CN102515247A - Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet - Google Patents
Zinc-aluminum binary hydrotalcite and application thereof as photocatalytic material used for degrading methyl violet Download PDFInfo
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- CN102515247A CN102515247A CN2011104098467A CN201110409846A CN102515247A CN 102515247 A CN102515247 A CN 102515247A CN 2011104098467 A CN2011104098467 A CN 2011104098467A CN 201110409846 A CN201110409846 A CN 201110409846A CN 102515247 A CN102515247 A CN 102515247A
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- pyoktanin blue
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Abstract
The invention relates to zinc-aluminum binary hydrotalcite and an application thereof as a photocatalytic material used for degrading methyl violet. The hydrotalcite has a chemical general formula of [Zn<2+>1-xAl<3+>x(OH)2](CO3<2->)x/2.mH2O], wherein x is the molar ratio of Al<3+>/[Al<3+>+Zn<2+>], x is no smaller than 0.2 and no greater than 0.33, m is the number of crystal water, and m is no smaller than 2 and no greater than 6. When dihydroxyl composite hydroxide of zinc-aluminum binary hydrotalcite provided by the invention is used for catalyzing the degradation of methyl violet in dye wastewater, the reaction condition is mild, the dye removal rate is high, and materials can easily be recycled after degradation.
Description
(1) technical field
The present invention relates to a kind of hydrotalcite and application thereof, particularly a kind of zinc-aluminium binary hydrotalcite and as the application of photocatalyst material degraded pyoktanin blue.
(2) background technology
In the current chemical industry, printing and dyeing industry is owing to high pollution, waste water are hard to manage, always by common concern.Waste water from dyestuff colourity height, complex chemical composition, biochemical are poor, and contain multiple organism with bio-toxicity or " three cause " performance, are difficult to handle by ordinary method.The organic cation type dye is important a kind of in the dyestuff of actual use, claims basic dyestuff and basic dyestuff again.Pyoktanin blue (Methyl Violet) belongs to organic cation dye, and molecular formula is: C
25H
30N
3Cl, structure is suc as formula shown in (I).Its waste water from dyestuff will cause ill effect if directly be discharged in the environment without handling.
Stratiform anionic clay (Layered Double Hydroxides is called for short LDHs) is one type of functional materials with special stratiform configuration, mainly comprises hydrotalcite, houghite and intercalated houghite.Its general formula is: [M
2+ 1-xM
3+ x(OH)
2] (A
N-)
X/nMH
2O], structure is similar to brucite Mg (OH) very much
2M wherein
2+And M
3+Represent divalence and trivalent metal cation respectively, be positioned on the main body laminate; Subscript x is the content of metallic element, A
N-Represent the tradable negatively charged ion of interlayer, like NO
3 -, CO
3 2-Deng.Because the singularity of veneer structure can be optimized laminate cation type and proportioning, or introduce various negatively charged ion at interlayer, makes the hydrotalcite Application Areas widen.And hydrotalcite not only self has certain photocatalytic activity because of the singularity of its structure, can carry out compoundly preferably with other photocatalyst materials again, is a kind of photocatalyst material of novel, efficient, environmental protection.
(3) summary of the invention
The object of the invention provides a kind of zinc-aluminium binary hydrotalcite and as the application of photocatalyst material degraded pyoktanin blue.
The technical scheme that the present invention adopts is:
The present invention provides a kind of zinc-aluminium binary hydrotalcite, and said hydrotalcite chemical general formula is [Zn
2+ 1-xAl
3+ x(OH)
2] (CO
3 2-)
X/2MH
2O], wherein x is Al
3+/ [Al
3++ Zn
2+] mol ratio, 0.2≤x≤0.33, m is a crystal water quantity, 2≤m≤6.
Said hydrotalcite chemical general formula is preferably [Zn
2+ 0.75Al
3+ 0.25(OH)
2] (CO
3 2-)
0.1254H
2O].
Hydrotalcite of the present invention is preparation as follows usually: get Zn (NO
3)
26H
2O (0.3mol) and Al (NO
3)
39H
2O (0.1mol) is dissolved in the 300ml water, is mixed with solution A, with 0.8molNaOH and 0.05molNa
2CO
3Be dissolved in the 300ml water, be mixed with solution B, solution A and solution B are added drop-wise to respectively in the deionized water of 100ml, keep 1 droplet/second rate of addition; 40 ℃ of following violent stirring of constant temperature keep the pH value between 9～10, dropwise continued and stir 60min, in 65 ℃ of crystallization 18h; Centrifugal, washing of precipitate obtains the ZnAl-LDHs sample to neutral behind 85 ℃ of dry 12h, and wherein the zinc-aluminium ratio is 3: 1; Be that x is 0.25, m is 4, and chemical general formula does
[Zn
2+ 0.75Al
3+ 0.25(OH)
2](CO
3 2-)
0.125·4H
2O]。
On the other hand, described zinc-aluminium binary hydrotalcite is as the application of degraded pyoktanin blue photocatalyst material.
Further, described zinc-aluminium binary hydrotalcite being applied as: zinc-aluminium binary hydrotalcite is placed the pyoktanin blue aqueous solution, 10～50 ℃ as degraded pyoktanin blue photocatalyst material; Under pH4.0～10.0 conditions; Dysprosium lamp irradiation 0.5～4.0h stirs, and makes the pyoktanin blue degraded; The initial mass concentration of the said pyoktanin blue aqueous solution is 10～200mg/L, and said zinc-aluminium binary hydrotalcite quality consumption is 1～100mg/mL.
The present invention adopts the water-bath temperature control, preferably regulates the pyoktanin blue pH value of aqueous solution with NaOH solution and HCl solution.
The higher injected volume of zinc-aluminium binary hydrotalcite can active adsorption dyestuff (pyoktanin blue) in material surface; So that carry out catalyzed degradation; The preferred 2mg/ml pyoktanin blue of the zinc-aluminium binary hydrotalcite quality consumption of the present invention aqueous solution; And the mass concentration of the pyoktanin blue aqueous solution is preferably 20mg/L, too low concentration, and dyestuff self the caused experimental error of degrading is bigger.
Hydrotalcite (LDHs) is zinc-aluminium hydrotalcite (ZnAl-LDHs) particularly; Certain energy gap is arranged, under suitable illumination, can produce the electron-hole pair that has catalytic activity, when organic dye (pyoktanin blue) is attracted to the hydrotalcite surface; Meeting trapped electron-hole is right, and dyestuff self is degraded.Zinc-aluminium binary hydrotalcite of the present invention (ZnAl-LDHs) can adopt the ordinary method preparation; As can be synthetic through two coprecipitation methods of dripping; And under anhydrous drying conditions, store, being used for the application of catalyzed degradation waste water from dyestuff pyoktanin blue, the structure of described pyoktanin blue 106 is suc as formula shown in (I):
Synthetic zinc-aluminium binary hydrotalcite is placed ultraviolet-visible pectrophotometer, measure its spectrogram that diffuses, in spectrogram, find ABSORPTION EDGE, it is long to do the ABSORPTION EDGE tangent line side wave that is absorbed, and calculates the energy gap of material through formula.Energy gap according to material is selected suitable light source, and the transition of electron in the enough excitation material valence band of the main peak energy of light source produces electron-hole pair in conduction band.
Confirm after the light source, select experimental model, main according to 2 points: 1. as to make full use of light source, reduce the luminous energy loss; 2. make reactor drum fully accept light source irradiation.Reaction model has three kinds of selections: 1. outer according to the parallel reactor model; 2. interior irradiation reaction model; 3. annular reaction model.
The zinc-aluminium hydrotalcite material can use formula (1) to calculate to the degradation rate η of pyoktanin blue in the reaction system, promptly
η=η
e-η
1-η
2Formula (1)
In the formula (1), η
eBe the total clearance of zinc-aluminium hydrotalcite to the pyoktanin blue aqueous solution, η
1Be pyoktanin blue self degradation rate under illumination, η
2For zinc-aluminium hydrotalcite under dark attitude condition to the adsorption rate of pyoktanin blue.
η
e, η
1, η
2Use formula (2) to calculate respectively, promptly
η=(C
i-C
e)/C
i* 100 formula (2)
In the formula (2), C
i(mgL
-1) and C
e(mgL
-1) being respectively reaction initial sum reaction concentration of pyoktanin blue in the reaction system when finishing, V (L) is the volume of the pyoktanin blue aqueous solution of original adding, m (g) is the dosage of zinc-aluminium hydrotalcite.
The degradation rate to the pyoktanin blue aqueous solution of zinc-aluminium binary hydrotalcite according to the invention adopts aforesaid method to calculate.
Compared with prior art; Beneficial effect of the present invention is mainly reflected in: two hydroxyl complex hydroxides of zinc-aluminium binary hydrotalcite according to the invention are used for catalyzed degradation waste water from dyestuff pyoktanin blue; Reaction conditions is gentle, and the dyestuff clearance is high, and the material behind the catalyzed degradation is easy to be recycled.
(4) description of drawings
Fig. 1 is the X-ray diffractogram of zinc-aluminium binary hydrotalcite among the embodiment 1;
Fig. 2 is the diffuse-reflectance spectrogram of zinc-aluminium binary hydrotalcite among the embodiment 2;
Fig. 3 is that reaction model figure: 3-1 is outer according to the parallel reactor model among the embodiment 3, and wherein 1 is reactor drum; 2 is light source; 3 is spectral filter; 3-2 is interior irradiation reaction model, and wherein 1 is reactor drum; 2 is light source; 3-3 is the annular reaction model, and wherein 1 is reactor drum; 2 is light source;
Fig. 4 is pyoktanin blue aqueous solution absorption curve and a light application time graph of a relation among the embodiment 4;
Fig. 5 is total clearance, degradation rate and the adsorption rate figure of the pyoktanin blue aqueous solution among the embodiment 4;
Fig. 6 is the typical curve of embodiment 5 pyoktanin blues.
(5) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
The preparation of embodiment 1 zinc-aluminium binary hydrotalcite
Get Zn (NO
3)
26H
2O (0.3mol) and Al (NO
3)
39H
2O (0.1mol) is dissolved in the 300ml water and is mixed with solution A, with 0.8molNaOH and 0.05molNa
2CO
3Be dissolved in the 300ml water and be mixed with solution B, solution A and solution B are added drop-wise to respectively in the deionized water of 100ml, keep 1 droplet/second rate of addition; 40 ℃ of following violent stirring of constant temperature keep the pH value between 9～10, dropwise continued and stir 60min; In 65 ℃ of crystallization 18h, centrifugal, the precipitate with deionized water washing is to neutral; Obtain zinc-aluminium binary hydrotalcite (ZnAl-LDHs) sample behind 85 ℃ of dry 12h, (XRD) is as shown in Figure 1 for X-ray diffractogram, and wherein the zinc-aluminium ratio is 3: 1; Be that x is 0.25, m is 4, and chemical general formula does
[Zn
2+ 0.75Al
3+ 0.25(OH)
2](CO
3 2-)
0.125·4H
2O]。
The zinc-aluminium ratio of getting the preparation of embodiment 1 method is 3: 1 zinc-aluminium binary hydrotalcite 2000mg, scanning 200～800nm wavelength region in ultraviolet-visible pectrophotometer (2550 types, Tianjin, island); Survey the diffuse reflection spectrum of zinc-aluminium binary hydrotalcite; See Fig. 2,, draw the ABSORPTION EDGE wavelength according to the ABSORPTION EDGE that records spectrogram; Calculate band-gap energy according to formula Eg=1240/ λ g (Eg is a band-gap energy, and λ g is the ABSORPTION EDGE wavelength) again.
Conclusion: the band-gap energy of zinc-aluminium binary hydrotalcite is 3.05eV, can select dysprosium lamp to do excitation light source.
Prepare 3 parts of 50ml 20mgL
-1The pyoktanin blue aqueous solution; Take by weighing three parts of the zinc-aluminium binary hydrotalcites of embodiment 1 method preparation; Every part of 100mg adds respectively in the above-mentioned pending pyoktanin blue aqueous solution and (forms 3 groups), and controlled temperature is 25 ℃; PH=7, (Fig. 3 3-1 is outer according to the parallel reactor model to place three kinds of differential responses models respectively; 3-2 is interior irradiation reaction model; 3-3 is the annular reaction model); Control dysprosium lamp irradiation time is 1h, after the stirring, with 3 groups of solution in the centrifugal 10min of 2000rpm; Get supernatant liquid respectively and measure the absorbancy of pyoktanin blue at the 590nm place; Calculate the concentration of pyoktanin blue according to the pyoktanin blue typical curve, according to formula (1) and (2), obtaining zinc-aluminium hydrotalcite in the outer photograph parallel reactor model is 35% to the degradation rate of the pyoktanin blue aqueous solution.
Conclusion: it is easy to shine parallel reactor model reaction device outward, and requirement for experiment condition is low, and light utilization efficiency is not less than other two kinds of models, therefore selects the outer parallel reactor model that shines, and under this model, hydrotalcite can reach 35% to the degradation rate of the pyoktanin blue aqueous solution.
Embodiment 4
Prepare 50ml 20mgL
-13 parts of the pyoktanin blue aqueous solution, be divided into 3 groups, group 1 takes by weighing the zinc-aluminium binary hydrotalcite 100mg of embodiment 1 method preparation; Controlled temperature is 25 ℃, and pH=7 places outer according to the parallel reactor model; Use the dysprosium lamp light source irradiation, stir, when irradiation 0,30,60,90,120min, take a sample respectively; Sample is got the absorbancy (Tianjin, island 2550 type ultraviolet-visible pectrophotometers) that supernatant liquid is determined at pyoktanin blue in 200～800nm scope in the centrifugal 10min of 2000rpm, is respectively X-coordinate with the wavelength; The absorbancy of pyoktanin blue is an ordinate zou, draws the absorption curve of different time points and sees Fig. 4.
Group 21 condition on the same group is following with operation; Measure the absorption situation of zinc-aluminium binary hydrotalcite to crystal violet under the dark attitude, promptly do not have light source irradiation, other conditions are identical; Measure the absorbance at the 590nm place of crystal violet behind the reaction 120min; Calculate crystal violet concentration based on the crystal violet calibration curve, under formula (2) calculated dark attitude, zinc-aluminium binary hydrotalcite is to the adsorption rate of crystal violet;
Group 31 condition on the same group is following with operation; Do not add zinc-aluminium binary hydrotalcite; Measure pyoktanin blue self degraded situation under the light source irradiation; Measure the absorbancy of pyoktanin blue behind the reaction 120min, calculate pyoktanin blue concentration, according to formula (2) calculating pyoktanin blue self degradation rate under illumination according to the pyoktanin blue typical curve at 590nm place.
Get the reaction solution after process 120min handles in the group 1, survey the absorbancy of pyoktanin blue, calculate pyoktanin blue concentration, calculate the total clearance of zinc-aluminium hydrotalcite the pyoktanin blue aqueous solution according to formula (2) according to the pyoktanin blue typical curve at the 590nm place.
The zinc-aluminium hydrotalcite material can use formula (1) to calculate to the degradation rate η of pyoktanin blue, promptly
η=η
e-η
1-η
2Formula (1)
In the formula (1), η
eBe the total clearance of zinc-aluminium talcum to pyoktanin blue, η
1Be pyoktanin blue self degradation rate under illumination, η
2For zinc-aluminium hydrotalcite under dark attitude condition to the adsorption rate of pyoktanin blue.
η
e, η
1, η
2Use formula (2) to calculate respectively, promptly
η=(C
i-C
e)/C
i* 100 formula (2)
In the formula (2), C
i(mgL
-1) and C
e(mgL
-1) concentration of pyoktanin blue in the reaction system when being respectively reaction 0min and 120min, V (L) is the volume of the pyoktanin blue aqueous solution of original adding, m (g) is the dosage of zinc-aluminium hydrotalcite.
According to total clearance (60%), pyoktanin blue self degradation rate (20%) and the adsorption rate (5%) of the formula (1) and formula (2) the calculating pyoktanin blue aqueous solution, the result sees Fig. 5.
Conclusion: under the dysprosium lamp light source irradiation, the zinc-aluminium ratio is 3: 1 the zinc-aluminium binary hydrotalcite pyoktanin blue of can degrading, and degradation rate has reached 35%.
The preparation of embodiment 5 pyoktanin blue typical curves
(1mg/L) is the basis with the pyoktanin blue initial soln; Compound concentration is the solution of 0.04mg/L, 0.09mg/L, 0.18mg/L, 0.35mg/L, 0.07mg/L; With deionized water as blank reference; Measure each solution absorbency in the 590nm place with Tianjin, island 2550 type ultraviolet-visible pectrophotometers, carry out the typical curve that linear fit obtains pyoktanin blue solution absorbance A-concentration C, see shown in Figure 6.
Claims (4)
1. a zinc-aluminium binary hydrotalcite is characterized in that said hydrotalcite chemical general formula is [Zn
2+ 1-xAl
3+ x(OH)
2] (CO
3 2-)
X/2MH
2O], wherein x is Al
3+With [Al
3++ Zn
2+] mol ratio, 0.2≤x≤0.33, m is a crystal water quantity, 2≤m≤6.
2. zinc-aluminium binary hydrotalcite as claimed in claim 1 is characterized in that said hydrotalcite chemical general formula is [Zn
2+ 0.75Al
3+ 0.25(OH)
2] (CO
3 2-)
0.1254H
2O].
3. zinc-aluminium binary hydrotalcite as claimed in claim 1 is as the application of degraded pyoktanin blue photocatalyst material.
4. zinc-aluminium binary hydrotalcite as claimed in claim 3 is as the application of degraded pyoktanin blue photocatalyst material; It is characterized in that described being applied as: zinc-aluminium binary hydrotalcite is placed the pyoktanin blue aqueous solution; 10～50 ℃, under pH4.0～10.0 conditions, dysprosium lamp irradiation 0.5～4.0h; Stir, make the pyoktanin blue degraded; The initial mass concentration of the said pyoktanin blue aqueous solution is 10～200mg/L, and said zinc-aluminium binary hydrotalcite quality consumption is 1～100mg/ml pyoktanin blue aqueous solution.
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