CN104525232B - Preparation method of anatase nano-titanium dioxide powder modified via codoping of iron element with other two non-metallic elements - Google Patents
Preparation method of anatase nano-titanium dioxide powder modified via codoping of iron element with other two non-metallic elements Download PDFInfo
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Abstract
The invention belongs to the technical field of photocatalysis material, and specifically relates to a preparation method of anatase nano-titanium dioxide powder modified via codoping of iron element with other two non-metallic elements. According to the preparation method, alkylphenol ethoxylates, and a monohydric alcohol with 4 to 7 carbon atoms are taken as surfactants; an alkane or a cycloparaffin with 5 to 8 carbon atoms are taken as an oil phase; inorganic or organic titanium source is taken as a raw material; a dilute acid solution containing iron element and the other two non-metallic elements are taken as water phase; and the anatase nano-titanium dioxide powder is prepared via solvothermal method; wherein one of the two non-metallic elements is selected from nitrogen, phosphorus, or arsenic, and the other one of the non-metallic elements is selected from oxygen, sulphur, selenium, or tellurium. Conditions of the preparation method are mild; influences on product morphology and stability caused by high temperature processing are avoided; size of the modified anatase nano-titanium dioxide powder is controllable, and uniform; diameter ranges from 8 to 20nm; the anatase nano-titanium dioxide powder can be used for degrading methyl orange in the presence of visible light, and degradation rate of methyl orange is as high as 96% after 1.5h of reaction.
Description
Technical field
The present invention relates to catalysis material technical field, more particularly, to a kind of ferrum element and two kinds of nonmetalloids
The preparation method of codoping modified octahedrite nano titanium dioxide powder.
Background technology
tio2It is always material science and the focus of catalytic chemistry research, nano level tio as catalysis material2Due to
Its particle diameter is little, surface activity is high and there is the small-size effect of uniqueness, skin effect and quantum effect, photoproduction can be efficiently reduced
Electronics and compound, the enhancing tio of photon2Redox ability；Nanometer tio simultaneously2Reactant can be inhaled by huge surface energy
It is attached to its surface, be conducive to the carrying out of catalytic reaction, meanwhile, tio2Nontoxic, there is good chemical stability, to many antibacterials
There is bactericidal action, be environment-friendly type catalyst, therefore nanometer tio2In photocatalytic degradation, electronic ceramics and high-grade paint, sun-proof
The various fields such as cosmetics have performance and the application of uniqueness.
tio2Mainly there are three kinds of crystalline phases: Anatase, Rutile Type and brookite.Wherein, brookite is unstable, sharp
The band gap of titanium ore phase is about 3.2 ev, and when being less than the light irradiation of 387 nm with incident illumination, electronics can be from valence
To conduction band, thus having photocatalysis performance, Rutile Type then because surface electronic-hole-recombination speed, does not almost have light
Catalysis activity.
tio2There are some defects in actual applications, such as: greater band gap (eg=3.2 ev), light absorbs are limited only to purple
Outer smooth region, and ultraviolet light only accounts for 3～5% in natural light, therefore relatively low to the utilization rate of natural light；This outer semiconductor current-carrying
The recombination rate of son is high, leads to photo-quantum efficiency very low, for overcoming these shortcomings, people take multiple means to tio2Changed
Property, what research was more is to use some metal ions, such as noble metal, transition metal, rare earth doped tio2, obtain many
Progress, but the tio through transition metallic ion-doping modification2, often exist multiple to thermally labile, easily generation electronics and hole
Conjunction center, moreover, most transition metal is all somewhat expensive with rare earth to be applied it is difficult to realize scale, thus explores new
Doping vario-property means be very important.At present, engender with nonmetallic ion-doped modified Nano tio2To improve it
The report of visible light photocatalysis active, the such as doping vario-property such as n, c, f, compared with doping metals, metal-oxide or metal ion,
Nonmetal doping modification tio2, not only can be by tio2Response wave length expand to visible region, and will not be reduced it to purple
The responding ability of outer light.
In terms of the preparation of modified nano-titanium dioxide powder body, current preparation method mainly has sol-gel process, hydro-thermal
Method, liquid-phase precipitation method, microemulsion method etc..The Chinese patent of Patent No. 200710011135.8 discloses a kind of hot using electric field
The method of highlight catalytic active nano titania powder is prepared in process although current sol-gel process is a kind of with more
Nano material preparation method, but the titanium dioxide that directly obtains of its technique mostly is unformed phase.And for example, Patent No.
200510133947.0 Chinese patent discloses a kind of response mechanism using for reference sol-gel process template and obtains titanium dioxide
The method of nano wire, the method needs high reaction temperature, and reaction time consumption.
Hydro-thermal method is that using compound, the dissolubility in high-temperature high-pressure water solution increases, ionic activity strengthens, compound
The properties such as crystal structure transition, in special closed reaction vessel, make reaction medium with aqueous solution, by heating to container,
Create the reaction environment of a kind of high temperature, high pressure, make indissoluble or the dissolving of insoluble material recrystallization, thus corresponding nanometer is obtained
tio2Powder body.The Chinese patent of Patent No. 200810070678.1 discloses a kind of high pure brookite type titanium dioxide and receives
The preparation method of mitron, the brookite type titanium dioxide nano-tube length of preparation is about several nanometers to more than ten micron, internal diameter
5-6 nanometer, purity is high.The Chinese patent of Patent No. 200710161058.4 is directed to the deficiency of hydrothermal synthesis method, discloses one
Kind by by titania nanoparticles, alkali metal hydroxide and ORGANIC SOLVENT MIXTURES heating after with surfactant fluid
The method preparing titanium dioxide nano-rod, prepared titanium dioxide nano-rod length is homogeneous, and reaction can be carried out at ambient pressure.
Micro-emulsion method for preparing nano tio2It is one of method more popular in recent years, refer to that Thermodynamically stable is scattered mutually not
Macroscopically homogeneous and uneven on the microcosmic liquid mixture of the liquid composition mixing.Using the principle of hydro-thermal method, in microemulsion
The research preparing ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders in the system of liquid there is presently no report.
Content of the invention
The technical problem to be solved is to overcome modified nano-titanium dioxide powder preparation method in prior art
In have that reaction temperature height, length reaction time, products therefrom pattern heterogeneity, stability is good, the low defect of photocatalytic, carry
For the preparation method of a kind of ferrum element and the codoping modified octahedrite nano titanium dioxide powder of two kinds of nonmetalloids, the party
Method selects cheap reagent as raw material, reacts under low temperature microemulsion thermal and hydric environment, and a kind of ferrum element and two kind non-gold are obtained
Belong to element ternary co-doping nano-titanium dioxide powders, solve high-temperature process to the pattern of product and asking of stability influence
Topic, has the advantages that preparation process is simple, with low cost, quick, energy-conservation, efficiency high.
Second object of the present invention is a kind of ferrum element and two kinds of nonmetalloids that offer said method prepares
Ternary co-doping nano-titanium dioxide powders, described ternary co-doping nano-titanium dioxide powders size is controlled, uniform in size, puts down
All diameters are in 8～20nm.
Third object of the present invention is to provide above-mentioned ternary co-doping nano-titanium dioxide powders as photocatalyst
Application, specifically, described ternary co-doping nano-titanium dioxide powders can be in fields such as photolysis water hydrogen, degradable organic pollutants
Acquisition is widely applied.
The purpose of the present invention is achieved by the following technical programs:
A kind of ferrum element and the preparation side of the codoping modified octahedrite nano titanium dioxide powder of two kinds of nonmetalloids
Method, with alkylphenol polyoxyethylene as nonionic surfactant, carbon number be 4～7 monohydric alcohol be help surface activity
Agent, carbon number be 5～8 alkane or cycloalkane be oil phase, inorganic or organic titanium source is raw material, containing ferrum element and two kinds of non-gold
The dilute acid soln belonging to element is aqueous phase, prepares a kind of ferrum element according to solvent-thermal method and changes with two kinds of nonmetalloid codopes
Property octahedrite nano titanium dioxide powder；One of described two nonmetalloids are selected from nitrogen, phosphorus or arsenic, and another kind is selected from
Sulfur, selenium or tellurium.
Have in prior art much with regard to nano-titanium dioxide modified research, wherein, nonmetalloid has been mixed
Miscellaneous, transition metal element doped or thulium doping all has been reported that, for a kind of transition metal and a kind of non-gold
The research belonging to element doping titanium dioxide also has been reported that, but its preparation method is complicated, and condition is harsh, and reaction temperature is high, Er Qiesuo
The product property obtaining is unstable.
Applicant on the basis of existing technology, mainly considers from preparation method, by substantial amounts of experimental analysiss, obtains
Reaction condition is gentle, product catalyst efficiency high and a kind of transition metal of stable performance and two kinds of nonmetalloids are co-doped with
Miscellaneous modified nano-titanium dioxide powder body, because the surface modification method of containing transition metal ion and nonmetallic ion can carry
High tio2Photocatalysis performance.Using the principle of hydro-thermal method, the system of microemulsion is prepared a kind of transition metal and two
The research planting the modified nano-titanium dioxide powder body of nonmetalloid codope there is presently no report.
Applicant finds in early-stage Study, as long as the nonmetalloid from suitable dose of dopants is it is possible to use the present invention
Above-mentioned preparation method is obtaining the modified nano-titanium dioxide powder body of a kind of ferrum element and two kinds of nonmetalloid codopes, described
Nonmetalloid is respectively selected from, main group nonmetalloid, and specifically, one of described two nonmetalloids are selected from
Nitrogen, phosphorus or arsenic, another kind is selected from sulfur, selenium or tellurium.
Preferably, the present invention provides a kind of specific ferrum element and nitrogen, the nano titanium oxide of element sulphur codope
Powder body, when with ferrum nitrogen and sulphur element codope, titanium elements in ferrum element in dilute acid soln, nitrogen, element sulphur and titanium source
Mol ratio be 0.005～0.2:0.005～0.25:0.005～0.25:1.
Preferably, in above-mentioned preparation method, carbon number is 4～7 monohydric alcohol can be butanol, amylalcohol, hexanol, heptan
Alcohol, carbon number be 5～8 alkane or cycloalkane can be pentane, Pentamethylene., hexane, hexamethylene, heptane, cycloheptane, pungent
Alkane, cyclooctane.
Preferably, in above-mentioned preparation method, described ferrum element is selected from the inorganic salt of iron content；Described nitrogen is selected from nitrogenous
Inorganic or Organic substance；Described element sulphur is selected from the inorganic or Organic substance of sulfur-bearing.It is highly preferred that described ferrum element is selected from fecl3·
6h2O or fe (no3)3·9h2o；Described nitrogen is selected from nh4Cl or carbamide；Described element sulphur is selected from thiourea or cysteine.
Preferably, in above-mentioned preparation method, described titanium source is selected from butyl titanate or titanium tetrachloride.
Preferably, in above-mentioned preparation method, described dilute acid soln is dilute hydrochloric acid or dust technology, the concentration of described dilute acid soln
For 0.1 mol/l.
Preferably, in above-mentioned preparation method, the concretely comprising the following steps of described solvent-thermal method:
S1. by the alkylphenol polyoxyethylene of half consumption, carbon number be 4～7 monohydric alcohol, carbon number be 5～
8 alkane or cycloalkane mix homogeneously obtain mixed liquor a；
S2. monohydric alcohol, the carbon number being 4～7 by the alkylphenol polyoxyethylene of remaining half consumption, carbon number
Alkane for 5～8 or cycloalkane are mixed homogeneously with the dilute acid soln of iron content and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium and are obtained mixed liquor b；
S3. mixed liquor b is instilled in mixed liquor a and obtain mixed liquor c；
S4. mixed liquor c 120～180 DEG C of reaction 1～12 h in hydro-thermal reaction container, cool down, wash, are drying to obtain
Ferrum and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope octahedrite nano titanium dioxide powder；
When titanium source is for organic titanium source, organic titanium source is mixed homogeneously with the raw material described in s1 and obtains mixed liquor a；When titanium source is
During inorganic ti sources, inorganic ti sources are mixed homogeneously with the raw material described in s2 and obtains mixed liquor b.
Preferably, hydro-thermal reaction container described in s4 is the hydrothermal reaction kettle of inner liner polytetrafluoroethylene, inner liner polytetrafluoroethylene
Hydrothermal reaction kettle one airtight and stable reaction environment can be provided, contribute to microemulsion in certain pressure and temperature bar
Under part, reaction obtains ferrum and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope octahedrite nano titanium dioxide powder.
Preferably, operation described in s4 is specially and the hydrothermal reaction kettle of inner liner polytetrafluoroethylene is placed in drying baker, keeps
120～180 DEG C of constant temperature, reacts 1～12 h, then naturally cools to room temperature；With each three times of distilled water, washes of absolute alcohol, often
Secondary 30～60 min, are centrifuged at a high speed, and then at 60～80 DEG C, are vacuum dried 12～24 h, prepared ferrum and nitrogen, phosphorus or arsenic
With sulfur, selenium or tellurium ternary codope octahedrite nano titanium dioxide powder；Described constant temperature keeps stable, temperature fluctuation range
For ± 1 DEG C.
Preferably, in above-mentioned preparation method, described in s1 or/and s2, alkylphenol polyoxyethylene, carbon number are 4～7
Monohydric alcohol, carbon number are 5～8 alkane or the volume ratio of cycloalkane is 1:1.5～6:2～10.
Preferably, in above-mentioned preparation method, carbon number described in s2 is 5～8 alkane or cycloalkane and iron content and nitrogen, phosphorus
Or the volume ratio of the dilute acid soln of arsenic and sulfur, selenium or tellurium is 2～20:1, that is, in Water-In-Oil w/o microemulsion, profit volume ratio is 2
～20:1.
Microemulsion be by surfactant (alkylphenol polyoxyethylene), cosurfactant (monohydric alcohol of carbon 4～7),
Thermodynamically stable that oily (alkane of carbon 5～8 or cycloalkane), water (or saline) are mixed to form with certain proportion, clarification or semi-transparent
Bright solution, prepares material using microemulsion and typically carries out in water-in-oil type w/o microemulsion, closes in Water-In-Oil w/o microemulsion
Suitable profit volume ratio just can make that the material granule of preparation is smaller, and uniformly, specific surface area is larger, and material property is preferable.
The ferrum being prepared by any one method above-mentioned and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope anatase
Type nano-titanium dioxide powder, described ternary codope octahedrite nano titanium dioxide powder is a diameter of 8～20 nm.
Above-mentioned ferrum and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope octahedrite nano titanium dioxide powder are as light
The application of catalyst.
Correlational study shows, ternary coblended nano TiO 2 there may be cooperative effect it is also possible to not exist collaborative
Effect, principle is more complicated, reason be probably by different elements between interaction cause, applicant is to the method for the invention
The ternary coblended nano TiO 2 obtaining is tested it was confirmed ferrum element and these three units of other two kinds of nonmetalloids
Plain codope has cooperative effect, and its photocatalysis effect is than any one element in two kinds of nonmetalloids of ferrum element and other
The effect of codope is well a lot.
Ferrum and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope anatase type nano titanium dioxide using present invention preparation
Titanium valve body is applied to catalytic degradation organic pollution under visible light, and for example at normal temperatures, photo-catalytic degradation of methyl-orange, during reaction
Between be 1.5 h, result shows that the ferrum of present invention preparation and nitrogen, phosphorus or arsenic and oxygen, sulfur, selenium or tellurium ternary codope Detitanium-ore-type are received
Rice titanium dioxide powder has very high catalysis activity.
Compared with prior art, the method have the advantages that
The invention provides a kind of ferrum element and the codoping modified anatase-type nanometer titanium dioxide of two kinds of nonmetalloids
Raw powder's production technology, it reacts under low temperature microemulsion thermal and hydric environment, and preparation condition is gentleer, and equipment is simple, from low
, as raw material, the complicated technology synthesizing without the conventional sol-gal process adopting, thus avoid high-temperature process for honest and clean reagent
Pattern to product and stability influence；The modified anatase-type nanometer titanium dioxide powder being obtained by preparation method of the present invention
Body size is controlled, uniform in size, particularly without high temperature crystallization, directly obtains anatase titanium dioxide；Specifically, by this
Ferrum and nitrogen, phosphorus or arsenic and sulfur, selenium or tellurium ternary codope anatase-type nanometer titanium dioxide powder that bright described preparation method obtains
The titanium dioxide that any one element codope in body and single element doping or two kinds of nonmetalloids of ferrum element and other is obtained
Titanium valve body phase ratio, its photocatalytic activity greatly improves, and declines solution methyl orange, response time 1.5h, methyl orange in visible light action
Degradation rate be up to 96%.
Brief description
Fig. 1 is prepared ferrum nitrogen and sulphur codope octahedrite nano titanium dioxide powder x- ray powder diffraction
(xrd) figure, the preparation condition such as embodiment 1 of in figure product.
Fig. 2 is prepared ferrum nitrogen and sulphur codope octahedrite nano titanium dioxide powder transmission electron microscope
(tem) figure, the preparation condition such as embodiment 2 of in figure product.
Fig. 3 is the photoelectron spectroscopy of prepared ferrum nitrogen and sulphur codope octahedrite nano titanium dioxide powder fe 2p
(xps) collection of illustrative plates, the preparation condition such as embodiment 2 of in figure product.
Fig. 4 is the photoelectron spectroscopy of prepared ferrum nitrogen and sulphur codope octahedrite nano titanium dioxide powder n 1s
(xps) collection of illustrative plates, the preparation condition such as embodiment 2 of in figure product.
Fig. 5 is the photoelectron spectroscopy of prepared ferrum nitrogen and sulphur codope octahedrite nano titanium dioxide powder s 2p
(xps) collection of illustrative plates, the preparation condition such as embodiment 2 of in figure product.
Fig. 6 is prepared each doped nano titanium dioxide powder body (a～e) and pure nano-titanium dioxide powder p25(f) carry out
The effectiveness comparison figure of (>=420 nm) photo-catalytic degradation of methyl-orange (mo, 20 mg/l) under visible light action；In figure a～e product
Preparation condition such as embodiment 2, simply each doped chemical is different, specially a: only plus source of iron and nitrogen source；B: only add source of iron and sulfur
Source；C: only add nitrogen source and sulphur source；D: plus source of iron nitrogen source and sulphur source；E: only add nitrogen source.
Specific embodiment
Below by Figure of description and specific embodiment, the present invention is specifically described further.The design of the present invention is thought
Think or the simple replacement of allied substances belongs to protection scope of the present invention.If following used experimental technique no specified otherwise,
It is the art existing conventional method, the dispensing being used or material, if no special instructions, be by commercial sources
Available dispensing or material, it is pure that all reagent are analysis.
Embodiment 1
A kind of preparation method of the codoping modified octahedrite nano titanium dioxide powder of three kinds of elements of ferrum nitrogen sulfur: include as
Lower step:
In a small beaker, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20ml
Hexamethylene (c6h12), 2 ml butyl titanate (ti (oc4h9)4, stir, obtain clarifying mixed liquor a, in another beaker,
Add 0.0921 g fecl3·6h2O, 0.0304 g nh4Cl, and 0.0432 g thiourea, add the hydrochloric acid of 4 ml 0.1 m,
Add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20 ml hexamethylene (c6h12), stir,
Obtain clarifying mixed liquor b, mixed liquor b lentamente instilled in mixed liquor a, stirs in instillation, obtain the mixed liquor c clarifying,
Then mixed liquor c is transferred in 100 ml inner liner polytetrafluoroethylene hydrothermal reaction kettles, put in drying baker, in solvent heat condition
Under, keep 160 DEG C of isothermal reaction 4 h.After reaction terminates, naturally cool to room temperature, with distilled water and washes of absolute alcohol each three
Secondary, 45 min every time, centrifugation, product is placed in 60 DEG C of drying baker and is obtained after vacuum drying 12～24 h.Using this step
The titanium dioxide powder diameter of rapid preparation is about 8～20 nm.In above-mentioned solution, alkylphenol polyoxyethylene: n-butyl alcohol: hexamethylene
The volume ratio of alkane is 2:3:10, and in Water-In-Oil w/o microemulsion, oil-water ratio is 10:1.
Product is produced using German bruker company d8 advance type x- ray powder diffractometer (xrd) (λ cu=
0.15418 nm) carry out Crystalline form analysis (as Fig. 1), result shows: products therefrom is anatase titanium dioxide.
It is catalyzed under visible light using the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders that the present embodiment prepares
Degrade the methyl orange of 20 mg/l, response time 1.5h, degradation rate is 90%.
Embodiment 2
A kind of preparation method of the codoping modified octahedrite nano titanium dioxide powder of three kinds of elements of ferrum nitrogen sulfur: include as
Lower step:
In a small beaker, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20ml
Hexamethylene (c6h12), 2 ml butyl titanate (ti (oc4h9)4, stir, obtain clarifying mixed liquor a, in another beaker,
Add 0.0921 g fecl3·6h2O, 0.0304 g nh4Cl, and 0.0432 g thiourea, add the hydrochloric acid of 4 ml 0.1 m,
Add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20 ml hexamethylene (c6h12), stir,
Obtain clarifying mixed liquor b, mixed liquor b lentamente instilled in mixed liquor a, stirs in instillation, obtain the mixed liquor c clarifying,
Then mixed liquor c is transferred in 100 ml inner liner polytetrafluoroethylene hydrothermal reaction kettles, put in drying baker, in solvent heat condition
Under, keep 180 DEG C of isothermal reaction 2 h.After reaction terminates, naturally cool to room temperature, with distilled water and washes of absolute alcohol each three
Secondary, 45 min every time, centrifugation, product is placed in 60 DEG C of drying baker and is obtained after vacuum drying 12～24 h.Using this reality
Apply a titanium dioxide powder diameter for methods described preparation and be about 8～20 nm(Fig. 2).In above-mentioned solution, alkylphenol-polyethenoxy
Ether: n-butyl alcohol: the volume ratio of hexamethylene is 2:3:10, in Water-In-Oil w/o microemulsion, oil-water ratio is 10:1.
Morphology analysis (as Fig. 2) are carried out using Japanese jeol-2010 type transmission electron microscope (tem), result shows: ferrum
Nitrogen sulfur codope titanium dioxide, granule is less and uniform, a diameter of 8～20 nm.
Light electric spectrum using Britain vg esm-lab has carried out xps analysis to prepared material, from Fig. 3, Fig. 4 and Fig. 5
As can be seen that product contains three kinds of elements of ferrum nitrogen sulfur, wherein, ferrum element is with fe3+Exist, nitrogen is mixed with substitute doping and gap
Miscellaneous two ways exists, and element sulphur is with s4+、s6+Exist simultaneously, illustrate that preparation-obtained titanium dioxide powder has ferrum nitrogen sulfur
Ternary codope phenomenon.
Using the present embodiment methods described, the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders preparing are can
See the methyl orange of catalytic degradation 20 mg/l under light, in 1.5h, the degradation rate of degraded methyl orange is up to 96%.
Embodiment 3
A kind of preparation method of the codoping modified octahedrite nano titanium dioxide powder of three kinds of elements of ferrum nitrogen sulfur: include as
Lower step:
In a small beaker, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20ml
Hexamethylene (c6h12), stir, obtain clarifying mixed liquor a, in another beaker, under the conditions of ice-water bath, add 2 ml
Titanium tetrachloride (ticl4), 0.0921 g fecl3·6h2O, 0.0304 g nh4Cl, and 0.0432 g thiourea, 4 ml 0.1 m
Hydrochloric acid, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20 ml hexamethylene (c6h12), stir
Mix uniformly, obtain clarifying mixed liquor b, mixed liquor b is lentamente instilled in mixed liquor a, stirs in instillation, obtain the mixed of clarification
Close liquid c, then transfer to mixed liquor c in 100 ml inner liner polytetrafluoroethylene hydrothermal reaction kettles, put in drying baker, in solvent
Under heat condition, keep 180 DEG C of isothermal reaction 2 h.After reaction terminates, naturally cool to room temperature, clear with distilled water and dehydrated alcohol
Wash each three times, 45 min every time, centrifugation, product is placed in 60 DEG C of drying baker and is obtained after vacuum drying 12～24 h.Adopt
It is about 8～20 nm with the titanium dioxide powder diameter of this step preparation.In above-mentioned solution, alkylphenol polyoxyethylene: positive fourth
Alcohol: the volume ratio of hexamethylene is 2:3:10, in Water-In-Oil w/o microemulsion, oil-water ratio is 10:1.
It is catalyzed under visible light using the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders that the present embodiment prepares
Degrade the methyl orange of 20 mg/l, response time 1.5h, degradation rate is 94%.
Embodiment 4
A kind of preparation method of the codoping modified octahedrite nano titanium dioxide powder of three kinds of elements of ferrum nitrogen sulfur: include as
Lower step:
In a small beaker, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-amyl alcohol (c5h11Oh), 20
Ml normal hexane (c6h14), 2 ml butyl titanate (ti (oc4h9)4, stir, obtain clarifying mixed liquor a, in another beaker
In, add 0.0921 g fecl3·6h2O, 0.0304 g nh4Cl, and 0.0432 g thiourea, add the salt of 4 ml 0.1 m
Acid, adds 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-amyl alcohol (c5h11Oh), 20 ml normal hexane (c6h14), stirring
Uniformly, obtain clarifying mixed liquor b, mixed liquor b is lentamente instilled in mixed liquor a, stirs in instillation, obtain the mixing clarified
Liquid c, then transfers to mixed liquor c in 100 ml inner liner polytetrafluoroethylene hydrothermal reaction kettles, puts in drying baker, in solvent thermal
Under the conditions of, keep 180 DEG C of isothermal reaction 2 h.After reaction terminates, naturally cool to room temperature, with distilled water and washes of absolute alcohol
Each three times, 45 min every time, centrifugation, product is placed in 60 DEG C of drying baker and is obtained after vacuum drying 12～24 h.Using
The titanium dioxide powder diameter of this step preparation is about 8～20 nm.In above-mentioned solution, alkylphenol polyoxyethylene: n-amyl alcohol:
The volume ratio of normal hexane is 2:3:10, and in Water-In-Oil w/o microemulsion, oil-water ratio is 10:1.
It is catalyzed under visible light using the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders that the present embodiment prepares
Degrade the methyl orange of 20 mg/l, response time 1.5h, degradation rate is 92%.
Embodiment 5
A kind of preparation method of the codoping modified octahedrite nano titanium dioxide powder of three kinds of elements of ferrum nitrogen sulfur: include as
Lower step:
In a small beaker, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20
Ml hexamethylene (c6h12), 2 ml butyl titanate (ti (oc4h9)4, stir, obtain clarifying mixed liquor a, in another beaker
In, add 0.1376 g fe (no3)3·9h2O, 0.0341 g carbamide, and 0.0688 g cysteine, add 4 ml 0.1 m
Nitric acid, add 4 ml alkylphenol polyoxyethylene (op-10), 6 ml n-butyl alcohol (c4h9Oh), 20 ml hexamethylene (c6h12), stir
Mix uniformly, obtain clarifying mixed liquor b, mixed liquor b is lentamente instilled in mixed liquor a, stirs in instillation, obtain the mixed of clarification
Close liquid c, then transfer to mixed liquor c in 100 ml inner liner polytetrafluoroethylene hydrothermal reaction kettles, put in drying baker, in solvent
Under heat condition, keep 180 DEG C of isothermal reaction 2 h.After reaction terminates, naturally cool to room temperature, clear with distilled water and dehydrated alcohol
Wash each three times, 45 min every time, centrifugation, product is placed in 60 DEG C of drying baker and is obtained after vacuum drying 12～24 h.Adopt
It is about 8～20 nm with the titanium dioxide powder diameter of this step preparation.In above-mentioned solution, alkylphenol polyoxyethylene: positive fourth
Alcohol: the volume ratio of hexamethylene is 2:3:10, in Water-In-Oil w/o microemulsion, oil-water ratio is 10:1.
It is catalyzed under visible light using the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders that the present embodiment prepares
Degrade the methyl orange of 20 mg/l, response time 1.5h, degradation rate is 93%.
Embodiment 6
Using embodiment 2 methods described, prepare the titanium dioxide powder (a～e) of different element dopings, wherein a: only
Plus source of iron and nitrogen source；B: only add source of iron and sulphur source；C: only add nitrogen source and sulphur source；D: plus source of iron nitrogen source and sulphur source；E: only add nitrogen
Source.
The nano-titanium dioxide powder of the different element dopings of above-mentioned acquisition and pure nano-titanium dioxide powder (p25) are used
Catalytic degradation methyl orange (mo, 20 mg/l) under visible ray, and compare the degradation effect (Fig. 6) of methyl orange, permissible from Fig. 6
Find out, the ferrum nitrogen and sulphur co-doping nano-titanium dioxide powders prepared by the present invention have most highly active, degrade in 1.5h
Up to 96%, it can in addition contain as seen from Figure 6, there is cooperative effect in the element doping of ferrum nitrogen and sulphur to the degradation rate of methyl orange, its light
Catalytic effect is well more a lot of than the effect of any two element codopes in three kinds of elements of ferrum nitrogen sulfur.
Very high catalytic capability is had by the photocatalyst that the method for the invention prepares, can be in photocatalytic water system
Hydrogen, degradable organic pollutant etc. are extensively applied.
Claims (8)
1. the preparation method of a kind of ferrum element and the codoping modified octahedrite nano titanium dioxide powder of two kinds of nonmetalloids,
It is characterized in that, with alkylphenol polyoxyethylene as nonionic surfactant, carbon number be 4～7 monohydric alcohol be help table
Face activating agent, carbon number be 5～8 alkane or cycloalkane be oil phase, inorganic or organic titanium source is raw material, containing ferrum element and two
The dilute acid soln planting nonmetalloid is aqueous phase, prepares a kind of ferrum element according to solvent-thermal method and two kinds of nonmetalloids are common
Doping vario-property octahedrite nano titanium dioxide powder；Described two nonmetalloids are nitrogen and sulfur；Ferrum unit in dilute acid soln
In element, nitrogen, element sulphur and titanium source, the mol ratio of titanium elements is 0.005～0.2:0.005～0.25:0.005～0.25:1；
The concretely comprising the following steps of described solvent-thermal method:
S1. by the alkylphenol polyoxyethylene of half consumption, carbon number be 4～7 monohydric alcohol, carbon number be 5～8
Alkane or cycloalkane mix homogeneously obtain mixed liquor a；
S2. by the alkylphenol polyoxyethylene of remaining half consumption, carbon number be 4～7 monohydric alcohol, carbon number be 5～
8 alkane or cycloalkane are mixed homogeneously with the dilute acid soln of iron content and nitrogen and sulfur and are obtained mixed liquor b；
S3. mixed liquor b is instilled in mixed liquor a and obtain mixed liquor c；
S4. mixed liquor c in hydro-thermal reaction container 120～180 DEG C reaction 1～12 h, cool down, wash, be drying to obtain ferrum and
Nitrogen and sulphur codope octahedrite nano titanium dioxide powder；
When titanium source is for organic titanium source, organic titanium source is mixed homogeneously with the raw material described in s1 and obtains mixed liquor a；When titanium source is inorganic
During titanium source, inorganic ti sources are mixed homogeneously with the raw material described in s2 and obtains mixed liquor b.
2. preparation method according to claim 1 is it is characterised in that described ferrum element is selected from the inorganic salt of iron content；Described
Nitrogen is selected from nitrogenous inorganic or Organic substance；Described element sulphur is selected from the inorganic or Organic substance of sulfur-bearing.
3. preparation method according to claim 2 is it is characterised in that described ferrum element is selected from fecl3·6h2O or fe
(no3)3·9h2o；Described nitrogen is selected from nh4Cl or carbamide；Described element sulphur is selected from thiourea or cysteine.
4. preparation method according to claim 1 is it is characterised in that described titanium source is selected from butyl titanate or titanium tetrachloride.
5. preparation method according to claim 1 is it is characterised in that alkylphenol polyoxyethylene, carbon described in s1 or/and s2
Atomic number is 4～7 monohydric alcohol, carbon number is 5～8 alkane or the volume ratio of cycloalkane is 1:1.5～6:2～10.
6. preparation method according to claim 1 is it is characterised in that carbon number described in s2 is 5～8 alkane or cycloalkanes
Hydrocarbon is 2～20:1 with the volume ratio of iron content and the dilute acid soln of nitrogen and sulfur.
7. any one of claim 1 to 6 methods described prepares ferrum and nitrogen and sulphur codope anatase type nano two
Titanium oxide powder.
8. ferrum described in claim 7 and nitrogen and sulphur codope octahedrite nano titanium dioxide powder are as photocatalyst
Application.
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