
Claims (9)
1. a kind of recyclable tetranitro copper (II) the phthalocyanine composite catalyst of magnetic, it is characterised in that：It is amorphous including being coated with
The ferroferric oxide magnetic carrier of carbon thin film layer, and it is supported on carrier surface, the tetranitro copper with " island shape " nanostructured
(II) phthalocyanine, is designated as Fe3O4@C@TNCuPc：The magnetic ferroferric oxide is micro-sphere structure of the diameter 700 to 900nm.
2. recyclable tetranitro copper (II) the phthalocyanine composite catalyst of magnetic according to claim 1, it is characterised in that：Institute
The load capacity for stating tetranitro copper (II) phthalocyanine is containing 2 to 3mg tetranitros copper (II) phthalocyanine per 15mg composite catalysts.
3. the preparation method of the recyclable tetranitro copper phthalocyanine composite catalyst of magnetic described in claim 1, it is characterised in that：
Prepared, comprised the following steps using solvent-thermal method：
Step (1)：Fe3O4The preparation of magnetic carrier：
By FeCl3·6H2O is added in the ethylene glycol solution containing neopelex and sodium acetate and is sufficiently stirred for making
It dissolves, 170-190 DEG C of 8-16h of reaction, obtains Fe3O4Magnetic carrier；
Step (2)：Fe3O4@C preparation：
Fe prepared by step (1)3O4Magnetic carrier is added in D/W, and ultrasonic disperse is uniform, and 170-190 DEG C anti-
2-6h are answered, the ferroferric oxide magnetic carrier Fe for being coated with amorphous c film layer is obtained3O4@C；
Step (3)：Fe3O4@C@TNCuPc preparation：
Phthalonitrile, copper acetate and ammonium molybdate are added in the glass beaker for filling ethylene glycol, stirring makes it fully dissolve,
It is subsequently added the Fe of step (2) preparation3O4@C powder simultaneously makes its ultrasonic disperse, liquid mixed above is transferred in reactor, 160
Reacted 10-12 hours to 180 DEG C.
4. the preparation method of the recyclable tetranitro copper phthalocyanine composite catalyst of magnetic according to claim 3, its feature
It is：In described step (1), FeCl3·6H2O：Neopelex：Sodium acetate：Ethylene glycol is 1.35-2.5g：
0.4-0.8g：3-4.5g：60-75mL；In described step (2), glucose：Fe3O4：The consumption of water is 6.5-9.0g：0.4-
0.8g：60-75mL；In described step (3), phthalonitrile：Copper acetate：Ammonium molybdate：Fe3O4@C are 17.3-34.6mg：
5.5-11mg：10-20mg：100-250mg.
5. the preparation method of the recyclable tetranitro copper phthalocyanine composite catalyst of magnetic according to claim 3, its feature
It is：Question response kettle naturally cools to room temperature, product deionized water, absolute ethyl alcohol point after the completion of described step (1) reaction
Xi Di not be three times, gained sample collects stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers；
Product after the completion of step (2) reaction is washed three times respectively with a small amount of deionized water and absolute ethyl alcohol, true at 60 DEG C
Collect stand-by after being dried 12 hours in empty drying box；
After completion of the reaction, reactor naturally cools to room temperature, black powder product a small amount of deionized water and nothing to the step (3)
Water-ethanol is washed three times respectively, is collected after being dried 12 hours in 60 DEG C of vacuum drying chambers.
6. recyclable tetranitro copper (II) the phthalocyanine composite catalyst of magnetic described in claim 1 is in phenolic comp ' ds pollution or chlorophenol
Application in pollutant colour developing identification reaction, it is characterised in that：It is constituted into catalytic oxidation system with TBHP
Accelerate phenolic comp ' ds pollution or the chromogenic reaction of chlorophenol pollutant and 4-AA, with the quinone imines pink colour dyestuff of generation
Phenolic comp ' ds pollution or chlorophenol pollutant in discriminance analysis system.
7. application according to claim 6, it is characterised in that：Described phenolic comp ' ds pollution or chlorophenol pollutant are benzene
Phenol, 2- chlorophenols, 4- chlorophenols or 2,4- chlorophenols.
8. application according to claim 6, it is characterised in that：Application process is concretely comprised the following steps：By Fe3O4@C@TNCuPc are urged
Agent is added in the aqueous solution of phenolic comp ' ds pollution to be detected or the chlorophenol pollutant aqueous solution and 4-AA, ultrasound
It is scattered, it is subsequently added TBHP and stirs, reaction starts timing, at regular intervals, is separated using magnet
Catalyst simultaneously collects reaction solution, and absorbance detection is carried out using ultraviolet-visible absorption spectroscopy instrument：Using deionized water as reference,
Detect the absorption values at absorbance of the reaction solution in the range of 200-800nm, record 510nm.
9. application according to claim 6, it is characterised in that：The Fe3O4@C@TNCuPc catalyst is recovered after purification
Reuse, method is as follows：Using magnet by Fe3O4@C@TNCuPc are adsorbed to beaker inwall, by the remaining pink aqueous solution
Carefully pour out, then add into empty beaker deionized water, ultrasonic disperse Fe3O4Adsorbed again simultaneously using magnet after@C@TNCuPc
Pouring soln, so repeatedly until the aqueous solution finally carries out elution action again in colourless using more than 60 DEG C of deionized water
Afterwards, collect stand-by after being dried 12 hours in 60 DEG C of vacuum drying chambers.
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