CN104888823A - Photochemically-modified double-metal hydroxide, preparation method and applications thereof - Google Patents
Photochemically-modified double-metal hydroxide, preparation method and applications thereof Download PDFInfo
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- CN104888823A CN104888823A CN201510180775.6A CN201510180775A CN104888823A CN 104888823 A CN104888823 A CN 104888823A CN 201510180775 A CN201510180775 A CN 201510180775A CN 104888823 A CN104888823 A CN 104888823A
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- ldhs
- phosphate
- metal hydroxide
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Abstract
The present invention provides a photochemically-modified double-metal hydroxide, a preparation method and applications thereof. The preparation method comprises: preparing a soluble phosphate into a phosphate buffer solution, adding double-metal hydroxide powder into the phosphate buffer solution, carrying out ultrasonic dispersing, and irradiating the dispersing solution with a light source having a continuous wavelength so as to modify the surface of the double-metal hydroxide with the phosphate to obtain the phosphate-modified double-metal hydroxide. According to the present invention, the method has characteristics of simple implementation process, no toxic and hazardous substance, mild reaction conditions, no requirement of heat treatment, energy saving and environmental protection; and the photochemically-modified double-metal hydroxide provides significantly-improved photocatalytic degradation efficiency on the dye in the water body than before, and can be used for photocatalytic degradation of the dye pollutant in the water body.
Description
Technical field
The invention belongs to field of material surface modification, be specifically related to double-metal hydroxide surface light chemical modification, the double-metal hydroxide of modification is used for the dyestuff contaminant in photocatalytic degradation water body.
Background technology
Along with developing rapidly of modern society's industry, the pollutant in the waste gas given off during industrial production, waste water becomes the threat health of the mankind and a large factor of ball ecological environment.The waste water such as produced in synthetic paint, plastics, process hides, fabrication processes etc. contains aldehyde or phenols harmful substance, and even daily life drinking water also can be subject to the stripping pollution of contacted water distribution pipeline, water storage container, supply equipment and the protective materials such as coating, liner containing laccol, epoxy (phenolic aldehyde) resin.Therefore the pollutant how processed in air and water body is all the focus of scientific research person all the time.Photocatalytic pollutant degradation technology is the means of a kind of effective process pollutant of development recently, it utilizes ultraviolet light or even sunshine as the energy, vitalizing semiconductor catalyst produces strong oxidizing property free radical, can most of organic matters successfully in degradation water.Its operating cost is low, is a kind of high-efficiency energy-saving technology, has a good application prospect, and provides new thinking and new method for thoroughly solving problem of environmental pollution.
TiO
2photochemical catalyst widely uses at present, but it also exists the shortcomings such as forbidden band is wider, quantum yield is lower, therefore becomes for the research of Photocatalyst and Development of Novel photochemical catalyst the focus that people pay close attention in recent years.Double-metal hydroxide is a kind of compound by interlayer anion and positively charged laminate ordered fabrication.Its laminate cation and interlayer anion can modulations flexibly, extensively studied by as catalyst.The people such as K.M.Parida have studied containing laminate bivalent cation different in chromium LDHs on the impact of its photo-catalytic degradation of methyl-orange performance, and wherein the absorption of LDHs to visible ray comes from bimetallic oxo bridge M in laminate
iI-O-Cr
iIImetal-metal Charger transfer [N.Baliarsingh, K.M.Parida, G.C.Pradhan.Ind.Eng.Chem.Res., 2014,53,3834-3841].Adopt F
-, SO
4 2-, PO
4 3-be one of method of lifting catalytic performance to metal-oxide semiconductor (MOS) modifying surface Deng metalloid anion, the people such as such as Honggang Fu have reported TiO
2light anode pickling, in sodium phosphate aqueous solution, is then calcined, is obtained the TiO of phosphate radical modification at 450 DEG C
2light anode, the performance of this light anode catalytic water oxidation and degradation of organic substances after modification is obviously promoted [L.Jing, J.Zhou, J.R.Durrant, J.Tang, D.Liu, H.Fu.Energy Environ.Sci., 2012,5,6552-6558].But current surface modification is mainly for metal-oxide semiconductor (MOS), and modifying process all needs calcination processing, the research for double-metal hydroxide photocatalyst surface photochemical modification there is no report.
Summary of the invention
The object of this invention is to provide a kind of photochemical modification double-metal hydroxide and preparation method thereof, the double-metal hydroxide of modification can be directly used in photocatalytic degradation of dye reaction.
Phosphate radical modified bimetallic hydroxide (hereinafter abbreviated as LDHs) provided by the invention: its chemical formula is: [M
2+ 1-xn
3+/4+ x(OH)
2] (CO
3 2-)
x/2(PO
4 3-)
ynH
2o, wherein M is the one in Ni, Zn, and N is the one in Cr, Ti, x=0.2 ~ 0.33, x:y=1 ~ 2:1, n=1 ~ 6.After LDHs surface modification, the molar content of phosphate radical is the crystallite dimension of 2-6%, LDHs is 30 ~ 200nm.
The method of modifying that the present invention adopts is: by LDHs ultrasonic disperse in phosphate buffer solution, utilize this LDHs dispersion liquid of light source irradiation with continuous wavelength under magnetic stirring, modified LDHs sample is spent deionized water, drying, obtains the LDHs photochemical catalyst of phosphate radical surface modification.This modifying process is fast and simple, and reaction condition is gentle, does not need high-temperature process, effectively can strengthen the performance of LDHs photochemical catalyst.
Above-mentioned double-metal hydroxide surface light chemical modification method, concrete steps are as follows:
A. be mixed with soluble phosphate the cushioning liquid that molar concentration is 0.05 ~ 1mol/L, wherein the pH of cushioning liquid is 6 ~ 9; Described soluble phosphate is: the one in potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and sodium hydrogen phosphate;
B. joined by LDHs in the phosphate buffer solution described in steps A, wherein the addition of LDHs is 1 ~ 10g/L, ultrasonic 10 ~ 60 minutes, and ultrasonic power is 350 ~ 700W; Use light source irradiation 0.5 ~ 4 hour more under magnetic stirring; Centrifugation goes out LDHs;
Described LDHs is [M
2+ 1-xn
3+/4+ x(OH)
2] (CO
3 2-)
x/2(PO
4 3-)
ynH
2o, wherein M is the one in Ni, Zn, and N is the one in Cr, Ti, x=0.2 ~ 0.33, x:y=1 ~ 2:1, n=1 ~ 6.This LDHs is prepared by bibliography [Claudia Gomes Silva, YounesBouizi, Vicente Fornes, and Hermenegildo Garcia.J.Am.Chem.Soc., 2009,131,13833-13839].
Described light source is the xenon lamp with continuous wavelength, and wave-length coverage is 300 ~ 2500nm, and intensity of illumination is 50 ~ 300mW/cm
2.
C. the LDHs deionized water centrifuge washing obtained by step B 3 times, in 70 DEG C of dryings 12 hours, obtains the double-metal hydroxide of phosphate radical surface modification; The rotating speed of described centrifuge washing is 4000rpm, and the time is 5-15min.
LDHs modified for above-mentioned phosphate radical directly can be used as the catalyst of the dyestuffs such as photocatalytic degradation methylene blue, methyl orange.Found out by embodiment test result, the photochemical catalyst that the present invention obtains is greater than 90% to the methyl orange degradation rate of 6 hours, is greater than commodity P25 photochemical catalyst degradation rate under the same conditions (40%).
The present invention has following remarkable result:
(1) surface modifying method process provided by the invention is simple, and mild condition, carries out under room temperature, without the need to subsequent calcination process, significantly energy-saving and cost-reducing, is suitable for scale process and production.
(2) light degradation property of modified photochemical catalyst to dyes significantly strengthens, and is applicable to carrying out light degradation process to the dyestuff contaminant in industrial production and environment, saves processing cost.
Detailed description of the invention
Embodiment 1
A. K is taken
2hPO
43H
2o 1.3921g, KH
2pO
40.5171g is dissolved in 100mL deionized water, and its molar concentration is 0.1mol/L, pH is 7;
B. be added in the phosphate buffer solution described in steps A by 0.2g ZnTi-LDHs photochemical catalyst, ultrasonic 20 minutes, ultrasonic power was 700W;
C. by the ZnTi-LDHs dispersion liquid after ultrasonic in step B under magnetic stirring, irradiate 1 hour with 300W xenon source, intensity of illumination is 100mW/cm
2;
D. by the centrifuge washing 5 times (rotating speed is 4000rpm, and the time is 5min) in centrifuges of the ZnTi-LDHs deionized water in step C, in 70 DEG C of dryings 12 hours, the ZnTi-LDHs photochemical catalyst of phosphate radical surface modification is obtained.
The semiconductor base obtained/containing chromium bimetallic subphosphate optoelectronic pole carried out XPS sign, and the atomic percentage conc recording P is 4.39%.
Performance evaluation: preparation 30ml concentration is that the methyl orange solution of 10ppm joins in quartzy bottle, add the ZnTi-LDHs photochemical catalyst of the phosphate radical surface modification that 0.01g step D obtains again, magnetic agitation 30min reaches adsorption equilibrium, sampling once, then irradiate with the xenon lamp of power 300W, and period sampling measuring methyl orange degradation rate.Concrete sampling procedure is: from quartzy bottle, take out 1ml solution with pipette, 10ml is diluted to by deionized water, afterwards with the centrifugal 5min of 4500rpm rotating speed, pour supernatant liquor into quartz colorimetric utensil, measure the concentration of dye solution in day part institute sample thief with Japanese Shimadzu UV-2501PC Ultravioblet spectrophotometer, measure the absorbance A of solution after the original solution and reaction of dyestuff maximum absorption wave strong point
0and At, utilize At/A
0=Ct/C
o=η calculates photochemical catalyst to the palliating degradation degree of dyestuff.Record methyl orange 1h, the degradation rate of 3h, 6h is respectively 60%, 83%, 95%.
Contrast experiment: adopt above-mentioned similarity condition, test ZnTi-LDHs without surface light chemical modification to methyl orange degradation rate, the methyl orange degradation rate after its 1h, 3h, 6h that records is respectively 49%, 64%, 76%.
Embodiment 2
A. K is taken
2hPO
43H
2o 2.7842g, KH
2pO
41.0342g is dissolved in 100mL deionized water, and its molar concentration is 0.2mol/L, pH is 7;
B. be added in the phosphate buffer solution described in steps A by 0.2g ZnTi-LDHs photochemical catalyst, ultrasonic 30 minutes, ultrasonic power was 700W;
C. by the ZnTi-LDHs dispersion liquid after ultrasonic in step B under magnetic stirring, irradiate 1.5 hours with 300W xenon source, intensity of illumination is 150mW/cm
2;
D. by the centrifuge washing 5 times (rotating speed is 4000rpm, and the time is 5min) in centrifuges of the ZnTi-LDHs deionized water in step C, in 70 DEG C of dryings 12 hours, the ZnTi-LDHs photochemical catalyst of phosphate radical surface modification is obtained.
The semiconductor base obtained/containing chromium bimetallic subphosphate optoelectronic pole carried out XPS sign, and the atomic percentage conc recording P is 3.35%.
Method with embodiment 1 carries out the degradation property evaluation to methyl orange solution, and the methyl orange degradation rate after 1h, 3h, 6h that records is respectively 57%, 88%, 95%.
Embodiment 3
A. K is taken
2hPO
43H
2o 6.9605g, KH
2pO
42.5855g is dissolved in 100mL deionized water, and its molar concentration is 0.5mol/L, pH is 7;
B. be added in the phosphate buffer solution described in steps A by 0.2g ZnCr-LDHs photochemical catalyst, ultrasonic 50 minutes, ultrasonic power was 600W;
C. by the ZnCr-LDHs dispersion liquid after ultrasonic in step B under magnetic stirring, irradiate 0.5 hour with 300W xenon source, intensity of illumination is 120mW/cm
2;
D. by the centrifuge washing 5 times (rotating speed is 4000rpm, and the time is 5min) in centrifuges of the ZnTi-LDHs deionized water in step C, in 70 DEG C of dryings 12 hours, the ZnCr-LDHs photochemical catalyst of phosphate radical surface modification is obtained.
The semiconductor base obtained/containing chromium bimetallic subphosphate optoelectronic pole carried out XPS sign, and the atomic percentage conc recording P is 4.05%.
Method with embodiment 1 carries out the degradation property evaluation to methyl orange solution, and the methyl orange degradation rate after 1h, 3h, 6h that records is respectively 62%, 87%, 96%.
Embodiment 4
A. K is taken
2hPO
43H
2o 3.8341g, KH
2pO
40.4355g is dissolved in 100mL deionized water, and its molar concentration is 0.2mol/L, pH is 7.5;
B. be added in the phosphate buffer solution described in steps A by 0.2g ZnCr-LDHs photochemical catalyst, ultrasonic 60 minutes, ultrasonic power was 700W;
C. by the ZnCr-LDHs dispersion liquid after ultrasonic in step B under magnetic stirring, irradiate 2 hours with 300W xenon source, intensity of illumination is 100mW/cm
2;
D. by the centrifuge washing 5 times (rotating speed is 4000rpm, and the time is 5min) in centrifuges of the ZnCr-LDHs deionized water in step C, in 70 DEG C of dryings 12 hours, the ZnCr-LDHs photochemical catalyst of phosphate radical surface modification is obtained.
The semiconductor base obtained/containing chromium bimetallic subphosphate optoelectronic pole carried out XPS sign, and the atomic percentage conc recording P is 5.12%.
Method with embodiment 1 carries out the degradation property evaluation to methyl orange solution, and the methyl orange degradation rate after 1h, 3h, 6h that records is respectively 56%, 85%, 96%.
Claims (3)
1. a double-metal hydroxide surface light chemical modification method, concrete steps are as follows:
A. be mixed with soluble phosphate the cushioning liquid that molar concentration is 0.05 ~ 1mol/L, wherein the pH of cushioning liquid is 6 ~ 9; Described soluble phosphate is: the one in potassium dihydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate and sodium hydrogen phosphate;
B. join in the phosphate buffer solution described in steps A by double-metal hydroxide LDHs, wherein the addition of LDHs is 1 ~ 10g/L, ultrasonic 10 ~ 60 minutes, and ultrasonic power is 350 ~ 700W; Use light source irradiation 0.5 ~ 4 hour more under magnetic stirring; Centrifugation goes out LDHs;
Described LDHs is [M
2+ 1-xn
3+/4+ x(OH)
2] (CO
3 2-)
x/2(PO
4 3-)
ynH
2o, wherein M is the one in Ni, Zn, and N is the one in Cr, Ti, x=0.2 ~ 0.33, x:y=1 ~ 2:1, n=1 ~ 6; Described light source is the xenon lamp with continuous wavelength, and wave-length coverage is 300 ~ 2500nm, and intensity of illumination is 50 ~ 300mW/cm
2;
C. the LDHs deionized water centrifuge washing obtained by step B 3 times, in 70 DEG C of dryings 12 hours, obtains the double-metal hydroxide of phosphate radical modification; The rotating speed of described centrifuge washing is 4000rpm, and the time is 5-15min.
2. the phosphate radical modified bimetallic hydroxide prepared of a method according to claim 1: its chemical formula is: [M
2+ 1-xn
3+/4+ x(OH)
2] (CO
3 2-)
x/2(PO
4 3-)
ynH
2o, wherein M is the one in Ni, Zn, and N is the one in Cr, Ti, x=0.2 ~ 0.33, x:y=1 ~ 2:1, n=1 ~ 6; After LDHs surface modification, the molar content of phosphate radical is the crystallite dimension of 2-6%, LDHs is 30 ~ 200nm.
3. phosphate radical modified bimetallic hydroxide according to claim 2 to be used as the dyestuff in photocatalytic degradation water body by one kind.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106179431A (en) * | 2016-07-26 | 2016-12-07 | 北京化工大学 | A kind of zinc titanium metal composite oxide and preparation thereof and application |
| CN109925512A (en) * | 2019-01-07 | 2019-06-25 | 安徽理工大学 | A kind of novel aspirin two-dimensional nano load medicine and slow-releasing system |
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| CN102872894A (en) * | 2012-11-02 | 2013-01-16 | 北京化工大学 | NiTi hydrotalcite nanosheet catalyst responding to visible light, and preparation method of catalyst |
| KR20130127018A (en) * | 2012-05-07 | 2013-11-22 | 포항공과대학교 산학협력단 | Synthesis of layered double hydroxide or mixed oxide embedding nanoparticles |
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2015
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| KR20130127018A (en) * | 2012-05-07 | 2013-11-22 | 포항공과대학교 산학협력단 | Synthesis of layered double hydroxide or mixed oxide embedding nanoparticles |
| CN102872918A (en) * | 2012-11-02 | 2013-01-16 | 北京化工大学 | ZnTi hydrotalcite nanosheet catalyst and application of catalyst in hydrogen preparation by photoactivating and decomposing water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179431A (en) * | 2016-07-26 | 2016-12-07 | 北京化工大学 | A kind of zinc titanium metal composite oxide and preparation thereof and application |
| CN106179431B (en) * | 2016-07-26 | 2018-08-03 | 北京化工大学 | A kind of zinc titanium metal composite oxide and its preparation and application |
| CN109925512A (en) * | 2019-01-07 | 2019-06-25 | 安徽理工大学 | A kind of novel aspirin two-dimensional nano load medicine and slow-releasing system |
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