CN102389837A - Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof - Google Patents
Magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a photocatalyst, in particular to a magnetic polypyrrole/titanium dioxide/clay nano-composite photocatalyst and a preparation method thereof. In the method, a nano-titanium dioxide/clay composite material is prepared by taking clay as a matrix by an in-situ synthesis method; meanwhile, hydrochloric acid generated through the hydrolysis of titanium tetrachloride is used for synthesizing conductive polypyrrole, and an oxidant for synthesizing the conductive polypyrrole forms a magnetic carrier, so that a high-activity recyclable nano-composite photocatalyst is prepared.
Description
Technical field
The present invention relates to photochemical catalyst, refer in particular to a kind of magnetic polypyrrole/titanium dioxide/clay nano composite photo-catalyst and preparation method thereof.
Background technology
Aggravation along with industrial development and environmental problem; Research to treatment of Organic Wastewater more and more receives publicity; The processing method of tradition organic wastewater mainly contains physisorphtion, bioanalysis, chemical oxidization method etc.; Exist to handle insufficient, cause secondary pollution problems; The photocatalytic degradation method is a kind of novel method for processing organic wastewater, can the organic pollution degree of depth in the water be degraded into carbon dioxide, water and other inorganic matter with semi-conducting material as photochemical catalyst, and common semi-conducting material photochemical catalyst has TiO
2, SnS, ZnO, CdS, CdSe etc., wherein because nano titanium oxide (TiO
2) nontoxic, stable performance, catalytic activity is high and as first-selected photocatalyst material, still, nano titanium dioxide photocatalyst is also deposited shortcoming in water treatment applications: the recovery problem of (1) nano titanium oxide.Because the nano titanium oxide particle diameter is little, be prone to run off, after reaction finishes, from water, separates nano-titania particle and reclaim very difficult.(2) photocatalytic activity problem; Titanium dioxide receives photonexcited electron from the valence to the conduction band, to form electron-hole pair; Thereby produce great amount of hydroxy group free radical cracking organic pollutant; But owing to lack electron acceptor, the electron-hole pair easy compound causes the minimizing of hydroxyl radical free radical quantity, and photocatalytic activity reduces.
Magnetic material has the magnetic response performance, can conveniently extract recovery through the magnetic field effect.Chinese patent CN1562464A discloses a kind of with Fe
3O
4Be core, SiO
2Be separation layer, TiO
2Double-coated type magnetic nanometer photocatalyst for external coating is easy in externally-applied magnetic field effect recover.This method is a raw material with ethyl orthosilicate, absolute ethyl alcohol, butyl titanate and tri-iron tetroxide, has increased cost, has limited the product scope of application; Chinese patent CN1724164A discloses the preparation method of composite photo-catalyst capable of magnetic separating; Earlier, coat the nickel ferrite based magnetic loaded nano particle with silica through liquid phase deposition then, at last titanium dioxide nano-particle is loaded on the nickel ferrite based magnetic loaded particle of coated silica through synthesizing magnetic carrier nickel ferrite based magnetic loaded particle; Prepared composite photo-catalyst capable of magnetic separating; This method prepares the process complicacy, and product yield is low, and the employing measure does not suppress the compound of electron-hole pair; Chinese patent CN101362087A announces a kind of preparation method of noble metal modified titanium dioxide photocatalyst; Through at nano titanium oxide being noble metals such as deposition Ag, Au, Pt, Pd; Promoted the separation that light induced electron-hole is right; Improved the activity of titanium dioxide optical catalyst, but noble metals such as the Ag that this method is used, Au, Pt, Pd cost an arm and a leg, limit it and apply.
Summary of the invention
In view of the existing problem of background technology, the object of the invention is to develop a kind of recyclable high catalytic activity nano-composite catalyst material and preparation method thereof.
Thinking of the present invention is: be matrix with the clay earlier; Adopt in-situ synthesis to prepare nano titanium oxide/clay composite material; The hydrochloric acid of titanium tetrachloride hydrolysis generation simultaneously is used for the compositing conducting polypyrrole; The used oxidant of compositing conducting polypyrrole forms magnetic carrier, thus the callable nano composite photo-catalyst of preparation high activity.
The present invention provides a kind of magnetic polypyrrole/titanium dioxide/clay nano composite photo-catalyst; Titanium dioxide and clay mass ratio are 0.25 ~ 0.9:1 in the nano composite photo-catalyst; The mass ratio of polypyrrole and clay is 0.03 ~ 0.1:1; The mass ratio of tri-iron tetroxide and clay is 0.1 ~ 0.3:1, and the preparation method of this composite comprises the steps:
(1) in clay, add deionized water and be mixed with the clay slurry, the mass ratio of water and clay is 5 ~ 20:1;
(2) in the time of 10 ~ 60 ℃, it is 0.5 ~ 4molL that resulting clay slurry in the step 1 is joined molar concentration
-1Titanium tetrachloride aqueous solution in, stir, acidifying 10 ~ 240 minutes is warming up to 80 ~ 120 ℃, insulation reaction 1 ~ 10 hour obtains titanium dioxide/clay nanocomposites slurries;
(3) with after resulting titanium dioxide/clay nanocomposites slurries are cooled to 0 ~ 40 ℃ in the step 2, using alkali lye regulation system pH value is 1.5 ~ 2.5, adds pyrrole monomer, and adding molar concentration again is 1 ~ 2.5molL
-1Ferric chloride aqueous solutions, insulation reaction 2 ~ 12 hours obtains electric polypyrrole/titanium dioxide/clay nanocomposites slurries;
(4) in the said electric polypyrrole/titanium dioxide of step 3/clay nanocomposites slurries, adding molar concentration is 0.5 ~ 2molL
-1Ferrous chloride aqueous solution, mix, stir on the limit, it is 1 ~ 3 molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 30 ~ 70 ℃, the system pH after making mixed slurry add is 7.5 ~ 9, continues insulation reaction 0.5 ~ 2 hour, obtains magnetic polypyrrole/titanium dioxide/clay composite photo-catalyst slurry;
(5) filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, drying, pulverizing obtains magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
The described clay of step 1 is a kind of in attapulgite, diatomite, bentonite and the sepiolite.
The described titanium tetrachloride consumption of step 2 is by the Mass Calculation of its complete reaction generation titanium dioxide, wherein titanium dioxide and clay mass ratio (titanium dioxide: clay) be 0.24 ~ 0.91:1;
The described alkali lye of step 3 is a kind of in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, the ammoniacal liquor.
The described pyrrole monomer consumption of step 3 is in the mass ratio of pyrroles and clay, pyrroles: clay=0.03 ~ 0.1:1.
The consumption of the described ferric chloride aqueous solutions of step 3 is in the mass ratio of ferric trichloride and clay, ferric trichloride: clay=0.13 ~ 0.43:1.
The consumption of the described ferrous chloride aqueous solution of step 4 is with the molar ratio computing of frerrous chloride and ferric trichloride, frerrous chloride: the mol ratio=0.5:1 of ferric trichloride.
The invention has the beneficial effects as follows:
1, electric polypyrrole is accepted titanium dioxide and is received photon excitation to produce electronics and quicken the titanium dioxide conduction band electron to as the electron acceptor transfer velocity, promotes separating of light induced electron and hole, significantly improves the titanium dioxide catalytic efficiency.
2, utilize titanium tetrachloride hydrolysis to produce hydrochloric acid, utilize the used oxidant of compositing conducting polypyrrole (ferric trichloride) as ferric iron source synthesizing magnetic Fe with as the required adulterant of compositing conducting polypyrrole
3O
4, and load on composite material surface, and make full use of raw material, practiced thrift cost.
3, utilize high specific area of clay and excellent absorption property to come the enrichment pollutant, increase titanium dioxide and organic contact rate.Utilize the high-efficiency photocatalysis oxidization effect of nano titanium oxide that the surface of clay adsorbed contaminants is decomposed, realize the regeneration of photochemical catalyst and recycle.Utilize the magnetic Fe of load
3O
4, can in magnetic field, realize the separation and the recovery of photochemical catalyst.
4, the hydrochloric acid that utilizes titanium tetrachloride hydrolysis to produce comes acidifying and activated clay as activator, both improved the specific area and the adsorption capacity of clay, saved again the clay activation required add sour step, practiced thrift sour consumption, simplified production technology.
The specific embodiment
Embodiment 1: in 20 gram attapulgites, add 200 gram deionized waters, with the ultrasonic dispersion of the intelligent ultrasonic cell disruptor of JYD650 0.5 hour, the mass ratio that is mixed with water and attapulgite was the slurry of 10:1.
Under 30 ℃, it is 2molL that the attapulgite slurry for preparing is joined 60 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 30 minutes, the heating make system be warming up to 90 ℃, insulation reaction 3 hours obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 10 ℃, and using molar concentration is 2 molL
-1Ammonia spirit regulation system pH value be 1.5, add 1.2 gram pyrroles, after mixing, stir on the limit, the limit drips 20 milliliters of molar concentrations in mixed system be 2molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries 10 ℃ of following insulation reaction 4 hours.
Adding 20 milliliters of molar concentrations in conductive polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries is 1molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 2molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 50 ℃, the system pH after mixed slurry adds is 8, continues insulation reaction 1 hour, obtains magnetic polypyrrole/titanium dioxide/attapulgite composite photocatalyst slurry.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 80 ℃ of following forced air dryings 3 hours, pulverizing obtained magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.06:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2315:1.
Embodiment 2: except that attapulgite is changed into the diatomite, other technological parameters are all identical with embodiment 1 with method of operating in embodiment 2, obtain magnetic polypyrrole/titanium dioxide/diatomite nano composite photo-catalyst powder.Titanium dioxide is 0.4793:1 with diatomite quality ratio in the nano composite photo-catalyst, and polypyrrole and diatomaceous mass ratio are 0.06:1, and tri-iron tetroxide and diatomaceous mass ratio are 0.2315:1.
Embodiment 3: except that attapulgite is changed into the bentonite, other technological parameters are all identical with embodiment 1 with method of operating in embodiment 3, obtain magnetic polypyrrole/titanium dioxide/bentonite nano composite photo-catalyst powder.Titanium dioxide and bentonite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and polypyrrole and diatomaceous mass ratio are 0.06:1, and tri-iron tetroxide and diatomaceous mass ratio are 0.2315:1.
Embodiment 4: except that attapulgite is changed into the sepiolite, other technological parameters are all identical with embodiment 1 with method of operating in embodiment 4, obtain magnetic polypyrrole/titanium dioxide/sepiolite nano composite photo-catalyst powder.
Titanium dioxide and sepiolite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and polypyrrole and diatomaceous mass ratio are 0.06:1, and tri-iron tetroxide and diatomaceous mass ratio are 0.2315:1.
Embodiment 5: in 200 gram attapulgites, add 1000 gram deionized waters, (east, Shanghai magnificent high pressure homogenizer factory) disperseed 1 hour with the minitype high voltage homogenizer, and the mass ratio that is mixed with water and attapulgite is the slurry of 5:1.
In the time of 10 ℃, it is 0.5molL that the attapulgite slurry for preparing is joined 1250 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 240 minutes, the heating make system be warming up to 80 ℃, insulation reaction 10 hours obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 0 ℃, use molar concentration to be 4molL
-1Sodium hydrate aqueous solution regulation system pH value be 2.0, add 6 gram pyrroles, after mixing, stir on the limit, the limit drips 68.8 milliliters of molar concentrations in mixed system be 2.5molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries 0 ℃ of following insulation reaction 12 hours.
Adding 43 milliliters of molar concentrations in conductive polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries is 2molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 3molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 30 ℃, the system pH after mixed slurry adds is 9, continues insulation reaction 2 hours, obtains magnetic polypyrrole/titanium dioxide/attapulgite composite photocatalyst slurry.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 60 ℃ of following forced air dryings 12 hours, pulverizing obtained magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.2496:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.03:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.0996:1.
Embodiment 6: in 100 gram attapulgites, add 2000 gram deionized waters, disperseed 3 hours with ME100 type high shearing mixing emulsor high speed (7000 rev/mins), the mass ratio that is mixed with water and attapulgite is the slurry of 20:1.
In the time of 60 ℃, it is 4molL that the attapulgite slurry for preparing is joined 282 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 10 minutes, the heating make system be warming up to 120 ℃, insulation reaction 1 hour obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 40 ℃, use molar concentration to be 1molL
-1Potassium hydroxide aqueous solution regulation system pH value be 2.5, add 10 gram pyrroles, after mixing, stir on the limit, the limit drips 259 milliliters of molar concentrations in mixed system be 1molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries 40 ℃ of following insulation reaction 2 hours.
Adding 259 milliliters of molar concentrations in conductive polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries is 0.5molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 1molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 70 ℃, the system pH after mixed slurry adds is 7.5, continues insulation reaction 0.5 hour, obtains magnetic polypyrrole/titanium dioxide/attapulgite composite photocatalyst slurry.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 100 ℃ of following forced air dryings 2 hours, pulverizing obtained magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.901:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.1:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2998:1.
Comparative example 1: in comparative example 1, except that the operation that adds attapulgite among the embodiment 1 was deleted, other operations were all identical with embodiment 1, and the concrete operations step is following:
Under 30 ℃, it is 2molL that 200 gram deionized waters are joined 60 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stirred 30 minutes, the heating make system be warming up to 90 ℃, insulation reaction 3 hours obtains nano titanium oxide dispersion.
Nano titanium oxide dispersion is cooled to 10 ℃, and using molar concentration is 2 molL
-1Ammonia spirit regulation system pH value be 1.5, add 1.2 gram pyrroles, after mixing, stir on the limit, the limit drips 20 milliliters of molar concentrations in mixed system be 2molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanic oxide nano compound material slurries 10 ℃ of following insulation reaction 4 hours.
Adding 20 milliliters of molar concentrations in conductive polypyrrole/titanic oxide nano compound material slurries is 1molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 2molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 50 ℃, the system pH after mixed slurry adds is 8, continues insulation reaction 1 hour, obtains magnetic polypyrrole/titanium dioxide composite photocatalyst slurry.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 80 ℃ of following forced air dryings 3 hours, pulverizing obtained magnetic polypyrrole/titanic oxide nano compound photocatalyst powder.
Comparative example 2: in comparative example 2, except that with step 3 operation is left out among the embodiment 1, other operations are all identical with embodiment 1, and the concrete operations step is following:
In 20 gram attapulgites, add 200 gram deionized waters, with the ultrasonic dispersion of the intelligent ultrasonic cell disruptor of JYD650 0.5 hour, the mass ratio that is mixed with water and attapulgite was the slurry of 10:1.
Under 30 ℃, it is 2molL that the attapulgite slurry for preparing is joined 60 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 30 minutes, the heating make system be warming up to 90 ℃, insulation reaction 3 hours obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 10 ℃, and using molar concentration is 2 molL
-1Ammonia spirit regulation system pH value be 1.5, in mixed system, dripping 20 milliliters of molar concentrations is 2molL
-1Ferric chloride aqueous solutions and 20 milliliters of molar concentrations be 1molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 2molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 50 ℃, the system pH after mixed slurry adds is 8, continues insulation reaction 1 hour, obtains magnetic titanium dioxide/attapulgite composite photocatalyst slurry.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 80 ℃ of following forced air dryings 3 hours, pulverizing obtained magnetic titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2315:1.
Comparative example 3: in comparative example 3, except that with step 4 operation is left out among the embodiment 1, other operations are all identical with embodiment 1, and the concrete operations step is following:
In 20 gram attapulgites, add 200 gram deionized waters, with the ultrasonic dispersion of the intelligent ultrasonic cell disruptor of JYD650 0.5 hour, the mass ratio that is mixed with water and attapulgite was the slurry of 10:1.
Under 30 ℃, it is 2molL that the attapulgite slurry for preparing is joined 60 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 30 minutes, the heating make system be warming up to 90 ℃, insulation reaction 3 hours obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 10 ℃, and using molar concentration is 2 molL
-1Ammonia spirit regulation system pH value be 1.5, add 1.2 gram pyrroles, after mixing, stir on the limit, the limit drips 20 milliliters of molar concentrations in mixed system be 2molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries 10 ℃ of following insulation reaction 4 hours.
Filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, 80 ℃ of following forced air dryings 3 hours, pulverizing obtained polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.06:1.
Comparative example 4: in comparative example 3, except that reaction temperature in the step 2 among the embodiment 1 is made as 70 ℃, other operations are all identical with embodiment 1, and the concrete operations step is following:
In 20 gram attapulgites, add 200 gram deionized waters, with the ultrasonic dispersion of the intelligent ultrasonic cell disruptor of JYD650 0.5 hour, the mass ratio that is mixed with water and attapulgite was the slurry of 10:1.
Under 30 ℃, it is 2molL that the attapulgite slurry for preparing is joined 60 milliliters of molar concentrations
-1Titanium tetrachloride aqueous solution in, stir, acidifying 30 minutes, the heating make system be warming up to 70 ℃, insulation reaction 3 hours obtains titanium dioxide/attapulgite clay nano composite material slurries.
Titanium dioxide/attapulgite clay nano composite material slurries are cooled to 10 ℃, and using molar concentration is 2 molL
-1Ammonia spirit regulation system pH value be 1.5, add 1.2 gram pyrroles, after mixing, stir on the limit, the limit drips 20 milliliters of molar concentrations in mixed system be 2molL
-1Ferric chloride aqueous solutions, and, obtain electric polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries 10 ℃ of following insulation reaction 4 hours.
Adding 20 milliliters of molar concentrations in conductive polypyrrole/titanium dioxide/attapulgite clay nano composite material slurries is 1molL
-1Ferrous chloride aqueous solution, mix, obtain containing the mixed slurry of ferric trichloride and frerrous chloride, stir on the limit, it is 2molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 50 ℃, the system pH after mixed slurry adds is 8, continues insulation reaction 1 hour, obtains magnetic polypyrrole/titanium dioxide/attapulgite composite photocatalyst slurry.
Filter, washing 80 ℃ of following forced air dryings 3 hours, is pulverized, and obtains magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.06:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2315:1.
Comparative example 5: in comparative example 3, except that reaction temperature in the step 2 among the embodiment 1 is made as 50 ℃, other operations are all identical with embodiment 1, obtain magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.06:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2315:1.
Comparative example 6: in comparative example 3, except that reaction temperature in the step 2 among the embodiment 1 is made as 30 ℃, other operations are all identical with embodiment 1, obtain magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
Titanium dioxide and attapulgite mass ratio are 0.4793:1 in the nano composite photo-catalyst, and the mass ratio of polypyrrole and attapulgite is 0.06:1, and the mass ratio of tri-iron tetroxide and attapulgite is 0.2315:1
Photocatalysis performance is estimated:
In XPA photochemical reaction appearance (the dynamo-electric factory of Nanjing Xu Jiang), add 0.5 and restrain the nano composite photocatalytic material that is equipped with, adding 500 milliliters of mass concentrations again is 0.1gL
-1 the reactive red M-2B aqueous solution open to stir and feeds from the bottom air of 0.02 liter/minute of flow, opens uviol lamp (15 watts of power, wavelength 254nm), whenever centrifugalizes at a distance from 15 milliliters of sampling in 10 minutes, gets supernatant liquor and tests.Under its maximum absorption wavelength, measure solution absorbency through spectrophotometer, degradation rate is calculated as follows:
ηFor degradation rate (
%);
A 0,
A tBe respectively the degraded before,
tSolution absorbance after time;
C 0,
C tBe respectively the degraded before,
tSolution concentration after time.
The calculating that the magnetic of photochemical catalyst reclaims:
In 3000 ml beakers, add 2000 gram deionized waters and 2 gram nano composite photocatalytic materials respectively; Disperseed 3 hours with ME100 type high shearing mixing emulsor high speed (7000 rev/mins), beaker is placed on the magnet base, magnetic photocatalyst can be drawn to beaker bottom by magnet; The upper strata liquid of clarification is taken out; Catalyst in the beaker is 200 ℃ of oven dry down, and the quality that weighing obtains photochemical catalyst is the X gram, and the computing formula of the magnetic rate of recovery (w) of photochemical catalyst is:
The photocatalysis of embodiment and comparative example products obtained therefrom and the magnetic rate of recovery are as shown in table 1 below, and be visible by table 1, and the nano composite photocatalytic material of the present invention's preparation not only photocatalytic activity is high, and has the higher magnetic rate of recovery.
The photocatalytic activity of table 1 embodiment and comparative example products obtained therefrom and the magnetic rate of recovery
Claims (10)
1. magnetic polypyrrole/titanium dioxide/clay nano composite photo-catalyst, adopt following method preparation:
(1) in clay, add deionized water and be mixed with the clay slurry, the mass ratio of water and clay is 5 ~ 20:1;
(2) in the time of 10 ~ 60 ℃, it is 0.5 ~ 4molL that resulting clay slurry in the step 1 is joined molar concentration
-1Titanium tetrachloride aqueous solution in, stir, acidifying 10 ~ 240 minutes is warming up to 80 ~ 120 ℃, insulation reaction 1 ~ 10 hour obtains titanium dioxide/clay nanocomposites slurries;
(3) with after resulting titanium dioxide/clay nanocomposites slurries are cooled to 0 ~ 40 ℃ in the step 2, using alkali lye regulation system pH value is 1.5 ~ 2.5, adds pyrrole monomer, and adding molar concentration again is 1 ~ 2.5molL
-1Ferric chloride aqueous solutions, insulation reaction 2 ~ 12 hours obtains electric polypyrrole/titanium dioxide/clay nanocomposites slurries;
(4) in the said electric polypyrrole/titanium dioxide of step 3/clay nanocomposites slurries, adding molar concentration is 0.5 ~ 2molL
-1Ferrous chloride aqueous solution, mix, stir on the limit, it is 1 ~ 3 molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 30 ~ 70 ℃, the system pH after making mixed slurry add is 7.5 ~ 9, continues insulation reaction 0.5 ~ 2 hour, obtains magnetic polypyrrole/titanium dioxide/clay composite photo-catalyst slurry;
(5) filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, drying, pulverizing obtains magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
2. magnetic polypyrrole/titanium dioxide as claimed in claim 1/clay nano composite photo-catalyst is characterized in that: the described clay of step (1) is a kind of in attapulgite, diatomite, bentonite and the sepiolite.
3. magnetic polypyrrole/titanium dioxide as claimed in claim 1/clay nano composite photo-catalyst; It is characterized in that: the described titanium tetrachloride consumption of step (2) is by the Mass Calculation of its complete reaction generation titanium dioxide, wherein titanium dioxide and clay mass ratio (titanium dioxide: clay) be 0.24 ~ 0.91:1.
4. magnetic polypyrrole/titanium dioxide as claimed in claim 1/clay nano composite photo-catalyst; It is characterized in that: the described alkali lye of step (3) is a kind of in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, the ammoniacal liquor; Described pyrrole monomer consumption is in the mass ratio of pyrroles and clay; The pyrroles: clay=0.03 ~ 0.1:1, the consumption of described ferric chloride aqueous solutions be in the mass ratio of ferric trichloride and clay, ferric trichloride: clay=0.13 ~ 0.43:1.
5. magnetic polypyrrole/titanium dioxide as claimed in claim 1/clay nano composite photo-catalyst; It is characterized in that: the consumption of the described ferrous chloride aqueous solution of step (4) is with the molar ratio computing of frerrous chloride and ferric trichloride, frerrous chloride: the mol ratio=0.5:1 of ferric trichloride.
6. the preparation method of magnetic polypyrrole/titanium dioxide as claimed in claim 1/clay nano composite photo-catalyst may further comprise the steps:
(1) in clay, add deionized water and be mixed with the clay slurry, the mass ratio of water and clay is 5 ~ 20:1;
(2) in the time of 10 ~ 60 ℃, it is 0.5 ~ 4molL that resulting clay slurry in the step 1 is joined molar concentration
-1Titanium tetrachloride aqueous solution in, stir, acidifying 10 ~ 240 minutes is warming up to 80 ~ 120 ℃, insulation reaction 1 ~ 10 hour obtains titanium dioxide/clay nanocomposites slurries;
(3) with after resulting titanium dioxide/clay nanocomposites slurries are cooled to 0 ~ 40 ℃ in the step 2, using alkali lye regulation system pH value is 1.5 ~ 2.5, adds pyrrole monomer, and adding molar concentration again is 1 ~ 2.5molL
-1Ferric chloride aqueous solutions, insulation reaction 2 ~ 12 hours obtains electric polypyrrole/titanium dioxide/clay nanocomposites slurries;
(4) in the said electric polypyrrole/titanium dioxide of step 3/clay nanocomposites slurries, adding molar concentration is 0.5 ~ 2molL
-1Ferrous chloride aqueous solution, mix, stir on the limit, it is 1 ~ 3 molL that the mixed slurry that ferric trichloride and frerrous chloride will be contained in the limit joins molar concentration
-1Ammonia spirit in, the control reaction temperature is 30 ~ 70 ℃, the system pH after making mixed slurry add is 7.5 ~ 9, continues insulation reaction 0.5 ~ 2 hour, obtains magnetic polypyrrole/titanium dioxide/clay composite photo-catalyst slurry;
(5) filter, and be washed till filtrating pH value with the washing deionized water and be neutrality, drying, pulverizing obtains magnetic polypyrrole/titanium dioxide/attapulgite clay nano composite photo-catalyst powder.
7. the preparation method of magnetic polypyrrole/titanium dioxide as claimed in claim 6/clay nano composite photo-catalyst is characterized in that: the described clay of step (1) is a kind of in attapulgite, diatomite, bentonite and the sepiolite.
8. the preparation method of magnetic polypyrrole/titanium dioxide as claimed in claim 6/clay nano composite photo-catalyst; It is characterized in that: the described titanium tetrachloride consumption of step (2) is by the Mass Calculation of its complete reaction generation titanium dioxide, wherein titanium dioxide and clay mass ratio (titanium dioxide: clay) be 0.24 ~ 0.91:1.
9. the preparation method of magnetic polypyrrole/titanium dioxide as claimed in claim 6/clay nano composite photo-catalyst; It is characterized in that: the described alkali lye of step (3) is a kind of in sodium hydrate aqueous solution, potassium hydroxide aqueous solution, the ammoniacal liquor; Described pyrrole monomer consumption is in the mass ratio of pyrroles and clay; The pyrroles: clay=0.03 ~ 0.1:1, the consumption of described ferric chloride aqueous solutions be in the mass ratio of ferric trichloride and clay, ferric trichloride: clay=0.13 ~ 0.43:1.
10. its preparation method of magnetic polypyrrole/titanium dioxide as claimed in claim 6/clay nano composite photo-catalyst; It is characterized in that: the consumption of the described ferrous chloride aqueous solution of step (4) is with the molar ratio computing of frerrous chloride and ferric trichloride, frerrous chloride: the mol ratio=0.5:1 of ferric trichloride.
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