CN101708454B - Flaky Mg-Al composite oxide for loading ZnO nano particles as well as preparation and application thereof - Google Patents
Flaky Mg-Al composite oxide for loading ZnO nano particles as well as preparation and application thereof Download PDFInfo
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- CN101708454B CN101708454B CN2009101998688A CN200910199868A CN101708454B CN 101708454 B CN101708454 B CN 101708454B CN 2009101998688 A CN2009101998688 A CN 2009101998688A CN 200910199868 A CN200910199868 A CN 200910199868A CN 101708454 B CN101708454 B CN 101708454B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a flaky Mg-Al composite oxide for loading ZnO nano particles, comprising ZnO nano particles and a Mg-Al composite oxide, wherein the Mg-Al composite oxide is flaky; the size of ZnO nano crystals is from 4 to 15nm, and the specific area is from 150 to 330m<2>/g. The preparation method comprises the steps of: calcining Mg-Al-CO3 LDH prepared by a coprecipitation method to generate the Mg-Al composite oxide; then putting the Mg-Al composite oxide in soluble carbonate for reducing to obtain flaky Mg-Al-CO3 LDH; dispersing to a soluble zinc salt solution; adding ammonia and stirring for 4 to 24 hours; and washing and calcining to obtain the Mg-Al composite oxide for loading ZnO. The Mg-Al composite oxide for loading ZnO has the advantages of strong absorption capability, good photocatalytic activity, good application prospect in the purifying field of dye waste water, simple preparation process, low requirement on production equipment, easy industrial production and the like.
Description
Technical field
The invention belongs to Mg-Al composite oxide and modification preparation and application, particularly a kind of flaky Mg-Al composite oxide of loading ZnO nano particles and preparation thereof and application.
Background technology
Along with the continuous quickening of industrial fast development and urbanization process, the trade effluent amount of in water environment, discharging is also in continuous increase, the generality and the seriousness of the water pollution phenomenon that is caused thus.The processing method of water pollution at present mainly contains following several kinds: (1) biological treatment: utilize microbial enzyme to come oxidation or reduction contaminant molecule.But microorganism has certain requirement to conditions such as nutriment, pH, temperature, and microorganism is difficult to existence in the environment that nutriment lacks, be difficult to reach gratifying effect.(2) chemical coagulation process: the object that chemical coagulation process is handled mainly is small suspension and colloidal impurity in the water, can't remove soluble ion type pollutant.(3) photocatalytic degradation method: catalysis material is penetrated down in illumination, with the pollutant oxidation, thereby removes water pollutant.But photochemical catalyst needs UV-irradiation just can play a role, but for the waters of pollution in wide area, photocatalysis efficiency is not high.(4) absorption method: absorption method is the pollutant that utilizes in the sorbing material adsorbed water of porous.But adsorbent is saturated easily, treatment effect in time prolongation and descend; The regeneration expense of adsorbent is higher, and the adsorbent that regeneration soiling solution and saturated dirt are abandoned causes secondary pollution easily.
Above the whole bag of tricks all respectively has deficiency, only is difficult to reach gratifying effect with a kind of material, so; Need the efficient cheap adsorbent of exploitation; Photochemical catalyst or microbial enzyme in load on the adsorbent, the advantage of comprehensive different materials reaches better scrubbing effect.
Layered double-hydroxide (layered double hydroxides is called for short LDH) is called anionic clay again, is a kind of novel absorption material.Its basic structure formula is: [M
2+ L-xM
3+ x(OH)
2]
X+A
M- X/mNH
2O, wherein: M
2+Be Mg
2+, Zn
2+And Fe
2+Deng divalent metal; M
3+Be Al
3+And Fe
3+Deng trivalent metal cation; A
M-Be CO
3 2-, Cl
-, NO
3 -And SO
4 2-Deng anion; X is 0.20～0.33.The structure of LDHs is based on the positive charge layer that is similar to shepardite, and the divalent metal part on the layer is replaced the unit two-dimensional layer strip positive electricity of formation by the trivalent metal cation isomorphous; Therefore interlayer exists tradable anion with balancing charge; Make crystallization be electroneutral (S.M.Auerbach, K.A.Carrado, P.K.Dutta.Handbook of Layered Materials.New York:Marcel Dekker.Inc.; 2004,387-393).Through roasting, the structural hydroxyl of LDHs and interlayer ion are overflowed, and former layered hydroxide structure is destroyed gradually, be converted into composite oxides (D.Tichit, B.Coq.Cattech, 2003, Vol.7, No.6,206-217).Thereby composite oxides can be reuptaked the LDH that anion in the water reverts to layer structure under certain condition, and this particular structure memory effect makes LDHs can be used as the high-efficiency anion absorbent and uses (L.E.Gaini, M.Lakraimi; E.Sebbar; A.Megheac, et al..J.Hazard.Mater., 2008; Vol.161,627-632).Compare with anion exchange resin, LDH has advantages such as ion exchange capacity is big, high temperature resistant, radiation hardness.
Use more semiconductor light-catalyst that TiO is arranged at present
2, ZnO, WO
3, CdS, SnO
2, Fe
2O
3, In
2O
3Deng.Generally believe TiO
2Be the optimal light catalyst, and there are a lot of problems as photochemical catalyst in it when handling waste water, mainly contain following some: 1) quantum efficiency low (less than 4%), difficulty are used to handle industrial waste gas and the waste water that quantity is big, concentration is high.2) lower to solar energy utilization rate, photochemical catalyst TiO commonly used
2Energy gap is 3.2eV, only can absorb the ultraviolet light of sunshine medium wavelength less than 380nm.When 3) adopting suspension to carry out photocatalysis, catalyst is difficult to reclaim and recycling, when adopting load technology, is difficult to keep higher photocatalytic activity.As another kind photochemical catalyst commonly used, ZnO compares TiO
2Exist weak point, yet the ZnO photochemical catalyst is in the middle of the process of degraded different dyes waste water; Its good catalytic activity (A.A.Khodja, T.Sehili, J.F.Pilichowski have also been shown; Et al..J.Photoch.Photobio.A2001, vol.141,231-239).People such as Sakthivel have studied ZnO and TiO
2Optical absorption spectra, semiconductor ZnO can absorb wavelength in a big way (sunshine (S.Sakthivel, the B.Neppolian of 350nm～470nm); M.V.Shankarb; Et al..Sol.Energ.Mal.Sol.C.2003, vol.77, No.1; 65-82), ZnO still is one of research focus of photocatalysis field as the research of photochemical catalyst.
But up to now, about the ZnO nano particle is not seen relevant report as yet to document and patent that Mg-Al composite oxide carries out the modification processing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of flaky Mg-Al composite oxide and preparation and application of loading ZnO nano particles; The Mg-Al composite oxide of this loading ZnO; Have characteristics such as the adsorptivity ability is strong, photocatalytic activity is good, have a good application prospect in the purified treatment field of waste water from dyestuff; And preparation technology is simple, and is low to the production equipment requirement, is easy to suitability for industrialized production.
The flaky Mg-Al composite oxide of a kind of loading ZnO nano particles of the present invention, its component comprises: ZnO nano particle and Mg-Al composite oxide, its mass ratio are 1: 10～5: 1;
In the Mg-Al composite oxide of this loading ZnO, Mg-Al composite oxide is laminar thickness 4～15nm, the size 5～15nm of zinc oxide nanocrystalline, specific area 150～330m
2/ g.
Described ZnO nano particle and Mg-Al composite oxide, its mol ratio or mass ratio are 1: 5～3: 1;
In the Mg-Al composite oxide of this loading ZnO, Mg-Al composite oxide is the laminar of thickness 5～10nm, the size 7～12nm of zinc oxide nanocrystalline, specific area 190～300m
2/ g.
The preparation method of the flaky Mg-Al composite oxide of a kind of loading ZnO nano particles of the present invention comprises:
(1) the magnalium carbonate stratiform double-hydroxide Mg-Al-CO that coprecipitation is prepared
3LDH obtained Mg-Al composite oxide in 2～4 hours in 400～600 ℃ of calcinings;
(2) at room temperature, the Mg-Al composite oxide after the calcining is put in 0.1～1mol/L soluble carbon acid salt solution, magnetic agitation 12～48h collects product, obtains laminar Mg-Al-CO
3LDH;
(3) at room temperature, with above-mentioned Mg-Al-CO
3LDH puts in 0.2～0.5mol/L soluble Zn salting liquid; Magnetic agitation is dispersed in laminar LDH and forms suspension in the solution, add 25～30wt% ammoniacal liquor and under room temperature, stirred 4～24 hours, collects product; Use deionized water and absolute ethanol washing respectively; In 60～100 ℃ of drying 12～24h, again in 400～600 ℃ of calcinings 2～4 hours, make the Mg-Al composite oxide of loading ZnO after letting.
Soluble carbon hydrochlorate in the said step (2) is selected from one or more the mixture in potash, sodium carbonate, the ammonium carbonate, and wherein the ratio of Mg-Al composite oxide and carbonate is 1g: 0.01～0.1mol;
Soluble zinc salt in the said step (3) is selected from one or more the mixture in acetate, zinc nitrate, zinc sulfate, the zinc chloride, wherein zinc salt and Mg-Al-CO
3The mass ratio of LDH is 1: 10～5: 1, and the mol ratio of zinc salt and ammoniacal liquor (mole of solute in the ammoniacal liquor) is 10: 1～1: 10.
The flaky Mg-Al composite oxide of a kind of loading ZnO nano particles of the present invention is applied to the degraded and the removal of anionic pollutant in the waste water from dyestuff.
The Mg-Al composite oxide of loading ZnO is dispersed in the Acid Red G solution, pours into again in the jacket type photo catalysis reactor, open mercury lamp; Behind UV-irradiation; Solution is become colorless by redness very soon, and composite powder becomes white by redness earlier, slowly becomes white by redness again.The concentration of the compound of dye molecule in water is 0.4g/L～20g/L, but bubbling air or oxygen quicken photocatalytic process in the photocatalytic process.
Mg-Al composite oxide of the present invention is laminar, have very strong adsorption capacity, and the particle of nano zine oxide is little; Good dispersion on Mg-Al composite oxide, photocatalytic activity is strong, quickly the adsorpting anion dyestuff; Utilize the photocatalytic activity of Zinc oxide nanoparticle; Through dye molecule further being decomposed behind the ultra violet lamp, and with the product intercalation of the catalytic degradation interlayer to Mg-Al composite oxide, thereby thoroughly remove the anionic pollutant in the waste water.
Beneficial effect
(1) Mg-Al composite oxide of the prepared loading ZnO of the present invention; The strong characteristics of the adsorptivity ability of adsorbent own have been kept; Possessed higher photocatalytic activity simultaneously; And specific area is big, and is strong to the degradation capability of anionic dye pollutant, has a good application prospect in the purified treatment field of waste water from dyestuff;
(2) this preparation technology is simple, and is environmentally friendly, low to the production equipment requirement, has good economic benefit, is easy to suitability for industrialized production.
Description of drawings
Fig. 1 is the X-ray diffractogram of embodiment 1 preparation LDHs and laminar LDH, (a) is LDH, (b) is laminar LDH;
Fig. 2 is the N of the laminar LDH of embodiment 2 preparations
2Adsorption-desorption isothermal curve and corresponding pore size distribution curve;
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the Mg-Al composite oxide of embodiment 3 preparation loading ZnOs;
Fig. 4 is the X-ray diffractogram of the Mg-Al composite oxide of embodiment 4 preparation loading ZnOs;
Fig. 5 is that the Mg-Al composite oxide of embodiment 4 preparation loading ZnOs adsorbs behind the Acid Red G and the infrared spectrum behind the photocatalysis Acid Red G, as a comparison, has provided the infrared spectrum of Acid Red G.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
At room temperature, the Mg-Al-CO that coprecipitation is prepared
3LDH calcines down at 500 ℃ and obtained Mg-Al composite oxide in 4 hours, gets the 21g natrium carbonicum calcinatum and puts into beaker, measures the 200ml deionized water again and adds in the beaker; Magnetic agitation, the Mg-Al composite oxide 3g that gets again after the above-mentioned calcining adds in the beaker, at room temperature magnetic agitation 12h; Filtration obtains product; Product is washed respectively 3 times with deionized water and absolute ethyl alcohol, 60 ℃ of dryings 12 hours, obtain laminar Mg-Al-CO then
3LDH.
Fig. 1 is the Mg-Al-CO of present embodiment preparation
3LDH and laminar Mg-Al-CO
3LDH (a) is Mg-Al-CO
3LDH (b) is laminar Mg-Al-CO
3LDH.From figure, find out, with Mg-Al-CO
3The characteristic peak of LDH is compared, laminar Mg-Al-CO
3Obvious wideization of the characteristic peak of LDH, abscissa is 2 θ among the figure, and unit is degree, and ordinate is a relative intensity.
At room temperature, the Mg-Al-CO that coprecipitation is prepared
3LDH calcines down at 500 ℃ and obtained Mg-Al composite oxide in 3 hours.Get the 10.5g natrium carbonicum calcinatum and put into beaker, measure the 200ml deionized water again and add in the beaker magnetic agitation; The Mg-Al composite oxide 3g that gets again after the above-mentioned calcining adds in the beaker; At room temperature magnetic agitation 24h filters and obtains product, and product is washed respectively 3 times with deionized water and absolute ethyl alcohol; 80 ℃ of dryings 12 hours, obtain laminar Mg-Al-CO then
3LDH.
Fig. 2 is the laminar Mg-Al-CO of present embodiment preparation
3The N of LDH
2Adsorption-desorption isothermal curve and corresponding pore size distribution curve are by N
2The adsorption-desorption isothermal curve is found out laminar Mg-Al-CO
3The adsorption curve of LDH has tangible hysteresis loop, shows laminar Mg-Al-CO
3LDH has the hole of layer structure, finds out laminar Mg-Al-CO by pore size distribution curve
3The distribution that two scopes are arranged in the hole of LDH is respectively 3.5-4nm and 5-15nm.Laminar Mg-Al-CO
3The BET specific surface of LDH is 192m
2/ g.
Embodiment 3
Take by weighing 8.8g zinc acetate dihydrate (219.51) and join in the 62.5ml water, stirred 5 minutes, the magnalium carbonate stratiform double-hydroxide that takes by weighing 1.5g embodiment 1 preparation again joins in the above-mentioned solution stirred suspension 5 minutes.Measure 25%～28% ammoniacal liquor 16ml, be diluted to 140ml after, join in the above-mentioned suspension, at room temperature magnetic agitation 12h.After reaction finishes, use absolute ethanol washing again 1 time 6 times, through 60 ℃ of oven dry 24 hours with the distilled water washing.With powder in air 500 ℃ the calcining 2 hours, obtain Zinc oxide nanoparticle/Mg-Al composite oxide.
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the Mg-Al composite oxide of the loading ZnO of present embodiment preparation; Can see among the figure that laminar stratiform composite oxides have kept its layer structure; Zinc oxide is graininess, lattice fringe is clearly arranged; Show that zinc oxide has good degree of crystallinity, the particle diameter of zinc oxide is about 10nm.
Take by weighing 4.4g zinc acetate dihydrate (219.51) and join in the 62.5ml water, stirred 5 minutes, the magnalium carbonate stratiform double-hydroxide that takes by weighing 6g embodiment 2 preparations again joins in the above-mentioned solution stirred suspension 5 minutes.Measure 25%～28% ammoniacal liquor 8ml, be diluted to 50ml after, join in the above-mentioned suspension, at room temperature magnetic agitation 24h.After reaction finishes, use absolute ethanol washing again 3 times 4 times, through 100 ℃ of oven dry 12 hours with the distilled water washing.With powder 500 ℃ of calcinings 4 hours in air, obtain the Mg-Al composite oxide of loading ZnO.
The Mg-Al composite oxide adding 500ml of 0.1g loading ZnO is arrived, and concentration is in the Acid Red G solution of 50mg/L, stirs 2 hours; Centrifugal after the question response balance; Collect powder,, obtain adsorbing the Mg-Al composite oxide of the loading ZnO of Acid Red G through 80 ℃ of oven dry 12 hours.The Mg-Al composite oxide that takes by weighing the 0.1g loading ZnO joins 500ml, and concentration is in the Acid Red G solution of 50mg/L, and aerating oxygen, oxygen gas flow rate are 100ml/min.With the mercury lamp irradiation, cessation reaction after 2 hours reclaims powder.
Fig. 4 is the X-ray diffractogram of the Mg-Al composite oxide of the loading ZnO of present embodiment preparation, and the zinc oxide characteristic peak shown in the figure is fairly obvious.The crystal face that has marked is all corresponding to buergerite phase oxidation zinc, and the magnalium laminar oxide occurs with unbodied form, and abscissa is 2 θ among the figure, and unit is degree, and ordinate is a relative intensity.After Fig. 5 has provided the Mg-Al composite oxide absorption Acid Red G of loading ZnO, and the infrared spectrum of compound behind the catalysis Acid Red G, the infrared spectrum that wherein gives Acid Red G compares.The material that pairing infrared spectrum is corresponding respectively among the figure is: (a) be the Mg-Al composite oxide through the loading ZnO after the photocatalytic degradation Acid Red G for Acid Red G, (b) for Mg-Al composite oxide, (c) that has adsorbed Acid Red G loading ZnO afterwards.Can see among the figure that the characteristic peak of a series of Acid Red Gs has appearred in this compound after having adsorbed Acid Red G: at 1498cm
-1The place occurred-characteristic peak of N=N-, at 1216cm
-1With the characteristic peak that O-S=O occurred, at 1050cm
-1With the characteristic peak that symmetrical stretching vibration occurred.The Mg-Al composite oxide of loading ZnO does not have the characteristic peak of Acid Red G behind the photocatalytic degradation Acid Red G, only at 1114cm
-1A SO has appearred in the place
4 2-Characteristic peak, thereby the proof Acid Red G is decomposed, and the sulfate radical intercalation that produces is on the interlayer of Mg-Al composite oxide.Abscissa among the figure is a wave number, and unit is reciprocal centimetre, and ordinate is a transmitance.
Claims (1)
1. the preparation method of the flaky Mg-Al composite oxide of a loading ZnO nano particles is characterized in that:
Described ZnO nano particle and flaky Mg-Al composite oxide, its mass ratio are 1: 5～3: 1;
In the flaky Mg-Al composite oxide of this loading ZnO nano particles, Mg-Al composite oxide is the laminar of thickness 5～10nm, the size 7～12nm of zinc oxide nanocrystalline, specific area 190～300m
2/ g;
Its concrete steps are following:
(1) the magnalium carbonate stratiform double-hydroxide Mg-Al-CO that coprecipitation is prepared
3LDH obtained Mg-Al composite oxide in 2～4 hours in 400～600 ℃ of calcinings;
(2) at room temperature, the Mg-Al composite oxide after the calcining is put in 0.1～1mol/L soluble carbon acid salt solution, magnetic agitation 12～48h collects product, obtains laminar Mg-Al-CO
3LDH;
Wherein, the soluble carbon hydrochlorate is selected from one or more the mixture in potash, sodium carbonate, the ammonium carbonate, and wherein the ratio of Mg-Al composite oxide and carbonate is 1g: 0.01～0.1mol;
(3) at room temperature, the Mg-Al-CO that step (2) is obtained
3LDH puts in 0.2～0.5mol/L soluble Zn salting liquid, and magnetic agitation makes laminar Mg-Al-CO
3LDH is dispersed in and forms suspension in the solution; Adding 25～30wt% ammoniacal liquor stirred under room temperature 4～24 hours; Collect product, use deionized water and absolute ethanol washing respectively, in 60～100 ℃ of drying 12～24h; And then, make the flaky Mg-Al composite oxide of loading ZnO nano particles in 400～600 ℃ of calcinings 2～4 hours;
Wherein, soluble zinc salt is selected from one or more the mixture in acetate, zinc nitrate, zinc sulfate, the zinc chloride, wherein the Mg-Al-CO that obtains of zinc salt and step (2)
3The mass ratio of LDH is 1: 10～5: 1, and the mol ratio of zinc salt and ammoniacal liquor is 10: 1～1: 10.
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| CN104311883A (en) * | 2014-10-15 | 2015-01-28 | 上海应用技术学院 | Flame retardant ultraviolet resistant material |
| CN105642275B (en) * | 2016-03-08 | 2018-03-23 | 济南大学 | A kind of CeO2/Bi2WO6/ MgAl LDH composite photo-catalysts and its preparation method and application |
| CN109046357A (en) * | 2018-08-27 | 2018-12-21 | 上海大学 | A kind of preparation method of metal oxide-LDH loaded catalyst |
| CN111604053B (en) * | 2020-06-07 | 2022-09-02 | 重庆工商大学 | Ternary hydrotalcite photocatalyst and preparation method and application thereof |
| CN112934167A (en) * | 2021-03-08 | 2021-06-11 | 浙江工业大学 | Titanium dioxide/layered double hydroxide non-carbon-based composite material and preparation method and application thereof |
| CN113058544A (en) * | 2021-04-06 | 2021-07-02 | 浙江工业大学 | Photo-assisted regeneration non-carbon-based adsorbent following 'two-stage' rate increase mechanism and preparation method and application thereof |
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