CN105056931B - A kind of have zinc-magnesium indium composite oxides of near infrared light catalysis activity and its preparation method and application - Google Patents
A kind of have zinc-magnesium indium composite oxides of near infrared light catalysis activity and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of have zinc-magnesium indium composite oxides of near infrared light catalysis activity and its preparation method and application, belong to field of photocatalytic material.The zinc-magnesium indium composite oxides of the present invention, its chemical structural formula is：Zn3Mg3In2O9；In irregular laminated structure, particle diameter 50 200nm.The zinc-magnesium indium composite oxides of the present invention, the houghite lamellar structure of its precursor is not destroyed completely, and zinc oxide, magnesium oxide and Indium sesquioxide. are not yet completely independent crystallization and split-phase, have porous laminated structure, diameter 50 200nm.This zinc-magnesium indium composite oxides is in addition to having photocatalytic activity near infrared light region, in Uv and visible light region, also all there is photocatalytic activity, there is to Organic substance under dark condition good absorption property, belong to the good wide spectrum photocatalyst of absorption property.Present invention also offers Zn3Mg3In2O9Preparation method, and its under the conditions of near infrared light, ultraviolet light and radiation of visible light, as the application of photocatalytic degradation catalysts.
Description
Technical field
The present invention relates to a kind of have zinc-magnesium indium composite oxides of near infrared light catalysis activity and preparation method thereof and answer
With belonging to field of photocatalytic material.
Background technology
Photocatalysis be using photocatalyst, the luminous energy that nature exists is converted into energy needed for chemical reaction thus
The catalytic action producing.Using photocatalyst come catalytic degradation organic pollution both can pollution administration, again can be utilized solar energy,
Reduce the dependence to non-renewable energy resources, thus more carried out extensive concern.Oxide semiconductor class photocatalyst such as dioxy
Change titanium, zinc oxide are cheap, environmental friendliness, and majority of organic pollutants all can be degraded to non-selectivity, in photocatalysis
Field occupies very important status.But the energy gap of titanium dioxide and zinc oxide is about 3.2eV, it is only capable of absorbing ultraviolet light,
And reaching in the sunlight on ground, contained ultraviolet is less than 5%, and accounts for the visible ray of sunshine gross energy about more than 90% and closely red
Outer light can not be obtained by.
In recent years, domestic and international researcher is attempted using various approach to semiconductor light-catalysts such as titanium dioxide, zinc oxide
Modified and modified, to widening its spectral response range and improving its photocatalytic activity.As by non-to carbon, nitrogen, sulfur, boron etc. gold
Belong to Lacking oxygen or the replacement part Lacking oxygen that element is introduced in metal oxide lattice, the energy gap of metal-oxide can be made to become
Narrow；Other transition metal ionss, rare earth ion and precious metal ion, shape impurity energy is introduced in metal oxide lattice
Level, makes the electronics in valence band can be excited by the light of longer wavelength by transitting to impurity energy level, after transitting to impurity energy level, leads to
Cross energy absorption again, conduction band transitted to again by impurity energy level, thus reduce can response light wavelength；In metal oxidation
Thing surface depositing noble metal, promotes light induced electron to outside migration, stops the compound of photo-generate electron-hole；By energy gap not
Two or more same semi-conducting materials are compound to together, form nano-heterogeneous structure, to promote the separation of electron hole, from
And spectral response range of expansion material etc..Additionally, by being co-precipitated zinc salt with aluminium salt, forming the mixing of hydrotalcite-like compound
Metal hydroxidess, then through suitable high-temperature calcination, zinc oxide and the aluminic acid zinc composite oxide of uniform " doping " also can be formed,
The light abstraction width of zinc oxide is extended with this.However, these approach only can be by the spectral response model of titanium dioxide and zinc oxide
Enclose and expand to and by light region, or its ultraviolet catalytic activity can be improved, the near infrared light accounting for solar energy nearly about 44% does not still obtain
To effectively utilizes.
Therefore, development just has the oxide-based photocatalyst of full spectrum of ultraviolet light, visible ray and near infrared light catalysis activity
More urgent.
Content of the invention
It is an object of the invention to provide a kind of prepared by using houghite as precursor in ultraviolet, visible and closely red
Outer smooth region all has the combined oxidation species photocatalyst of photocatalytic activity.
Present invention also offers the preparation side of the above-mentioned combined oxidation species photocatalyst near infrared light catalysis activity
Method, and the application of above-mentioned combined oxidation species photocatalyst.
Technical scheme
A kind of zinc-magnesium indium composite oxides near infrared light catalysis activity, its chemical structural formula is：Zn3Mg3In2O9.
Above-mentioned zinc-magnesium indium composite oxides, in irregular laminated structure, particle diameter 50-200nm；Transmission electron microscope photo such as accompanying drawing
Shown in 1.
The zinc-magnesium indium composite oxides of the present invention, the houghite lamellar structure of its precursor is not destroyed completely, oxidation
Zinc, magnesium oxide and Indium sesquioxide. are not yet completely independent crystallization and split-phase, have porous laminated structure, diameter 50-200nm.This zinc-magnesium
Indium composite oxides, in addition to having photocatalytic activity near infrared light region, also all have light in Uv and visible light region and urge
Change activity, there is to Organic substance under dark condition good absorption property, belong to the good wide spectrum photocatalysis of absorption property
Agent.
The zinc-magnesium indium composite oxides of the present invention, its zinc ion, magnesium ion, the mol ratio of indium ion can only be the present invention
3:3:2；Otherwise, photocatalytic Degradation will not be produced to organic pollution under near infrared light.
The preparation method of above-mentioned zinc-magnesium indium composite oxides, first prepares zinc-magnesium indium hybrid metal hydroxide using coprecipitation
Thing, then in 400-600oCalcine 3 hours under C, obtain zinc-magnesium indium composite oxides.The present invention passes through zinc-magnesium indium in control process
Ratio and each parameter, make the product of acquisition have the catalysis characteristicses of wide spectrum catalytic degradation organic pollution.
Above-mentioned preparation method, comprises the following steps：
（1）Prepare in proportion containing zinc ion, magnesium ion, indium ion nitrate solution；Sodium hydroxide and sodium carbonate are pressed
3:1 mol ratio is dissolved in the water, and forms mixed ammonium/alkali solutions；
（2）Under agitation nitrate solution and mixed ammonium/alkali solutions are mixed, control reactant mixture pH 10-11 it
Between, form co-precipitate colloid；Stirring co-precipitate colloid disperses to it, is warming up to 55oC, is stirred for 3 hours, is cooled to room
Temperature, taking precipitate；Wash precipitate with water to neutral, then in 55oC is vacuum dried and grinds, then be placed in Muffle furnace in
400-600oProcess 3 hours under C.
Above-mentioned preparation method, in nitrate solution, zinc ion, magnesium ion, the mol ratio of indium ion can only be 3:3:2；Otherwise
Even preparing the complex in houghite layer structure, through calcining after nor obtain near infrared light, ultraviolet light, can
See under light irradiation, all organic pollution is produced with the zinc-magnesium indium composite oxides of good catalytic degradation effect.
Above-mentioned preparation method, the pH of reactant mixture must control between 10-11, to guarantee to form zinc, magnesium, three kinds of indium
The co-precipitation hydroxide of metal ion, otherwise cannot form preferable hydrotalcite-like compound；And the temperature in Muffle furnace, if
The too low decomposition being unfavorable for zinc-magnesium indium mixed hydroxides and its interlayer carbanion, and temperature is too high, causes zinc, magnesium, indium
The split-phase of oxide, causes prepared product near infrared light catalysis activity poor, or even loses near infrared light catalysis activity；Cause
This, muffle furnace must control in 400-600oBetween C.Preferably, pH is 10.5, and the temperature in Muffle furnace is 500oC；?
Under this pH, temperature conditionss, the catalytic degradation performance of prepared zinc-magnesium indium composite oxides is more preferable.
Above-mentioned preparation method is it is preferred that step（2）Concrete operations as follows：
Under agitation nitrate solution and mixed ammonium/alkali solutions are simultaneously added dropwise in reactor, control reactant mixture
PH, forms co-precipitate colloid；
High degree of agitation co-precipitate colloid, is completely dispersed uniformly to it, then heats to 55 DEG C, slight stirring 3 hours, from
So it is cooled to room temperature and stand 12h, taking precipitate；
Wash precipitate with water to be vacuum dried and grind after 55 DEG C to neutrality, be subsequently placed in Muffle furnace and process 3 hours.
The zinc-magnesium indium composite oxides of the present invention are under the conditions of near infrared light, ultraviolet light and radiation of visible light as photocatalysis
The application of degradation reaction catalyst.Preferably, under the conditions of near infrared light, answering as photocatalytic degradation catalysts
With.
Above-mentioned application, described photocatalytic degradation reacts the photocatalytic degradation reaction for organic pollution, particularly methyl orange
Photocatalytic degradation reaction.This light-catalyzed reaction can be using general quartz reactor or quartz test tube under conditions of stirring
To complete.
Above-mentioned application it is preferable that
Described ultraviolet light is provided by the medium pressure mercury lamp of 300W；
Described can see that light is provided by the middle pressure xenon lamp of 300W；
It is to carry after 200nm-780nm light that described near infrared light filters wavelength by the infrared lamp source filter plate of 275W
For.
In the present invention, if no special instructions, described water is deionized water.
Beneficial effect：
The zinc-magnesium indium composite oxides of the present invention have excellent near infrared light, ultraviolet light and visible light catalytic performance, and 3 is little
When near-infrared photo-catalytic degradation of methyl-orange clearance be 83%, the degrade clearance rate of methyl orange of 2 hours ultraviolet catalytics reaches
95%, the clearance of 2 hours visible light photocatalytic degradation methyl orange reaches 92%.Therefore, the zinc-magnesium indium composite oxides of the present invention are
A kind of wide spectrum photocatalytic agent, the rapid photocatalysis degradation organic contaminant of energy, have broad application prospects.The zinc that the present invention provides
The preparation method of magnesium indium wide spectrum photocatalytic agent is simple to operate, easy to spread.
Brief description
Fig. 1 is the transmission electron microscope photo of the zinc-magnesium indium composite oxides of the present invention.
Specific embodiment
With reference to specific embodiment, the invention will be further described；Except as otherwise indicating, the described number in embodiment
All in mass.
Embodiment 1
By 8.93 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 4.8 parts of NaOH and 4.24 part of Na2CO3It is scattered in 200 parts of deionized waters, form mixed ammonium/alkali solutions.In the reactor plus
Enter about 20 parts of deionized waters, be titrated to after pH10.5 with mixed ammonium/alkali solutions, under 1000 revs/min of mixing speed, by salt-mixture
It is simultaneously added dropwise in reactor with mixed ammonium/alkali solutions, and adjusts rate of addition, reaction pH is maintained 10.5, and guarantees salt-mixture
It is simultaneously added dropwise with mixed ammonium/alkali solutions and finish.After completion of dropping, continue to stir 1 hour under 1000 revs/min of mixing speed.Afterwards
Agitator speed is reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cold
But, to after room temperature, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace
Interior, with 2oThe speed of C/ minute is warmed up to 500oC, and in 500oIt is incubated 3 hours under C, after natural cooling, obtain zinc-magnesium indium and be combined
About 4.67 parts of oxidation photocatalyst.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in the dark
Adsorption reaction 3 hours, the eliminating rate of absorption to methyl orange is 57.4%.Take 1 part, put into 2000 parts of concentration 20mg/L first
In base orange solution, there is to methyl orange under conditions of near infrared light catalytic degradation effect, react 3 hours, methyl orange drops
Solution rate reaches 77.6%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, under visible light illumination, instead
Answer 2 hours, methyl orange clearance can reach 94.1%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions,
Under UV Light is penetrated, react 2 hours, methyl orange clearance can reach 95.3%.
Embodiment 2
By 8.93 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 4.8 parts of NaOH and 4.24 part of Na2CO3It is scattered in 200 parts of deionized waters, form mixed ammonium/alkali solutions.In the reactor plus
Enter about 10 parts of deionized waters, be titrated to after pH10 with mixed ammonium/alkali solutions, under 1200 revs/min of mixing speed, by salt-mixture and
Mixed ammonium/alkali solutions are simultaneously added dropwise in reactor, and adjust rate of addition, reaction pH is maintained 10, and guarantees salt-mixture with mixed
Conjunction aqueous slkali is simultaneously added dropwise and finishes.After completion of dropping, continue to stir 1 hour under 1200 revs/min of mixing speed.To stir afterwards
Mix device rotating speed and be reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cooled to
After room temperature, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace, with
2oThe speed of C/ minute is warmed up to 500oC, and in 500oIt is incubated 3 hours under C, after natural cooling, obtain zinc-magnesium indium composite oxides
About 4.67 parts of photocatalyst.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, adsorb anti-in the dark
Answer 3 hours, the eliminating rate of absorption to methyl orange is 56.7%.Take 1 part, put into 2000 parts of concentration 20mg/L methyl oranges molten
In liquid, there is to methyl orange under conditions of near infrared light catalytic degradation effect, react 3 hours, methyl orange degradation rate reaches
To 75.3%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, under visible light illumination, reaction 2 is little
When, methyl orange clearance can reach 93.2%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in purple
Under outer smooth light irradiation, react 2 hours, methyl orange clearance can reach 94.1%.
Embodiment 3
By 8.93 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 4.8 parts of NaOH and 4.24 part of Na2CO3It is scattered in 200 parts of deionized waters, form mixed ammonium/alkali solutions.In the reactor plus
Enter about 10 parts of deionized waters, be titrated to after pH11 with mixed ammonium/alkali solutions, under 1200 revs/min of mixing speed, by salt-mixture and
Mixed ammonium/alkali solutions are simultaneously added dropwise in reactor, and adjust rate of addition, reaction pH is maintained 11, and guarantees salt-mixture with mixed
Conjunction aqueous slkali is simultaneously added dropwise and finishes.After completion of dropping, continue to stir 1 hour under 1200 revs/min of mixing speed.To stir afterwards
Mix device rotating speed and be reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cooled to
After room temperature, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace, with
2oThe speed of C/ minute is warmed up to 500oC, and in 500oIt is incubated 3 hours under C, after natural cooling, obtain zinc-magnesium indium composite oxides
About 4.67 parts of photocatalyst.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, adsorb anti-in the dark
Answer 3 hours, the eliminating rate of absorption to methyl orange is 57.1%.Take 1 part, put into 2000 parts of concentration 20mg/L methyl oranges molten
In liquid, there is to methyl orange under conditions of near infrared light certain catalytic degradation effect, react 3 hours, methyl orange drops
Solution rate reaches 75.9%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, under visible light illumination, instead
Answer 2 hours, methyl orange clearance can reach 93.3%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions,
Under UV Light is penetrated, react 2 hours, methyl orange clearance can reach 94.8%.
Embodiment 4
By 8.93 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 4.8 parts of NaOH and 4.24 part of Na2CO3It is scattered in 200 parts of deionized waters, form mixed ammonium/alkali solutions.In the reactor plus
Enter about 10 parts of deionized waters, be titrated to after pH10.5 with mixed ammonium/alkali solutions, under 1200 revs/min of mixing speed, by salt-mixture
It is simultaneously added dropwise in reactor with mixed ammonium/alkali solutions, and adjusts rate of addition, reaction pH is maintained 10.5, and guarantees salt-mixture
It is simultaneously added dropwise with mixed ammonium/alkali solutions and finish.After completion of dropping, continue to stir 1 hour under 1200 revs/min of mixing speed.Afterwards
Agitator speed is reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cold
But, to after room temperature, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace
Interior, with 2oThe speed of C/ minute is warmed up to 400oC, and in 400oIt is incubated 3 hours under C, after natural cooling, obtain zinc-magnesium indium and be combined
About 4.67 parts of oxidation photocatalyst.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in the dark
Adsorption reaction 3 hours, the eliminating rate of absorption to methyl orange is 44.3%.Take 1 part, put into 2000 parts of concentration 20mg/L first
In base orange solution, there is to methyl orange under conditions of near infrared light certain catalytic degradation effect, react 3 hours, first
Base orange degradation rate reaches 63.2%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in radiation of visible light
Under, react 2 hours, methyl orange clearance can reach 87.3%.Take 1 part, put into 2000 parts of concentration 20mg/L methyl oranges molten
In liquid, under UV Light is penetrated, react 2 hours, methyl orange clearance can reach 89.1%.
Embodiment 5
By 8.93 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 4.8 parts of NaOH and 4.24 part of Na2CO3It is scattered in 200 parts of deionized waters, form mixed ammonium/alkali solutions.In the reactor plus
Enter about 10 parts of deionized waters, be titrated to after pH10.5 with mixed ammonium/alkali solutions, under 1200 revs/min of mixing speed, by salt-mixture
It is simultaneously added dropwise in reactor with mixed ammonium/alkali solutions, and adjusts rate of addition, reaction pH is maintained 10.5, and guarantees salt-mixture
It is simultaneously added dropwise with mixed ammonium/alkali solutions and finish.After completion of dropping, continue to stir 1 hour under 1200 revs/min of mixing speed.Afterwards
Agitator speed is reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cold
But, to after room temperature, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace
Interior, with 2oThe speed of C/ minute is warmed up to 600oC, and in 600oIt is incubated 3 hours under C, after natural cooling, obtain zinc-magnesium indium and be combined
About 4.67 parts of oxidation photocatalyst.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in the dark
Adsorption reaction 3 hours, the eliminating rate of absorption to methyl orange is 55.1%.Take 1 part, put into 2000 parts of concentration 20mg/L first
In base orange solution, there is to methyl orange under conditions of near infrared light certain catalytic degradation effect, react 3 hours, first
Base orange degradation rate reaches 71.4%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in radiation of visible light
Under, react 2 hours, methyl orange clearance can reach 96.4%.Take 1 part, put into 2000 parts of concentration 20mg/L methyl oranges molten
In liquid, under UV Light is penetrated, react 2 hours, methyl orange clearance can reach 97.3%.
Comparative example 1
By 8.93 parts of Zn (NO3)2∙6H2O and 3.75 part of Al (NO3)3∙9H2O is dissolved in 50 parts of deionized waters, by 2.4 parts
NaOH and 2.12 part of Na2CO3It is scattered in 100 parts of deionized waters, form mixed ammonium/alkali solutions.About 20 parts are added to go in the reactor
Ionized water, is titrated to after pH10.5 with mixed ammonium/alkali solutions, under 1000 revs/min of mixing speed, by salt-mixture and mixing alkali soluble
Liquid is simultaneously added dropwise in reactor, and adjusts rate of addition, reaction pH is maintained 10.5, and guarantees salt-mixture with mixing alkali soluble
Liquid is simultaneously added dropwise and finishes.After completion of dropping, continue to stir 1 hour under 1000 revs/min of mixing speed.Afterwards agitator is turned
Speed is reduced to 500 revs/min, reactant liquor is warmed up to 55 simultaneouslyoC, and in 55oAging 3 hours of C.Naturally standing is cooled to room temperature
Afterwards, precipitate is washed with deionized to neutrality, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace, with 2oC/ divides
The speed of clock is warmed up to 500oC, and in 500oIt is incubated 3 hours under C, after natural cooling, obtain Zn Al composite oxide photocatalyst
About 2.95 parts.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, adsorption reaction 3 hours in the dark,
Eliminating rate of absorption to methyl orange is 60.7%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, near
Under conditions of Infrared irradiation, methyl orange is not had catalytic degradation to act on, react 3 hours, do not have when methyl orange clearance and dark
Difference, is 60.3%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, under visible light illumination, reaction
2 hours, methyl orange clearance did not still have a substantial variation, and only 61.2%.Take 1 part, put into 2000 parts of concentration
In 20mg/L methyl orange solution, under UV Light is penetrated, react 2 hours, methyl orange clearance can reach 93.8%.
Comparative example 2
By 8.9 parts of Zn (NO3)2∙6H2O, 7.7 parts of Mg (NO3)2∙6H2O and 6 part of In (NO3)3It is dissolved in 100 parts of deionized waters
In, by 13.4 parts of Na2C2O4It is scattered in 200 parts of deionized waters, form sodium oxalate solution.About 20 parts are added to go in the reactor
Ionized water, under 1000 revs/min of mixing speed, salt-mixture and Disodium oxalate. is simultaneously added dropwise in reactor, and adjusts Deca
Speed is it is ensured that salt-mixture and sodium oxalate solution are simultaneously added dropwise and finish.After completion of dropping, continue the mixing speed at 1000 revs/min
Lower stirring 1 hour, and naturally stand aging 12 hours at room temperature, by unnecessary oxalate denominationby deionized water in precipitate
Wash away, and in 55oAfter C is vacuum dried and grinds, it is placed in Muffle furnace, with 2oThe speed of C/ minute is warmed up to 500oC, and in
500oIt is incubated 3 hours under C, after natural cooling, obtain about 4.67 parts of zinc-magnesium indium composite oxides.Take 1 part, put into 2000
In part concentration 20mg/L methyl orange solution, adsorption reaction 3 hours in the dark, the eliminating rate of absorption to methyl orange is 15.1%.Take
1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, under conditions of near infrared light to methyl orange almost
There is no photocatalytic Degradation, react 3 hours, methyl orange degradation rate is only 19.8%.Take 1 part, put into 2000 parts of concentration
In 20mg/L methyl orange solution, under visible light illumination, there is to methyl orange preferable photocatalytic Degradation, react 3 hours,
Methyl orange clearance can reach 70.9%.Take 1 part, put in 2000 parts of concentration 20mg/L methyl orange solutions, in ultraviolet light
Under light irradiation, react 3 hours, methyl orange clearance can reach 40.4%.
Comparative example 3
Table 1
| Zn(NO3)2∙6H2O | Mg(NO3)2∙6H2O | In(NO3)3 | Mol ratio | |
| Comparative example 3-1 | 8.93 part | 7.7 part | 3 parts | 3：3:1 |
| Comparative example 3-2 | 8.93 part | 5.13 part | 6 parts | 3:2:2 |
| Comparative example 3-3 | 8.93 part | 10.26 parts | 9 parts | 3:4:3 |
The proportioning being respectively adopted table 1 prepares mixing salt solution, and other operations, with embodiment 1, obtain contrast product zinc respectively
Copper and indium compound oxide photocatalyst about 5.04 parts of part, about 6.03 parts, about 8.22 parts.Take 1 part respectively, put into 2000 parts
In concentration 20mg/L methyl orange solution, adsorption reaction 3 hours in the dark, 43.3% is respectively to the eliminating rate of absorption of methyl orange
（Comparative example 3-1）、37.2%（Comparative example 3-2）、55.6%（Comparative example 3-3）.Take 1 part respectively, put into 2000 parts of concentration
In 40mg/L methyl orange solution, can not substantially be catalyzed the degraded of methyl orange under conditions of near infrared light, react 3 hours,
Methyl orange degradation rate is only respectively 54.1%（Comparative example 3-1）、42.5%（Comparative example 3-2）、59.4%（Comparative example 3-3）.Take respectively
1 part, put in 2000 parts of concentration 40mg/L methyl orange solutions, under visible light illumination, reacted 3 hours, methyl orange is gone
Except rate is respectively 57.3%（Comparative example 3-1）、50.8%（Comparative example 3-2）、67.7%（Comparative example 3-3）.Take 1 part respectively, thrown
Enter in 2000 parts of concentration 40mg/L methyl orange solutions, under UV Light is penetrated, react 3 hours, methyl orange clearance is respectively
For 90.3（Comparative example 3-1）、89.6%（Comparative example 3-2）、91.1%（Comparative example 3-3）.
Claims (10)
1. a kind of zinc-magnesium indium composite oxides near infrared light catalysis activity, its chemical structural formula is：Zn3Mg3In2O9.
2. according to claim 1 zinc-magnesium indium composite oxides it is characterised in that be in irregular laminated structure, particle diameter 50-
200nm.
3. a kind of preparation method of zinc-magnesium indium composite oxides described in claim 1 or 2 is it is characterised in that it includes following step
Suddenly：
（1）Prepare in proportion containing zinc ion, magnesium ion, indium ion nitrate solution；Sodium hydroxide and sodium carbonate are pressed 3:1
Mol ratio is dissolved in the water, and forms mixed ammonium/alkali solutions；
（2）Under agitation nitrate solution and mixed ammonium/alkali solutions are mixed, control reactant mixture pH between 10-11,
Form co-precipitate colloid；Stirring co-precipitate colloid disperses to it, is warming up to 55 DEG C, is stirred for 3 hours, is cooled to room temperature,
Taking precipitate；Wash precipitate with water to neutral, be then vacuum dried and grind in 55 DEG C, then be placed in Muffle furnace in 400-
Process 3 hours at 600 DEG C.
4. it is characterised in that pH is 10.5, the temperature in Muffle furnace is 500 DEG C to preparation method according to claim 3.
5. the preparation method according to claim 3 or 4 is it is characterised in that step（2）Concrete operations as follows：
Under agitation nitrate solution and mixed ammonium/alkali solutions are simultaneously added dropwise in reactor, control reactant mixture pH,
Form co-precipitate colloid；
High degree of agitation co-precipitate colloid, is completely dispersed uniformly to it, then heats to 55 DEG C, slight stirring 3 hours, naturally cold
But arrive room temperature and stand 12h, taking precipitate；
Wash precipitate with water to be vacuum dried and grind after 55 DEG C to neutrality, be subsequently placed in Muffle furnace and process 3 hours.
6. zinc-magnesium indium composite oxides described in a kind of claim 1 or 2 are under the conditions of near infrared light, ultraviolet light and radiation of visible light
Application as photocatalytic degradation catalysts.
7. application according to claim 6 is it is characterised in that under the conditions of near infrared light, as photocatalytic degradation
The application of catalysts.
8. the application according to claim 6 or 7 is it is characterised in that described photocatalytic degradation reacts for organic pollution
Photocatalytic degradation reacts.
9. application according to claim 8 is it is characterised in that the photocatalytic degradation of described organic pollution reacts for methyl
The photocatalytic degradation reaction of orange.
10. according to claim 9 application it is characterised in that
Described ultraviolet light is provided by the medium pressure mercury lamp of 300W；
Described visible ray is provided by the middle pressure xenon lamp of 300W；
Described near infrared light filters wavelength for providing after 200nm-780nm light by the infrared lamp source filter plate of 275W.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600424A (en) * | 2003-09-22 | 2005-03-30 | 中国科学院化学研究所 | Photocatalyst responding to visible light, and preparation method and application |
| CN101168127A (en) * | 2007-11-28 | 2008-04-30 | 北京化工大学 | Nanometer semiconductor oxidation photocatalyst and preparation method thereof |
| CN101391201A (en) * | 2008-10-15 | 2009-03-25 | 东华大学 | Zinc oxide nano-rod/ magnalium laminar double-hydroxide preparation method and use thereof |
| CN101638492A (en) * | 2009-08-31 | 2010-02-03 | 安徽中鼎密封件股份有限公司 | Layered double hydroxide and preparation method of montmorillonite nanometer composite material |
| CN102876287A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material |
| CN103157457A (en) * | 2011-12-08 | 2013-06-19 | 北京化工大学 | Mg/Zn/In composite metal oxide photocatalyst, preparation method and applications thereof |
| CN103433060A (en) * | 2013-08-22 | 2013-12-11 | 华南理工大学 | Core-shell TiO2/ZnIn2S4 composite photocatalyst and preparation method and application thereof |
| JP2014114339A (en) * | 2012-12-07 | 2014-06-26 | Panasonic Corp | Thermoplastic resin recycled material |
-
2015
- 2015-08-28 CN CN201510535707.7A patent/CN105056931B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1600424A (en) * | 2003-09-22 | 2005-03-30 | 中国科学院化学研究所 | Photocatalyst responding to visible light, and preparation method and application |
| CN101168127A (en) * | 2007-11-28 | 2008-04-30 | 北京化工大学 | Nanometer semiconductor oxidation photocatalyst and preparation method thereof |
| CN101391201A (en) * | 2008-10-15 | 2009-03-25 | 东华大学 | Zinc oxide nano-rod/ magnalium laminar double-hydroxide preparation method and use thereof |
| CN101638492A (en) * | 2009-08-31 | 2010-02-03 | 安徽中鼎密封件股份有限公司 | Layered double hydroxide and preparation method of montmorillonite nanometer composite material |
| CN103157457A (en) * | 2011-12-08 | 2013-06-19 | 北京化工大学 | Mg/Zn/In composite metal oxide photocatalyst, preparation method and applications thereof |
| CN102876287A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material |
| JP2014114339A (en) * | 2012-12-07 | 2014-06-26 | Panasonic Corp | Thermoplastic resin recycled material |
| CN103433060A (en) * | 2013-08-22 | 2013-12-11 | 华南理工大学 | Core-shell TiO2/ZnIn2S4 composite photocatalyst and preparation method and application thereof |
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