CN102515247B - 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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- CN102515247B CN102515247B CN201110409846.7A CN201110409846A CN102515247B CN 102515247 B CN102515247 B CN 102515247B CN 201110409846 A CN201110409846 A CN 201110409846A CN 102515247 B CN102515247 B CN 102515247B
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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 Zn-Al binary hydrotalcite and as the application of catalysis material degraded crystal violet.
(2) background technology
In current chemical industry, printing and dyeing industry is because high pollution, waste water are difficult, always by common concern.Waste water from dyestuff colourity is high, complex chemical composition, biochemical are poor, and contains the multiple organic matter with bio-toxicity or " three cause " performance, is difficult to process according to a conventional method.Organic cation type dye is important a kind of in the dyestuff of actual use, claims again basic dyestuff and basic-dyeable fibre.Crystal violet (Methyl Violet) belongs to organic cation dye, and molecular formula is: C
25h
30n
3cl, structure is suc as formula shown in (I).If its waste water from dyestuff is directly discharged in environment without processing, will cause ill effect.
Stratiform anionic clay (Layered Double Hydroxides is called for short LDHs) is the functional material that a class has 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 very similar to shepardite Mg (OH)
2.M wherein
2+and M
3+represent respectively divalence and trivalent metal cation, be positioned on main body laminate; Subscript x is the changes of contents of metallic element, A
n-represent the tradable anion of interlayer, as NO
3 -, CO
3 2-deng.Due to the particularity of veneer structure, can be optimized laminate cation type and proportioning, or introduce various anion at interlayer, hydrotalcite application is widened.And hydrotalcite is because of the particularity of its structure, not only self there is certain photocatalytic activity, can carry out preferably compoundly with other catalysis materials again, be a kind of catalysis material of novel, efficient, environmental protection.
(3) summary of the invention
The object of the invention is to provide a kind of Zn-Al binary hydrotalcite and as the application of catalysis material degraded crystal violet.
The technical solution used in the present invention is:
The invention provides a kind of Zn-Al binary hydrotalcite, described 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 crystallization water quantity, 2≤m≤6.
Described 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 conventionally: get Zn (NO
3)
26H
2o (0.3mol) and Al (NO
3)
39H
2o (0.1mol) is dissolved in 300ml water, is mixed with solution A, by 0.8molNaOH and 0.05molNa
2cO
3be dissolved in 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 the rate of addition of 1 drop/sec, strong agitation at 40 ℃ of constant temperature, keeps pH value between 9～10, dropwise rear continuation and stir 60min, in 65 ℃ of crystallization 18h, centrifugal, washing of precipitate is to neutral, after 85 ℃ of dry 12h, obtain ZnAl-LDHs sample, wherein zinc-aluminium ratio is 3: 1, and x is 0.25, m is 4, and chemical general formula is
[Zn
2+ 0.75Al
3+ 0.25(OH)
2](CO
3 2-)
0.125·4H
2O]。
On the other hand, described Zn-Al binary hydrotalcite is as the application of degraded crystal violet catalysis material.
Further, described Zn-Al binary hydrotalcite being applied as degraded crystal violet catalysis material: Zn-Al binary hydrotalcite is placed in to the crystal violet aqueous solution, 10～50 ℃, under the condition of pH4.0～10.0, dysprosium lamp irradiates 0.5～4.0h, stirs, and makes crystal violet degraded; The initial mass concentration of the described crystal violet aqueous solution is 10～200mg/L, and described Zn-Al binary hydrotalcite quality consumption is 1～100mg/mL.
The present invention adopts water-bath temperature control, preferably with NaOH solution and HCl solution, regulates the pH value of the crystal violet aqueous solution.
The higher injected volume of Zn-Al binary hydrotalcite effectively absorbing dye (crystal violet) in material surface, so that carry out catalytic degradation, the preferred 2mg/ml crystal violet of the Zn-Al binary hydrotalcite quality consumption of the present invention aqueous solution, and the mass concentration of the crystal violet aqueous solution is preferably 20mg/L, too low concentration, dyestuff self the caused experimental error of degrading is larger.
Hydrotalcite (LDHs) is zinc-aluminum hydrotalcite (ZnAl-LDHs) particularly, there is certain energy gap, under suitable illumination, can produce the electron-hole pair with catalytic activity, when organic dyestuff (crystal violet) is attracted to hydrotalcite surface, meeting trapped electron-hole pair, degrades dyestuff self.Zn-Al binary hydrotalcite of the present invention (ZnAl-LDHs) can adopt conventional method preparation, as synthesized by two coprecipitations of dripping, and store under anhydrous drying condition, for the application of catalytic degradation waste water from dyestuff crystal violet, the structure of described crystal violet 106 is suc as formula shown in (I):
Synthetic Zn-Al binary hydrotalcite is placed in to ultraviolet-uisible spectrophotometer, measures its spectrogram that diffuses, in spectrogram, find ABSORPTION EDGE, do the ABSORPTION EDGE tangent line side wave that is absorbed long, and by formula, calculate the energy gap of material.According to the energy gap of material, select suitable light source, the electron transition in the enough excitation material valence band of main peak energy of light source produces electron-hole pair in conduction band.
After determining light source, choice experiment model, Main Basis 2 points: 1. make full use of light source, reduce luminous energy loss; 2. making reactor fully accept light source irradiates.Reaction model has three kinds of selections: 1. outer according to parallel reaction model; 2. interior irradiation reaction model; 3. annular reaction model.
Zinc-aluminum hydrotalcite material can use formula (1) to calculate to the degradation rate η of crystal violet in reaction system,
η=η
e-η
1-η
2formula (1)
In formula (1), η
efor the total clearance of zinc-aluminum hydrotalcite to the crystal violet aqueous solution, η
1for crystal violet self degradation rate under illumination, η
2for the adsorption rate of zinc-aluminum hydrotalcite to crystal violet under dark state condition.
η
e, η
1, η
2use respectively formula (2) to calculate,
η=(C
i-C
e)/C
i* 100 formula (2)
In formula (2), C
i(mgL
-1) and C
e(mgL
-1) being respectively the initial and reaction of reaction concentration of crystal violet in reaction system while finishing, V (L) is the volume of the original crystal violet aqueous solution adding, the dosage that m (g) is zinc-aluminum hydrotalcite.
The degradation rate to the crystal violet aqueous solution of Zn-Al binary hydrotalcite of the present invention adopts said method to calculate.
Compared with prior art, beneficial effect of the present invention is mainly reflected in: two hydroxyl complex hydroxides of Zn-Al binary hydrotalcite of the present invention are for catalytic degradation waste water from dyestuff crystal violet, reaction condition is gentle, and dyestuff clearance is high, and the material after catalytic degradation is easy to be recycled.
(4) accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of Zn-Al binary hydrotalcite in embodiment 1;
Fig. 2 is the diffuse reflection spectrogram of Zn-Al binary hydrotalcite in embodiment 2;
Fig. 3 is that in embodiment 3, reaction model figure: 3-1 is outer according to parallel reaction model, and wherein 1 is reactor; 2 is light source; 3 is optical filter; 3-2 is interior irradiation reaction model, and wherein 1 is reactor; 2 is light source; 3-3 is annular reaction model, and wherein 1 is reactor; 2 is light source;
Fig. 4 is crystal violet aqueous solution absorption curve and light application time graph of a relation in embodiment 4;
Fig. 5 is total clearance, degradation rate and the adsorption rate figure of the crystal violet aqueous solution in embodiment 4;
Fig. 6 is the calibration curve of embodiment 5 crystal violets.
(5) specific 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 Zn-Al binary hydrotalcite
Get Zn (NO
3)
26H
2o (0.3mol) and Al (NO
3)
39H
2o (0.1mol) is dissolved in 300ml water and is mixed with solution A, by 0.8molNaOH and 0.05molNa
2cO
3be dissolved in 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 the rate of addition of 1 drop/sec, strong agitation at 40 ℃ of constant temperature, keep pH value between 9～10, dropwise rear continuation and stir 60min, in 65 ℃ of crystallization 18h, centrifugal, precipitate with deionized water washing is to neutral, after 85 ℃ of dry 12h, obtain Zn-Al binary hydrotalcite (ZnAl-LDHs) sample, as shown in Figure 1, wherein zinc-aluminium ratio is 3: 1 to X-ray diffractogram (XRD), and x is 0.25, m is 4, and chemical general formula is
[Zn
2+ 0.75Al
3+ 0.25(OH)
2](CO
3 2-)
0.125·4H
2O]。
The Zn-Al binary hydrotalcite 2000mg that to get zinc-aluminium ratio prepared by embodiment 1 method be 3: 1, in ultraviolet-uisible spectrophotometer (2550 types, Shimadzu) scanning 200～800nm wave-length coverage in, survey the diffuse reflection spectrum of Zn-Al binary hydrotalcite, see Fig. 2, according to the ABSORPTION EDGE that records spectrogram, draw ABSORPTION EDGE wavelength, according to formula Eg=1240/ λ g (Eg is band-gap energy, and λ g is ABSORPTION EDGE wavelength), calculate band-gap energy again.
Conclusion: the band-gap energy of Zn-Al binary hydrotalcite is 3.05eV, can select dysprosium lamp to do excitation source.
Prepare 3 parts of 50ml 20mgL
-1the crystal violet aqueous solution, take three parts of Zn-Al binary hydrotalcites prepared by embodiment 1 method, every part of 100mg, add respectively in the above-mentioned pending crystal violet aqueous solution and (form 3 groups), controlling temperature is 25 ℃, pH=7, (Fig. 3 3-1 is outer according to parallel reaction model to be placed in respectively three kinds of differential responses models; 3-2 is interior irradiation reaction model; 3-3 is annular reaction model), controlling dysprosium lamp irradiation time is 1h, after stirring, by 3 groups of solution in the centrifugal 10min of 2000rpm, get respectively supernatant liquor and measure crystal violet in the absorbance at 590nm place, according to crystal violet calibration curve, calculate the concentration of crystal violet, according to formula (1) and (2), obtaining outer is 35% according to zinc-aluminum hydrotalcite in parallel reaction model to the degradation rate of the crystal violet aqueous solution.
Conclusion: shine parallel reaction model reaction device outward easy, requirement for experiment condition is low, is not less than other two kinds of models to light utilization efficiency, therefore selects the outer parallel reaction model that shines, and under this model, hydrotalcite can reach 35% to the degradation rate of the crystal violet aqueous solution.
Embodiment 4
Prepare 50ml 20mgL
-13 parts of the crystal violet aqueous solution, be divided into 3 groups, group 1 takes Zn-Al binary hydrotalcite 100mg prepared by embodiment 1 method, controlling temperature is 25 ℃, pH=7, be placed in outer according to parallel reaction model, with dysprosium lamp light source, irradiate, stir, irradiating 0 respectively, 30, 60, 90, during 120min, sample, sample is in the centrifugal 10min of 2000rpm, get supernatant liquor and be determined at the absorbance (Shimadzu 2550 type ultraviolet-uisible spectrophotometers) of crystal violet within the scope of 200～800nm, take wavelength respectively as abscissa, the absorbance of crystal violet is ordinate, draw the absorption curve of different time points and see Fig. 4.
Get the reactant liquor after 120min processes in group 1, survey crystal violet in the absorbance at 590nm place, according to crystal violet calibration curve, calculate crystal violet concentration, according to formula (2), calculate the total clearance of zinc-aluminum hydrotalcite to the crystal violet aqueous solution.
Zinc-aluminum hydrotalcite material can use formula (1) to calculate to the degradation rate η of crystal violet,
η=η
e-η
1-η
2formula (1)
In formula (1), η
efor the total clearance of zinc-aluminium talcum to crystal violet, η
1for crystal violet self degradation rate under illumination, η
2for the adsorption rate of zinc-aluminum hydrotalcite to crystal violet under dark state condition.
η
e, η
1, η
2use respectively formula (2) to calculate,
η=(C
i-C
e)/C
i* 100 formula (2)
In formula (2), C
i(mgL
-1) and C
e(mgL
-1) concentration of crystal violet in reaction system while being respectively reaction 0min and 120min, V (L) is the volume of the original crystal violet aqueous solution adding, the dosage that m (g) is zinc-aluminum hydrotalcite.
Total clearance (60%), crystal violet self degradation rate (20%) and adsorption rate (5%) according to formula (1) and formula (2) the calculating crystal violet aqueous solution, the results are shown in Figure 5.
Conclusion: under dysprosium lamp light source irradiates, the Zn-Al binary hydrotalcite that zinc-aluminium ratio is 3: 1 crystal violet of can degrading, and degradation rate has reached 35%.
The preparation of embodiment 5 crystal violet calibration curves
Take crystal violet initial soln (1mg/L) as basis, compound concentration is the solution of 0.04mg/L, 0.09mg/L, 0.18mg/L, 0.35mg/L, 0.07mg/L, using deionized water as blank reference, with Shimadzu 2550 type ultraviolet-uisible spectrophotometers, in 590nm place, measure the absorbance of each solution, carry out linear fit and obtain the calibration curve of crystal violet solution absorbance A-concentration C, as shown in Figure 6.
Claims (2)
1. Zn-Al binary hydrotalcite, as an application for degraded crystal violet catalysis material, is characterized in that described being applied as: Zn-Al binary hydrotalcite is placed in to the crystal violet aqueous solution, 10～50 ℃, pH is under 4.0～10.0 conditions, dysprosium lamp irradiates 0.5～4.0h, stirs, and makes crystal violet degraded; The initial mass concentration of the described crystal violet aqueous solution is 10～200mg/L, and described Zn-Al binary hydrotalcite quality consumption is 1～100mg/mL crystal violet aqueous solution; Described hydrotalcite chemical general formula is [Zn
2+ 1-xal
3+ x(OH)
2]
x+(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 crystallization water quantity, 2≤m≤6.
2. application as claimed in claim 1, is characterized in that described hydrotalcite chemical general formula is [Zn
2+ 0.75al
3+ 0.25(OH)
2]
x+(CO
3 2-)
0.1254H
2o.
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| CN108993377B (en) * | 2018-08-13 | 2021-04-27 | 武汉理工大学 | Ultrathin zinc-aluminum hydrotalcite nanosheet and preparation method and application thereof |
| CN114653368A (en) * | 2022-01-28 | 2022-06-24 | 浙江工业大学 | Cu-doped hydrotalcite-based photocatalytic material and preparation method and application thereof |
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