Background technology
Zinc oxide is a kind of extremely wide photoelectric semiconductor material of range of application, and under its room temperature, band gap is 3.37 ev, exciton bundle
Tie up and can be up to 60 mev.Modified zinc oxide will have the excellent properties such as special electricity, catalysis and sterilization.Such as, mix aluminum
Zinc oxide is the substitutional solid solution that zinc oxide is formed with aluminium oxide, and not only UV absorbing properties are good, chemical stability is high, and
And there is the characteristics such as of light color, visible light transmissivity is high, good conductivity, can be widely applied to antistatic coating, rubber and mould
The fields such as material, substituted good conductivity but expensive ito(in2o3: sn) material trend.Side using precious metal doping
Formula, it is possible to obtain urge the nano-powder of degradation catalyst for light.Such as, Wang Libo etc. carrys out doping zinc-oxide using noble metal and receives
Rice flour body, comprises the steps: that organic alcohol solvent is heated to 150 190 DEG C by (1);(2) zinc acetate-precious metal salt is added to mix
The aqueous solution of compound, reacts 5 60min at 150 190 DEG C, after reaction terminates, centrifugation, and gained solid sample is washed;
(3) by step (2) gained sample drying, gained precious metal doping zinc oxide nano-powder particle diameter is 30-50nm.This invention obtains
Product can be applicable in photocatalysis treatment organic sewage field (cn201410137559).Patent of invention cn201110383611
Disclose application in water process antibacterial for the tantalum-doped zinc oxide nano powder photocatalyst agent, it is withered that strain includes gram positive bacteria
Careless bacillus cereuss, staphylococcus aureuses, gram negative bacteria escherichia coli and pseudomonas aeruginosa.Research shows that tantalum adulterates
Zinc oxide nano powder can under dark situation and visible ray bacteria growing inhibiting, and antibiotic property be better than pure zinc oxide nano powder
End, and photocatalysis can effectively reduce the mic under dark situation, less addition just can reach higher fungistatic effect.
At present zinc oxide is doped with modification to improve or to improve the performances such as its photocatalysis, sterilization, has been in recent years
Carry out one of focus of environmentally conscious materials field research.According to the difference of dopant classification, the doping of zinc oxide based material can divide
For several classes as follows:
1, metal atom doped Chinese invention patent cn201310636925 discloses one kind and has visible light catalysis activity
Nickel doping zinc-oxide hierarchical structure photocatalytic nano material and preparation method thereof, this material component is: zn1-xnixO, x=in formula
0.5–10mol%.The method is: zinc salt, nickel salt and alkali dissolution is obtained presoma in alcoholic solvent or alcohol/water mixed solvent molten
Liquid, metal ion total concentration is 0.0625 0.25mol/l, and the molar concentration of alkali is 0.0625 2.5mol/l;It is placed in high pressure anti-
Answer sealing reaction in kettle;Washing with alcohol after cooling, air drying, be obtained have nano-granular, hollow ball, icosahedron, six
Multiple hierarchical structure photocatalytic nano material such as prism or class ball-type.Patent of invention cn201310122285 is related to a kind of bamboo charcoal and bears
Supported with zinc oxide mixes preparation and its application of copper catalytic composite material.Oxygen on bamboo charcoal is carried on using sol-gel process preparation
Change zinc and mix copper catalyst precursor thing, preparation after high-temperature roasting has the catalytic composite material of photocatalytic activity.Patent of invention
Cn201210106093 discloses a kind of nanometer doped zinc oxide powder body and preparation method thereof, using co-precipitation-calcining one-step method
The nanometer Zinc oxide powder of synthesizing Si-Al codope, doped chemical aluminum, doped chemical silicon are each with the mol ratio of zinc oxide
0.03: 1~0.18: 1.Cn201010275787 disclose have visible light catalysis activity transition metal doping zinc oxide mesoporous
Material and preparation method thereof.The transient metal doped zno mesoporous material group of the present invention is divided into: zn1-xrexO (wherein re=mn,
Fe, co, cu;X=0.1mol~6mol%).By zinc salt, carbamide and be used for adulterate dissolving metal salts stir in distilled water
Obtain precursor solution, metal ion total concentration is controlled to 0.05mol/l-0.2mol/l, carbamide and metal ion mole it
Ratio is controlled to 5-15;It is placed in sealing reaction in autoclave;Cooling, deionized water wash, vacuum drying;Then roasting, system
The transition metal doping zinc oxide mesoporous material obtaining.Cn201010104899 is related to a kind of alcohol full-boiled process and prepares Co-doped ZnO
coxzn1-xThe method of o multifunctional magnetic nano powder, comprising: (1) at room temperature, soluble cobalt and zinc salt are dissolved in second two
In alcohol, mechanical agitation, add anhydrous sodium acetate and Polyethylene Glycol, ultrasonic disperse obtains reaction solution;(2) reaction solution is carried out
Alcohol thermal response, reaction temperature is 180 DEG C~220 DEG C, reacts 10~14 hours, naturally cools to room temperature;(3) by above-mentioned product from
The heart separates, washing, is dried to obtain coxzn1-xO multifunctional magnetic nano powder.Cn200810021689 discloses a kind of tantalum doping
Zinc oxide nano powder photocatalyst agent, its preparation method and application.This method for preparing catalyst is to be dissolved in soluble zinc salt
Form zinc solution in ionized water, add appropriate citric acid to obtain clear solution a;Take appropriate tantalum precursor solution again, add suitable
Amount ethylene glycol forms solution b;Two kinds of solution are mixed, in whipping process, adds pvp and nitric acid, stir 0.5~1 hour, obtain
To clear solution;Clear solution is heated, is evaporated to the 50~70% of proper mass, add as dispersant and stabilizer, stirring
After be placed in the air, aging, dry, formed powder precursor;Made annealing treatment again, obtained sample.Cn200510095053 relates to
And the nano zine oxide preparation method of silver-doped, rare earth metal and its application of photocatalytic degradation Organic substance and antibacterial, this invention
By organic complex method mix in nano zine oxide silver-colored ag, rare earth metal (lanthanum la, cerium ce, praseodymium pr, neodymium nd, samarium sm, europium eu,
Gadolinium gd, dysprosium dy, erbium er, yttrium y) etc., to improve the photocatalytic activity of nano zine oxide.
2, non-metallic atom adulterates such as, and it is multiple that patent of invention cn201110164917 is related to a kind of expanded graphite zinc oxide
Closing light catalyst and preparation method thereof, composite photo-catalyst composition includes: by weight percentage, 10%~99% expanded graphite
With 1%~90% zinc oxide.Preparation method includes: (1) is added by mass volume ratio 1~2g: 100ml in sodium hydroxide solution
Enter expanded graphite, stir 0.5~3 hour under room temperature, obtain reactant liquor;(2) will be 1: 0.1~5 second with sodium hydroxide mol ratio
Sour zinc solution adds in above-mentioned reactant liquor, reacts 2~6 hours at 50 DEG C~90 DEG C, and by mixed liquor vacuum filtration, filtering residue is 60
DEG C~120 DEG C at drying.Chinese invention patent cn201310589707 discloses one kind to be prepared and mixes with multilevel hierarchy carbon
The method of miscellaneous ZnO microsphere, zinc gluconate is dissolved in water, and obtains gluconic acid zinc solution;By gluconic acid zinc solution
Ph value adjust after carry out supersound process;Again gluconic acid zinc solution is put in microwave attenuation materials instrument, carries out synthetic reaction,
Reaction naturally cools to room temperature after terminating, and obtains intermediate product;Intermediate product is centrifuged, obtains solid, by solid
Calcining, obtains with multilevel hierarchy carbon doping ZnO microsphere.Patent of invention cn201210015819 discloses a kind of solvent thermal
The method of method synthesizing zinc oxide/graphene composite material, method is to be mixed using graphite oxide, solvent and zinc source, obtains
Mixed solution;Mixed solution, last vacuum drying are processed using solvent heat treatment method, obtains final product zinc oxide/Graphene composite wood
Material.Cn201010294546 is related to a kind of zno porous array of prisms thin film of f- doping and preparation method thereof, and this thin film is with one kind
The method preparation that cryochemistry bath is combined with subsequent heat treatment.The method adopts simple zn (no3)2And nh4The mixing water of f
Solution, under the conditions of 70 DEG C of low temperature water-bath, directly prepares zn (oh) the f presoma battle array of prism-shaped in electro-conductive glass substrate
Row film, then through 500 DEG C of heat treatment, obtain the zno-f array of prisms film of nano-porous structure.Cn200410099023 provides
A kind of method preparing the CNT/zinc oxide composite powder with photocatalytic activity.It is mainly characterized by with anionic surface
Activating agent is successfully introduced into electronegative active group for dispersant in carbon nano tube surface, and does not change the structure of CNT.
Raw material with zinc salt, Lithium hydrate as synthesizing zinc oxide again, utilizes the electrostatic of reactive ion and active group in ethanol medium
Chemical reaction between effect and reactive ion, you can obtain the composite powder that zinc oxide nanocrystalline is covered in carbon nano tube surface
Body, crystal grain diameter is about 5~10nm.
3, Organic substance doping patent of invention cn201310064916 discloses a kind of zinc oxide/polyaniline composite light
The preparation method of catalyst.Using direct precipitation method and hydro-thermal method, prepare nano zine oxide respectively, with silane coupler to institute
Obtain nano zine oxide and carry out surface chemical modification, so that it is combined with polyaniline (pani) by emulsion polymerization and obtain different-shape
Nano zine oxide/polyaniline composite photocatalyst.Patent of invention cn201310013813 discloses one kind side's acid cyanines dye
The preparation method of the zinc oxide visible-light-inducephotocatalyst photocatalyst of material sensitization, by zn (ac)22h2O and glucose are dissolved in deionized water, ultrasonic
Form settled solution, after solution is proceeded in politef autoclave inner bag, 140~180 DEG C of hydro-thermal reaction 12~24h,
After being cooled to room temperature, by the black powder obtaining, deionized water and dehydrated alcohol carry out centrifuge washing respectively, in 60 DEG C of conditions
Under be dried to obtain the composite precursor of zinc oxide and carbon, presoma is placed in 400~600 DEG C of calcining 3h in Muffle furnace and obtains final product oxidation
Zinc microsphere, ZnO microsphere is mixed with squarylium cyanine dyes and organic solvent, at a temperature of 30~50 DEG C, said mixture is surpassed
Then organic solvent is removed by sonication 0.5~2 hour at reduced pressure conditions, finally dries the solidss obtaining at 60 DEG C
Dry, you can to obtain the zinc oxide visible-light-inducephotocatalyst photocatalyst of squarylium cyanine dyes sensitization.Cn201010513013 adopts mini-emulsion polymerization
Vinyl monomer and organosiloxane are carried out the polymer microballoon that the active silicone hydroxyl of surface band is prepared in copolymerization by method;Pass through again
Organic amine alkali source acts on polymer microballoon surface in situ generation nanometer with the active silicone hydroxyl on described polymer microballoon surface
Zno, prepared polymer/zno composite nano-microsphere.
4, such as, it is multiple that patent of invention cn201110352185 proposes a kind of Zinc oxide/titanium dioxide to doped metallic oxide
The preparation method closing nanometer rods is it is characterised in that comprise the steps, in whipping process, aqueous slkali and ethylenediamine to be added respectively
Enter to zinc ion solution;After stirring, after adding titanium dioxide powder to be uniformly mixed in mixed solution, will suspend
Liquid is put in the stainless steel autoclave of teflon lined, carries out hydro-thermal reaction;Prepared precipitated product is washed with deionized water
Wash drying, obtain zinc oxide/titanium dioxide composite nanorod material.Chinese invention patent cn201410081116 disclose α-
fe2o3Nanoparticle is modified zno composite photocatalyst system its preparation method and is included two steps: the alcohol/aqueous solution of (1) zinc salt is placed in high pressure
In reactor, 140 180 DEG C of reaction 1.5 9h;Product washing with alcohol, 60 DEG C of drying 2 6h, obtain Hemicentrotus seu Strongylocentrotuss shape zno microsphere.
(2) dipping-sedimentation method are utilized, by Hemicentrotus seu Strongylocentrotuss shape zno ultrasonic disperse in iron salt solutions, wherein iron salt and the mass ratio of zno are
Under 0.05 0.2,40 DEG C of stirring conditions, Deca ammonia reacts 1 12h;Collect solid and at 350 DEG C roasting 2h finally produced
Thing.Patent of invention cn201210258435 discloses a kind of preparation method of zinc oxide/stannic oxide composite microsphere, and the method is
Using wet chemistry method, in organic solvent with block polymer as template, with water miscible zinc salt and pink salt presoma, by mould
The feature such as the ordered structure of plate mesoscopic size and hydrophilic, oleophylic controlling size, the shape of granule, then removing template thus
Obtain metal oxide microspheres.Patent of invention cn201210246994 discloses a kind of system of zinc oxide/cuprous oxide heterojunction
Preparation Method, technical scheme is to be cleaned by ultrasonic flexible ito substrate, weighs zn (no3)2·6h2O and hexamethylenetetramine, be dissolved in from
It is made into electrolyte in sub- water, electrochemical deposition is carried out on electrochemical workstation, flexible ito substrate is working electrode, platinized platinum is
To electrode, control 40-70 DEG C of depositing temperature, transverse electric position -1.3~-1.6v, obtain zno nanometer stick array, rinse, dry, adopt
cuso4Prepare electrolyte with citric acid, electrochemical deposition carried out on electrochemical workstation, flexible ito substrate is working electrode,
Platinized platinum is to electrode, controls depositing temperature at 40-70 DEG C, sedimentation potential is -0.5~-0.6v, deposits in zno nanometer rods
cu2O, obtains zno/cu2O hetero-junctions.Patent of invention cn201210004993 discloses a kind of visible light-responded zinc oxide-oxygen
Change bismuth composite photo-catalyst and preparation method thereof.This complex by mass ratio be 1: 0.05~1: 0~2 nano zine oxide, oxygen
Change bismuth and graphene oxide is composited.Step is as follows: water-soluble zinc salt, bismuth salt and carbamide are added separately in aqueous solution, altogether
After precipitation, product, after centrifugation, washing, drying and calcination, product is placed in the graphene oxide after ultrasonic disperse
Heated in water solution stirring is reacted, and after reaction terminates, product, after centrifugation, washing and being dried, obtains zinc oxide-bismuth oxide
Composite photo-catalyst.Patent of invention cn201110153091 is related to the zinc-oxide nano linear array modified based on Red copper oxide quantum dot
Row catalysis material and its preparation method and application.This invention is the zinc-oxide nano linear array being firmly grown in conductive substrates
Arrange as working electrode, using platinum electrode as to electrode, using saturated calomel electrode as reference electrode, with the dimethyl of copper nitrate
Sulfoxide solution, as electrolyte, has prepared the zinc oxide nano of Red copper oxide quantum dot modification by electrochemical cyclic voltammetry
Nanowire arrays catalysis material.Cn200910014385 provides a kind of zinc oxide/indium oxide nano heterojunction photocatalysis material
And preparation method thereof.The chemical formula of this catalysis material is zno/in2o3, the mol ratio of zinc nitrate and indium nitrate is 1: 5-5: 1.
Its preparation method be (1) by mol ratio be 1: 5-5: 1 zinc nitrate and indium nitrate mixing, be dissolved completely in shape in deionized water
Become clear solution, ammonia be added drop-wise in this clear solution, make the ph value of solution be adjusted to 9, be aged 24 hours, by zinc nitrate with
Indium nitrate fully precipitates;(2) deionized water filtration washing, after precipitation three times, at 95 DEG C, precipitate is evaporated, then at 600 DEG C
~1000 DEG C of annealing.Cn200710039531 is related to a kind of Zinc oxide/titanium dioxide composite photo-catalyst of core/shell structure, system
, it is characterised in that the stratum nucleare in core/shell structure is the zinc oxide of four-footed or polypody shape, shell is uniform cladding for Preparation Method and application
In the titanium dioxide layer on the zinc oxide stratum nucleare surface of four-footed or polypody shape, in the composite photo-catalyst granule of single core/shell structure
The distance of adjacent sufficient end is more than 10 microns.With four-footed or polypody shape zinc oxide as carrier, by the method for vapor phase hydrolysis by two
The nano-particle of titanium oxide is fixed on the surface of zinc oxide, and the thickness of titanium oxide layer is 5 nanometers and arrives hundreds of nanometers, can be former according to titanium
The consumption of material is adjusting.
5, inorganic salt blended patent of invention cn201310429225 discloses a kind of silver phosphate/zinc oxide composite photocatalyst
Material and preparation method thereof.It specifically comprises the following steps that ultrasonic disperse obtains zinc oxide fluid dispersion in deionized water by zinc oxide;
Silver nitrate is dissolved in deionized water, is added drop-wise in above-mentioned zinc oxide fluid dispersion under the conditions of magnetic agitation, obtains mixed solution,
After stirring a period of time;The phosphate solution having configured is slowly dropped in zinc oxide and the mixed solution of silver nitrate and continues to stir
Mix a period of time, the mixed solution obtaining after completion of dropping continues stirring, after product sucking filtration, use dehydrated alcohol and deionized water anti-
After backwashing is washed and is repeatedly vacuum dried afterwards, obtains silver phosphate/zinc oxide composite photocatalyst material.Patent of invention cn201310400890 is public
Open a kind of preparation method of zinc oxide/silver bromide nanometer composite, method is first distilled water to be heated to uniform temperature and protect
Hold constant temperature, add zinc source predecessor, boron hydride and surfactant, reaction a period of time, be subsequently added silver-colored source predecessor,
Continue reaction certain time.Gained sample obtains product through centrifuge washing post-drying several times.
Found by analysis contrast, the existing technology of preparing with regard to Zinc oxide doped carbon, the technical process of employing is relatively multiple
Miscellaneous, and be not suitable for carrying out large-scale production, and carbon doping Zinc oxide-base visible light catalyst is huge in environmental area application potential,
Therefore, explore its magnanimity technology of preparing, there is realistic meaning.
The present invention be directed to the deficiency of the preparation present situation of existing carbon doping Zinc oxide-base visible light catalyst powder body material, wound
Propose to the property made a kind of new method preparing carbon doping Zinc oxide-base visible light catalyst nano-powder material, i.e. small molecule
Material helps combustion method.Currently invention addresses improving the visible light catalysis activity of carbon doping Zinc oxide-base visible light catalyst powder body,
Realize the diffusive mixing in precursor molecules level using the spontaneous combustion of small-molecule substance, so that carbon doping Zinc oxide-base visible ray is urged
In agent crystal, the doping of carbon is more uniform sequential, promotes to stablize the formation of solid solution;Meanwhile, the addition of small-molecule substance overcomes
Reunion between powder body, the effective control grain size of product, improve the dispersibility of product.In addition, the present invention explores
Technology of preparing focus on control to process conditions, the first is dried predecessor using far above at a temperature of system boiling point, with
Flowing between acceleration molecular, the more efficiently doping of system of realizing;Its two be product after calcining using quick cooling by the way of,
Compared with the natural cooling adopting with prior art, more catalytic active sites can be retained.Therefore, using small-molecule substance of the present invention
The carbon doping Zinc oxide-base visible light catalyst not only good dispersion that auto-combustion method obtains, size is homogeneous, and visible ray
Catalytic performance is very excellent, compared with the existing technology, shows in technology of preparing and two aspects of product visible light catalytic performance
Advantage.
The present invention helps combustion method magnanimity to prepare carbon modification zinc oxide visible light catalyst using small organic molecule.Its preparation
Principle be using under small organic molecule high temperature combustion reaction heat, realize carbon to the effective deposition in zincite crystal,
Doping;Produce substantial amounts of gas during simultaneous reactions, effectively product " can be crushed ", thus obtaining undersized carbon doping
Zinc oxide nano-particle, realizes the magnanimity preparation of carbon doping Zinc oxide-base visible light catalyst.
The method there is no people to adopt in carbon doping Zinc oxide-base visible light catalyst preparation field, and pertinent literature is also no direct
Reference value, therefore, this invention has important for the technical staff being engaged in the preparation of carbon doping Zinc oxide-base visible light catalyst
Evocation.Because the preparation method that the present invention adopts has, equipment is simple, combined coefficient is high, low production cost, product divide
The features such as scattered property and visible light catalytic efficiency are high, therefore, has very strong commercial viability.
Content of the invention
It is an object of the invention to proposing a kind of magnanimity preparation method of carbon doping Zinc oxide-base visible light catalyst, obtain
Uniform particle sizes, the nano-powder of visible light catalytic excellent performance, the production reducing carbon doping Zinc oxide-base visible light catalyst becomes
This, be better achieved the uniform, controllable of particle size size and distribution.
The present invention weighs small molecule organic material and zinc source according to a certain percentage and is placed in mortar, is fully ground and to system is in
Existing clear viscous shape, then transfers to transparency liquid in crucible, and is dried under certain condition to not having vapor to release.?
Afterwards material fluffy for the brown obtaining is calcined again, calcining is quick after terminating to be cooled down, and the carbon doping Zinc oxide-base obtaining light color can
See photocatalyst nano-powder.
Concrete preparation condition is:
The ratio of the amount of the material in small molecule organic material and zinc source is 2 ~ 5:1;
Predecessor baking temperature is 180 ~ 220 DEG C, and drying time is 2 ~ 6 h;
Predecessor calcining heat is 500 ~ 800 DEG C, calcination time 1 ~ 5 h.
The preparation method of the carbon doping Zinc oxide-base visible light catalyst in the present invention, zinc source is zinc nitrate.
The preparation method of the carbon doping Zinc oxide-base visible light catalyst in the present invention, small organic molecule be glycine or
Person's oxalic acid or one kind of citric acid.
In the present invention, grinding is in order that reaction raw materials being capable of mix homogeneously;
In the present invention, drying is to carry out under the conditions of being above the boiling point, partly in order to boil off in mixture free from
By hydrone, in order to subsequent operation;On the other hand, can speed up intermolecular diffusion, thus realizing Effective Doping.
In the present invention, the predecessor due to gained can produce substantial amounts of gas in catabolic process, makes reaction system loose,
Effectively prevent the generation of product agglomeration.
The present invention quickly cools down after calcining, in order that retaining catalytic active site as much as possible in product structure, makes
It has higher visible light catalytic efficiency.The coloured product obtaining is very light powder body, and particle diameter reaches nanometer scale, and has
Good dispersibility.
The present invention has the advantage that
1st, proposing small molecule organic material first helps combustion method to prepare carbon doping Zinc oxide-base visible light catalyst powder body.
The addition of small molecule organic material, expands and produces a large amount of gases in catabolic process, makes reaction system loose, effectively prevent
The generation of agglomeration.
2nd, the raw material sources used by the present invention enrich and cheap, and preparation process is simple does not produce useless in production process
The industrial pollution such as water, waste residue.
3rd, using the present invention preparation product compared with other technologies, the carbon doping Zinc oxide-base visible light catalyst of preparation
Not only have the advantages that purity is high, of light color, particle diameter is little and size is homogeneous, soilless sticking phenomenon, be easily dispersed, and it can
See that photocatalysis efficiency is higher than the product obtaining using existing technology of preparing.
4th, the technology of preparing that the present invention explores focuses on the control to process conditions, using the temperature far above system boiling point
Under predecessor is dried, with acceleration molecular between flowing, the more efficiently doping of system of realizing;Its two be calcining after product adopt
The mode of quick cooling, compared with the natural cooling adopting with prior art, can retain more catalytic active sites.
5th, prepare carbon doping Zinc oxide-base visible light catalytic using small molecule organic material proposed by the present invention combustion-supporting burning method
Agent powder body, directly with sunlight as light source, can quickly and efficiently degradating organic dye it is seen that light utilization efficiency is high, commercial Application
Prospect is big.