CN104148047A - Macro preparation method for carbon doped zinc oxide-based visible-light catalyst - Google Patents
Macro preparation method for carbon doped zinc oxide-based visible-light catalyst Download PDFInfo
- Publication number
- CN104148047A CN104148047A CN201410435665.5A CN201410435665A CN104148047A CN 104148047 A CN104148047 A CN 104148047A CN 201410435665 A CN201410435665 A CN 201410435665A CN 104148047 A CN104148047 A CN 104148047A
- Authority
- CN
- China
- Prior art keywords
- zinc
- preparation
- zinc oxide
- light catalyst
- visible light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of material chemistry, and particularly relates to a macro preparation method for a carbon doped zinc oxide-based visible-light catalyst. The method disclosed by the invention adopts a micro-molecular organic matter combustion-supporting method for macroscopically preparing the carbon commingled zinc oxide-based visible-light catalyst. The preparation principle of the catalyst is that the reaction heat of the combustion of the micro-molecular organic matter at a high temperature is used to realize effective sedimentation and doping of a carbon element in zinc oxide crystals; at the same time, a large number of gases are generated in reaction processes, products can be crushed effectively, so that small-sized carbon doped zinc oxide-based nano particles are obtained, and the macro preparation of the carbon doped zinc oxide-based visible-light catalyst is realized. Prepared nano-powder has the advantages that the dispersibility is good, the particle sizes are small, the sizes are uniform, the visible-light catalytic property is excellent, and the chemical stability is high; at the room temperature of 27 DEG C-33 DEG C and sunlight exposures, the visible-light catalyst can completely degrade an organic dyestuff rhodamine B in 15 minutes, so that the catalyst can be applied to the fields of controlling environmental pollutants and the like.
Description
Technical field
The invention belongs to materials chemistry field, be specifically related to a kind of preparation in macroscopic quantity method of carbon doping zinc-oxide base visible light catalyst.
Background technology
Zinc oxide is the photoelectric semiconductor material that a kind of range of application is extremely wide, and under its room temperature, band gap is 3.37 eV, and exciton bind energy is up to 60 meV.Zinc oxide after modification will have the excellent properties such as special electricity, catalysis and sterilization.Such as, Al-Doped ZnO is the substitutional solid solution that zinc oxide and aluminium oxide form, not only UV absorbing properties is good, chemical stability is high, and there is of light color, the characteristic such as visible light transmissivity is high, good conductivity, can be widely used in the fields such as antistatic coating, rubber and plastics, have the good conductivity of replacement but expensive ITO(In
2o
3: Sn) trend of material.The mode that adopts precious metal doping, can obtain the nano-powder of urging degradation catalyst for light.Such as, the employing noble metals such as Wang Libo carry out doped zinc oxide nano powder, comprise the steps: that organic alcohol solvent is heated to 150-190 DEG C by (1); (2) add the aqueous solution of zinc acetate-precious metal salt mixture, at 150-190 DEG C of reaction 5-60min, after reaction finishes, centrifugation, washs gained solid sample; (3), by step (2) gained sample drying, gained precious metal doping zinc oxide nano-powder particle diameter is 30-50nm.The product that this invention obtains can be applicable in photocatalysis treatment organic sewage field (CN201410137559).Patent of invention CN201110383611 discloses the application of tantalum-doped zinc oxide nano powder photocatalyst agent in water treatment is antibacterial, and bacterial classification comprises gram-positive bacteria bacillus subtilis, staphylococcus aureus, Gram-negative bacteria Escherichia coli and pseudomonas aeruginosa.Research show tantalum-doped zinc oxide nano powder can be under dark situation and visible ray bacteria growing inhibiting, and antibiotic property is better than pure zinc oxide nanometer powder, and photocatalysis can effectively reduce the MIC under dark situation, less addition just can reach higher fungistatic effect.
At present zinc oxide being carried out to doping and modification to improve or to improve the performances such as its photocatalysis, sterilization, has been one of focus of environment in recent years Material Field research.According to the difference of dopant classification, the doping of Zinc oxide-base material can be divided into following a few class:
1, metal atom doped Chinese invention patent CN201310636925 discloses a kind of nickel doping zinc-oxide hierarchical structure photocatalytic nano material with visible light catalysis activity and preparation method thereof, and this material component is: Zn
1-xni
xo, x=0.5 – 10mol% in formula.The method is: zinc salt, nickel salt and alkali are dissolved in alcoholic solvent or alcohol/water mixed solvent and obtain precursor solution, and metal ion total concentration is 0.0625 – 0.25mol/L, and the molar concentration of alkali is 0.0625 – 2.5mol/L; Be placed in autoclave sealed reaction; Cooling rear ethanol washing, air drying, make there is nano-granular, the multiple hierarchical structure photocatalytic nano material such as hollow ball, icosahedron, six prisms or class ball-type.Patent of invention CN201310122285 relates to a kind of preparation and application thereof of loaded on bamboo charcoal doped zinc oxide copper composite catalyzing agent material.Adopt sol-gel process preparation to be carried on the doped zinc oxide copper catalyst precursor thing on bamboo charcoal, after high-temperature roasting, preparation has the composite catalyzing agent material of photocatalytic activity.Patent of invention CN201210106093 discloses a kind of nanometer doped zinc oxide powder and preparation method thereof, utilizing the nanometer Zinc oxide powder of co-precipitation-calcining one-step method synthesizing Si-Al codope, doped chemical aluminium, doped chemical silicon is 0.03: 1 with the mol ratio of zinc oxide separately～and 0.18: 1.CN201010275787 discloses transition metal doping zinc oxide mesoporous material having visible light catalysis activity and preparation method thereof.Transient metal doped ZnO mesoporous material component of the present invention is: Zn
1-xre
xo (wherein Re=Mn, Fe, Co, Cu; X=0.1mol～6mol%).By zinc salt, urea and be dissolved in distilled water for the slaine adulterating and stir and obtain precursor solution, the control of metal ion total concentration is 0.05mol/L-0.2mol/L, urea and metal ion mole ratio control be 5-15; Be placed in autoclave sealed reaction; Cooling, deionized water washing, vacuum drying; Then roasting, the transition metal doping zinc oxide mesoporous material making.CN201010104899 relates to the hot legal system of a kind of alcohol for Co-doped ZnO Co
xzn
1-xthe method of O multifunctional magnetic nano powder, comprising: (1) at room temperature, is dissolved in solubility cobalt salt and zinc salt in ethylene glycol, and mechanical agitation, adds anhydrous sodium acetate and polyethylene glycol, and ultrasonic dispersion obtains reaction solution; (2) reaction solution is carried out to 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 centrifugation, washing, the dry Co that obtains
xzn
1-xo multifunctional magnetic nano powder.CN200810021689 discloses a kind of tantalum-doped zinc oxide nano powder photocatalyst agent, its preparation method and application.This method for preparing catalyst is that soluble zinc salt is dissolved in deionized water and forms zinc solution, adds appropriate citric acid to obtain clear solution A; Get again appropriate tantalum precursor solution, add proper amount of glycol to form solution B; Two kinds of solution are mixed, in whipping process, add PVP and nitric acid, stir 0.5～1 hour, obtain clear solution; By clear solution heating, be evaporated to 50～70% of proper mass, then be incorporated as dispersant and stabilizing agent, to stir and be placed in air, aging, oven dry, forms powder precursor; Carry out again annealing in process, obtain sample.CN200510095053 relates to nano zine oxide preparation method and photocatalysis to degrade organic matter and the antibacterial application of silver-doped, rare earth metal, this invention is mixed 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. by organic complex method in nano zine oxide, improves the photocatalytic activity of nano zine oxide.
2, non-metallic atom doping such as, patent of invention CN201110164917 relates to a kind of expanded graphite zinc oxide composite photocatalyst and preparation method thereof, and composite photo-catalyst composition comprises: by weight percentage, and 10%～99% expanded graphite and 1%～90% zinc oxide.Preparation method comprises: (1) in sodium hydroxide solution by mass volume ratio 1～2g: 100ml adds expanded graphite, stirs 0.5～3 hour under room temperature, obtains reactant liquor; (2) by being 1: 0.1～5 with NaOH mol ratio, acetic acid zinc solution adds in above-mentioned reactant liquor, at 50 DEG C～90 DEG C, reacts 2～6 hours, and by mixed liquor vacuum filtration, filter residue is dried and be get final product at 60 DEG C～120 DEG C.Chinese invention patent CN201310589707 discloses a kind of method with multilevel hierarchy carbon doping zinc-oxide microballoon of preparing, and zinc gluconate is dissolved in water, obtains gluconic acid zinc solution; After being regulated, the pH value of gluconic acid zinc solution carries out ultrasonic processing; Again gluconic acid zinc solution is put into microwave hydrothermal synthesizer, carry out synthetic reaction, after reaction finishes, naturally cool to room temperature, obtain intermediate product; Intermediate product is carried out to centrifugation, obtain solid, by solid calcining, obtain having multilevel hierarchy carbon doping zinc-oxide microballoon.Patent of invention CN201210015819 discloses a kind of method of solvent-thermal method synthesizing zinc oxide/graphene composite material, and method is to adopt graphite oxide, solvent and zinc source to mix, and obtains mixed solution; Adopt solvent heat treatment method to process mixed solution, last vacuum drying, obtains zinc oxide/graphene composite material.CN201010294546 relates to ZnO porous prism array film of a kind of F-doping and preparation method thereof, and this film is bathed the method preparation combining with subsequent heat treatment with a kind of cryochemistry.The method adopts simple Zn (NO
3)
2and NH
4the mixed aqueous solution of F under the low temperature water bath condition of 70 DEG C, is directly prepared Zn (OH) the F presoma array films of prism-shaped in electro-conductive glass substrate, then through the heat treatment of 500 DEG C, obtains the ZnO-F prism array films of nano-porous structure.CN200410099023 provides a kind of method of preparing the CNT/zinc oxide composite powder with photocatalytic activity.Principal character is successfully to introduce electronegative active group taking anion surfactant as dispersant in carbon nano tube surface, and does not change the structure of CNT.Raw material taking zinc salt, lithium hydroxide as synthesizing zinc oxide again, in ethanol medium, utilize the chemical reaction between electrostatic interaction and the reactive ion of reactive ion and active group, can obtain the composite granule that zinc oxide nanocrystalline is covered in carbon nano tube surface, crystal grain diameter is about 5～10nm.
3, doped with organic matter patent of invention CN201310064916 discloses a kind of preparation method of zinc oxide/polyaniline composite material photochemical catalyst.Adopt direct precipitation method and hydro-thermal method, prepare respectively nano zine oxide, gained nano zine oxide is carried out to surface chemical modification with silane coupler, make itself and the compound nano zine oxide/polyaniline composite material photochemical catalyst that obtains different-shape of polyaniline (PANI) by emulsion polymerization.Patent of invention CN201310013813 discloses a kind of preparation method of zinc oxide visible light catalyst of squarylium cyanine dyes sensitization, by Zn (Ac)
22H
2o and glucose are dissolved in deionized water, ultrasonic formation settled solution, after solution is proceeded in polytetrafluoroethylene (PTFE) autoclave inner bag, hydro-thermal reaction 12～the 24h of 140～180 DEG C, be cooled to after room temperature, the black powder obtaining is carried out to centrifuge washing with deionized water and absolute ethyl alcohol respectively, the dry composite precursor that obtains zinc oxide and carbon under 60 DEG C of conditions, presoma is placed in to 400～600 DEG C of calcining 3h of Muffle furnace and obtains ZnO microsphere, ZnO microsphere mixes with squarylium cyanine dyes and organic solvent, at the temperature of 30～50 DEG C, by ultrasonic said mixture processing 0.5～2 hour, then organic solvent is removed under reduced pressure, finally the solids obtaining is dried at 60 DEG C, can obtain the zinc oxide visible light catalyst of squarylium cyanine dyes sensitization.The method that CN201010513013 adopts mini-emulsion polymerization is carried out vinyl monomer and organosiloxane copolymerization preparation table and wears the polymer microballoon of activated silica hydroxyl; Act on polymer microballoon surface in situ by the activated silica hydroxyl on organic amine alkali source and described polymer microballoon surface again and generate nano-ZnO, make polymer/ZnO nano complex microsphere.
4, doped metallic oxide such as, patent of invention CN201110352185 proposes a kind of preparation method of Zinc oxide/titanium dioxide composite nanorod, it is characterized in that comprising the steps in whipping process, and aqueous slkali and ethylenediamine are added to respectively in zinc ion solution; After stirring, after adding titanium dioxide powder to be uniformly mixed in mixed solution, suspension is put into the stainless steel autoclave of teflon lined, carried out hydro-thermal reaction; To make the washing of precipitated product deionized water dry, obtain Zinc oxide/titanium dioxide composite Nano bar material.Chinese invention patent CN201410081116 discloses α-Fe
2o
3nanoparticle is modified ZnO composite photocatalyst system its preparation method and is comprised two steps: the alcohol/aqueous solution of (1) zinc salt is placed in autoclave, 140 180 DEG C of – reaction, 1.5 – 9h; Product washs with ethanol, and 60 DEG C of dry 2 – 6h, obtain sea urchin shape ZnO microballoon.(2) utilize dipping-precipitation method, be scattered in iron salt solutions ultrasonic sea urchin shape ZnO, wherein the mass ratio of molysite and ZnO is under 0.2,40 DEG C of stirring condition of 0.05 –, to drip ammoniacal liquor to react 1 – 12h; Collect solid and at 350 DEG C roasting 2h obtain end product.Patent of invention CN201210258435 discloses a kind of preparation method of zinc oxide/tin ash complex microsphere, the method is to utilize wet chemistry method, in organic solvent taking block polymer as template, with water miscible zinc salt and pink salt presoma, the features such as the ordered structure by template mesoscopic size and hydrophilic, oleophylic are controlled size, the shape of particle, obtain metal oxide microballoon thereby then remove template.Patent of invention CN201210246994 discloses a kind of preparation method of zinc oxide/cuprous oxide heterojunction, and technical scheme is the flexible ITO substrate of ultrasonic cleaning, weighs Zn (NO
3)
26H
2o and hexa, be dissolved in and in deionized water, be made into electrolyte, on electrochemical workstation, carry out electrochemical deposition, flexible ITO substrate is working electrode, and platinized platinum is to electrode, controls depositing temperature 40-70 DEG C, transverse electric position-1.3～-1.6V, obtain ZnO nano-rod array, rinse, dry, adopt CuSO
4with citric acid preparation electrolyte, on electrochemical workstation, carry out electrochemical deposition, flexible ITO substrate is working electrode, and platinized platinum is to electrode, controls depositing temperature at 40-70 DEG C, and sedimentation potential is-0.5～-0.6V, deposits Cu on ZnO nanorod
2o, obtains ZnO/Cu
2o hetero-junctions.Patent of invention CN201210004993 discloses a kind of visible light-responded zinc oxide-bismuth oxide composite photo-catalyst and preparation method thereof.Nano zine oxide, bismuth oxide and graphene oxide that this compound is 1: 0.05～1: 0～2 by mass ratio are composited.Step is as follows: water-soluble zinc salt, bismuth salt and urea join respectively in the aqueous solution, after coprecipitation reaction, product is after centrifugal, washing, being dried and calcining, the graphene oxide heated in water solution stirring that product is placed in after ultrasonic dispersion is reacted, after reaction finishes, product through centrifugal, washing and dry after, obtain zinc oxide-bismuth oxide composite photo-catalyst.Patent of invention CN201110153091 relates to zinc oxide nano-wire array catalysis material of modifying based on cuprous oxide quantum dot and its preparation method and application.This invention is firmly to grow in zinc oxide nano-wire array in conductive substrates as working electrode, using platinum electrode as to electrode, using saturated calomel electrode as reference electrode, using the dimethyl sulphoxide solution of copper nitrate as electrolyte, prepare by electrochemical cyclic voltammetry the zinc oxide nano-wire array catalysis material that cuprous oxide quantum dot is modified.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/In
2o
3, the mol ratio of zinc nitrate and indium nitrate is 1: 5-5: 1.Its preparation method is that (1) is 1 by mol ratio: 5-5: 1 zinc nitrate and indium nitrate mix, be dissolved in completely and in deionized water, form clear solution, ammoniacal liquor is added drop-wise in this clear solution, make the pH value of solution be adjusted to 9, ageing 24 hours, fully precipitates zinc nitrate and indium nitrate; (2) with after deionized water filtration washing, precipitation three times, at 95 DEG C by sediment evaporate to dryness, then 600 DEG C～1000 DEG C annealing.CN200710039531 relates to a kind of Zinc oxide/titanium dioxide composite photo-catalyst, preparation method and application of core/shell structure, it is characterized in that the stratum nucleare in core/shell structure is the zinc oxide of four-footed or polypody shape, shell is the titanium dioxide layer that is evenly coated on the zinc oxide stratum nucleare surface of four-footed or polypody shape, and in the composite photo-catalyst particle of single core/shell structure, the distance of adjacent sufficient end is greater than 10 microns.Taking four-footed or polypody shape zinc oxide as carrier, by the method for vapor phase hydrolysis, the nano particle of titanium dioxide is fixed on to the surface of zinc oxide, the thickness of titanium oxide layer be 5 nanometers to hundreds of nanometers, can regulate according to the consumption of titanium material.
5, inorganic salt blended patent of invention CN201310429225 discloses a kind of phosphoric acid silver/zinc oxide composite photocatalyst material and preparation method thereof.Its concrete steps are as follows: zinc oxide is disperseed to obtain zinc oxide fluid dispersion in deionized water for ultrasonic; Silver nitrate is dissolved in deionized water, under magnetic agitation condition, is added drop-wise in above-mentioned zinc oxide fluid dispersion, obtain mixed solution, stir after a period of time; The phosphate solution configuring is slowly added drop-wise in the mixed solution of zinc oxide and silver nitrate and continues to stir a period of time, the mixed solution obtaining after dropwising continues to stir, repeatedly final vacuum is dry after product suction filtration, to use absolute ethyl alcohol and deionized water cyclic washing, obtains phosphoric acid silver/zinc oxide composite photocatalyst material.Patent of invention CN201310400890 discloses a kind of preparation method of zinc oxide/silver bromide nano-complex, method is first distilled water be heated to uniform temperature and keep constant temperature, add again zinc source predecessor, boron hydride and surfactant, reaction a period of time, add subsequently silver-colored source predecessor, continue reaction certain hour.Gained sample obtains product through centrifuge washing post-drying several times.
Contrast discovery by analysis, the existing technology of preparing about Zinc oxide doped carbon, the technical process relative complex adopting, and be not suitable for carrying out large-scale production, and carbon doping zinc-oxide base visible light catalyst is huge at environmental area application potential, therefore, explore its preparation in macroscopic quantity technology, 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, creatively proposed a kind of new method of preparing carbon doping zinc-oxide base visible light catalyst nano-powder material, small-molecule substance helps combustion method.The present invention is conceived to improve the visible light catalysis activity of carbon doping zinc-oxide base visible light catalyst powder, the diffusion that utilizes the spontaneous combustion of small-molecule substance to realize in precursor molecules level mixes, make the doping of carbon in carbon doping zinc-oxide base visible light catalyst crystal more uniform sequential, promote the formation of stablizing solid solution; Meanwhile, small-molecule substance add the reunion having overcome between powder, effectively controlled the grain size of product, improved the dispersiveness of product.In addition, the technology of preparing that the present invention explores is focused on the control to process conditions, and the first adopts far above dry predecessor at the temperature of system boiling point, with flowing between acceleration molecular, the more efficiently doping of the system that realizes; It two is that product after calcining adopts fast cooling mode, adopt with prior art naturally cooling compared with, can retain more catalytic active site.Therefore, the not only good dispersion of carbon doping zinc-oxide base visible light catalyst that utilizes small-molecule substance auto-combustion method of the present invention to obtain, particle size homogeneous, and visible light catalytic performance is very excellent, compared with the existing technology, show the advantage in technology of preparing and two aspects of product visible light catalytic performance.
The present invention adopts small organic molecule to help combustion method preparation in macroscopic quantity carbon modification zinc oxide visible light catalyst.Its preparation principle is the combustion reaction heat of utilizing under small organic molecule high temperature, realizes carbon to effective deposition, doping in zincite crystal; In simultaneous reactions process, produce a large amount of gas, " fragmentation " product effectively, thus obtain undersized carbon doped zinc oxide nano particle, realize the preparation in macroscopic quantity of carbon doping zinc-oxide base visible light catalyst.
The method there is no people in carbon doping zinc-oxide base visible light catalyst preparation field to be adopted, and pertinent literature is also without direct reference value, and therefore, this invention has important evocation for being engaged in technical staff prepared by carbon doping zinc-oxide base visible light catalyst.Because the preparation method of the present invention's employing has, equipment is simple, combined coefficient is high, production cost is low, product is dispersed and visible light catalytic efficiency high, therefore, has very strong commercial viability.
Summary of the invention
The object of the invention is to propose a kind of preparation in macroscopic quantity method of carbon doping zinc-oxide base visible light catalyst, acquisition particle diameter is even, the nano-powder of visible light catalytic excellent performance, reduce the production cost of carbon doping zinc-oxide base visible light catalyst, realize better the evenly controlled of particle size were size and distribution.
The present invention takes according to a certain percentage small organic molecule matter and zinc source is placed in mortar, and the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and is dried to and does not have steam to emit under certain condition.Finally the material fluffy brown obtaining is calcined again, calcining finishes rear cooling fast, obtains light carbon doping zinc-oxide base visible light catalyst nano-powder.
Concrete preparation condition is:
The ratio of the amount of substance in small organic molecule matter and zinc source is 2 ~ 5:1;
Predecessor baking temperature is 180 ~ 220 DEG C, and be 2 ~ 6 h drying time;
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 is the one of glycine or oxalic acid or citric acid.
In the present invention, grinding is for reaction raw materials can be mixed;
In the present invention, oven dry is to carry out under the condition of being above the boiling point, and is in order to boil off free water molecule free in mixture, so that subsequent operation on the one hand; On the other hand, the diffusion between can acceleration molecular, thus realize Effective Doping.
In the present invention, because the predecessor of gained can produce a large amount of gas in decomposable process, make reaction system loose, effectively prevented the generation of product agglomeration.
The present invention is cooling fast after calcining, in order to make to retain catalytic active site as much as possible in product structure, makes it have higher visible light catalytic efficiency.The product color obtaining is very light powder, and particle diameter reaches nanometer scale, and has good dispersiveness.
Tool of the present invention has the following advantages:
1, proposing first small organic molecule matter helps combustion method to prepare carbon doping zinc-oxide base visible light catalyst powder.Adding of small organic molecule matter, in decomposable process, expand and produce a large amount of gas, make reaction system loose, effectively prevent the generation of agglomeration.
2, the present invention raw material source used is enriched and is cheap, and preparation technology is simple, does not produce the industrial pollution such as waste water, waste residue in production process.
3, utilize product prepared by the present invention to compare with other technologies, the carbon doping zinc-oxide base visible light catalyst of preparation not only has that purity is high, of light color, particle diameter is little and particle size homogeneous, without agglomeration, be easy to the advantages such as dispersions, and its visible light catalytic efficiency is higher than the product that utilizes existing technology of preparing acquisition.
4, the technology of preparing that the present invention explores is focused on the control to process conditions, adopts far above dry predecessor at the temperature of system boiling point, with flowing between acceleration molecular, the more efficiently doping of the system that realizes; It two is that product after calcining adopts fast cooling mode, adopt with prior art naturally cooling compared with, can retain more catalytic active site.
5, the combustion-supporting burning legal system of small organic molecule matter of utilizing the present invention to propose is for carbon doping zinc-oxide base visible light catalyst powder, directly taking sunshine as light source, and degradating organic dye quickly and efficiently, visible ray utilization rate is high, and prospects for commercial application is large.
embodiment:
Below by specific embodiment, the present invention is further illustrated.
embodiment 1:
Be that 2:1 takes raw material and is placed in mortar according to the molar ratio of small organic molecule glycine and zinc nitrate, the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and under 200 DEG C of conditions dry 6h to not having steam to emit.Finally the material fluffy brown obtaining is calcined after 2h under 600 DEG C of conditions, cooling fast, obtain pale pink powder.Be about 65 nm by the particle diameter of transmission electron microscope observation product, product has good dispersiveness.Get this carbon doping zinc-oxide base visible light catalyst powder of 0.1g and join 30 mL 2 × 10
-5in the rhodamine B solution of mol/L, carry out catalysis.Under room temperature is 30 DEG C ± 3 DEG C and solar light irradiation, can be at 15 minutes by the degraded of organic dyestuff rhodamine B completely.
embodiment 2
Be that 2:1 takes raw material and is placed in mortar according to the molar ratio of small organic molecule oxalic acid and zinc nitrate, the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and under 180 DEG C of conditions dry 5h to not having steam to emit.Finally the material fluffy brown obtaining is calcined after 2h under 600 DEG C of conditions, cooling fast, obtain pale pink powder.Be about 75 nm by the particle diameter of transmission electron microscope observation product, product has good dispersiveness.Get this carbon doping zinc-oxide base visible light catalyst powder of 0.1g and join 30 mL 2 × 10
-5in the rhodamine B solution of mol/L, carry out catalysis.Under room temperature is 30 DEG C ± 3 DEG C and solar light irradiation, can be at 25 minutes by the degraded of organic dyestuff rhodamine B completely.
embodiment 3
Be that 5:1 takes raw material and is placed in mortar according to the molar ratio of small organic molecule citric acid and zinc nitrate, the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and under 200 DEG C of conditions dry 6h to not having steam to emit.Finally the material fluffy brown obtaining is calcined after 2h under 800 DEG C of conditions, cooling fast, obtain pale pink powder.Be about 50 nm by the particle diameter of transmission electron microscope observation product, product has good dispersiveness.Get this carbon doping zinc-oxide base visible light catalyst powder of 0.1g and join 30 mL 2 × 10
-5in the rhodamine B solution of mol/L, carry out catalysis.Under room temperature is 30 DEG C ± 3 DEG C and solar light irradiation, can be at 40 minutes by the degraded of organic dyestuff rhodamine B completely.
embodiment 4
Be that 4:1 takes raw material and is placed in mortar according to the molar ratio of small organic molecule oxalic acid and zinc nitrate, the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and under 220 DEG C of conditions dry 2h to not having steam to emit.Finally the material fluffy brown obtaining is calcined after 5h under 600 DEG C of conditions, cooling fast, obtain pale pink powder.Be about 55 nm by the particle diameter of transmission electron microscope observation product, product has good dispersiveness.Get this carbon doping zinc-oxide base visible light catalyst powder of 0.1g and join 30 mL 2 × 10
-5in the rhodamine B solution of mol/L, carry out catalysis.Under room temperature is 30 DEG C ± 3 DEG C and solar light irradiation, can be at 30 minutes by the degraded of organic dyestuff rhodamine B completely.
?
embodiment 5
Be that 2:1 takes raw material and is placed in mortar according to the molar ratio of small organic molecule citric acid and zinc nitrate, the system that is fully ground to presents thickness transparence, then transparency liquid is transferred in crucible, and under 200 DEG C of conditions dry 5h to not having steam to emit.Finally the material fluffy brown obtaining is calcined after 2h under 700 DEG C of conditions, cooling fast, obtain pale pink powder.Be about 70 nm by the particle diameter of transmission electron microscope observation product, product has good dispersiveness.Get this carbon doping zinc-oxide base visible light catalyst powder of 0.1g and join 30 mL 2 × 10
-5in the rhodamine B solution of mol/L, carry out catalysis.Under room temperature is 30 DEG C ± 3 DEG C and solar light irradiation, can be at 35 minutes by the degraded of organic dyestuff rhodamine B completely.
Claims (3)
1. the preparation in macroscopic quantity method of a carbon doping zinc-oxide base visible light catalyst, it is characterized in that the present invention adopts small organic molecule to help combustion method preparation in macroscopic quantity carbon doping zinc-oxide base visible light catalyst, its preparation principle is to utilize organic molecule combustion reaction heat at high temperature, realizes carbon to effective deposition, doping in zinc oxide lattice; In simultaneous reactions process, produce a large amount of gas, " fragmentation " product effectively, thereby obtain undersized carbon doping zinc-oxide base nano particle, realize the preparation in macroscopic quantity of carbon doping zinc-oxide base visible light catalyst, concrete steps are: mortar is put into as raw material in zinc source and small molecule organic compound, fully grind, at the temperature higher than system boiling point in baking oven, dry, obtain predecessor; Then predecessor is proceeded in Muffle furnace and is calcined, fast cooling after, can obtain the carbon doping zinc-oxide base visible light catalyst nano-powder with high catalytic activity, concrete preparation condition is:
The ratio of the amount of substance in small organic molecule and zinc source is 2 ~ 5:1;
Predecessor bake drying temperature is 180 ~ 220 DEG C, and be 2 ~ 6 h drying time;
Predecessor calcining heat is 500 ~ 800 DEG C, calcination time 1 ~ 5 h.
2. the preparation method of carbon doping zinc-oxide base visible light catalyst according to claim 1, is characterized in that zinc source is zinc nitrate.
3. the preparation method of carbon doping zinc-oxide base visible light catalyst according to claim 1, is characterized in that small organic molecule is the one of glycine or oxalic acid or citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410435665.5A CN104148047B (en) | 2014-08-31 | 2014-08-31 | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410435665.5A CN104148047B (en) | 2014-08-31 | 2014-08-31 | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104148047A true CN104148047A (en) | 2014-11-19 |
| CN104148047B CN104148047B (en) | 2017-02-01 |
Family
ID=51873786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410435665.5A Expired - Fee Related CN104148047B (en) | 2014-08-31 | 2014-08-31 | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104148047B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445372A (en) * | 2014-11-26 | 2015-03-25 | 燕山大学 | Method for preparing carbon doped zinc oxide nanoparticles |
| CN107376940A (en) * | 2017-07-31 | 2017-11-24 | 江苏金环环保设备有限公司 | A kind of catalytic composite material of rapidly and efficiently renovation of organic pollution soil and preparation method thereof |
| CN107376882A (en) * | 2017-08-01 | 2017-11-24 | 洛阳理工学院 | A kind of nanometer titanium dioxide composite material circulation utilization method |
| CN107552034A (en) * | 2017-08-21 | 2018-01-09 | 信阳师范学院 | A kind of simple, quick method for preparing carbon doping Zinc oxide nano sheet |
| CN108927137A (en) * | 2018-07-20 | 2018-12-04 | 河南师范大学 | A kind of preparation method of carbon doping bismuth oxide catalysis material |
| CN108970629A (en) * | 2018-07-20 | 2018-12-11 | 河南师范大学 | A kind of preparation method of carbon doping BiOCl visible light responsible photocatalytic material |
| CN109718755A (en) * | 2017-10-30 | 2019-05-07 | 东北林业大学 | A kind of hydro-thermal charcoal doping zinc-oxide photochemical catalyst |
| CN110398478A (en) * | 2018-04-25 | 2019-11-01 | 厦门量研新材料科技有限公司 | NDGCN synthetic method, aqueous solution method for detecting mercury content, cell developing method, conductive material and infrared transmitting device |
| CN110975933A (en) * | 2019-12-31 | 2020-04-10 | 江苏理工学院 | Carbon/zinc oxide/polytriazine imine ternary composite visible light catalyst and preparation method and application thereof |
| CN111137984A (en) * | 2019-12-30 | 2020-05-12 | 广东博源环保科技有限公司 | Thin-layer surface flow wastewater treatment carrier, wastewater treatment and thallus recovery system and method |
| CN112844425A (en) * | 2021-01-30 | 2021-05-28 | 哈尔滨商业大学 | C/ZnO/BiOI ternary composite photocatalytic material |
| CN114272930A (en) * | 2021-11-24 | 2022-04-05 | 东莞理工学院 | Heterojunction photocatalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693479A1 (en) * | 2003-12-09 | 2006-08-23 | Central Research Institute of Electric Power Industry | Method for producing substrate having carbon-doped titanium oxide layer |
| CN103496733A (en) * | 2013-09-30 | 2014-01-08 | 陕西科技大学 | Method for preparing carbon doped zinc oxide |
-
2014
- 2014-08-31 CN CN201410435665.5A patent/CN104148047B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693479A1 (en) * | 2003-12-09 | 2006-08-23 | Central Research Institute of Electric Power Industry | Method for producing substrate having carbon-doped titanium oxide layer |
| CN103496733A (en) * | 2013-09-30 | 2014-01-08 | 陕西科技大学 | Method for preparing carbon doped zinc oxide |
Non-Patent Citations (1)
| Title |
|---|
| KRISHNAN RAJESHWAR: ""Combustion synthesis, in-situ doping and visible light photocatalytic activity of oxide semiconductors for solar applications"", 《214TH ECS MEETING》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445372B (en) * | 2014-11-26 | 2016-03-02 | 燕山大学 | A kind of method preparing carbon doping Zinc oxide nanoparticle |
| CN104445372A (en) * | 2014-11-26 | 2015-03-25 | 燕山大学 | Method for preparing carbon doped zinc oxide nanoparticles |
| CN107376940A (en) * | 2017-07-31 | 2017-11-24 | 江苏金环环保设备有限公司 | A kind of catalytic composite material of rapidly and efficiently renovation of organic pollution soil and preparation method thereof |
| CN107376940B (en) * | 2017-07-31 | 2020-12-08 | 江苏金环环保设备有限公司 | Composite catalyst material for quickly and efficiently repairing organic contaminated soil and preparation method thereof |
| CN107376882A (en) * | 2017-08-01 | 2017-11-24 | 洛阳理工学院 | A kind of nanometer titanium dioxide composite material circulation utilization method |
| CN107552034A (en) * | 2017-08-21 | 2018-01-09 | 信阳师范学院 | A kind of simple, quick method for preparing carbon doping Zinc oxide nano sheet |
| CN109718755A (en) * | 2017-10-30 | 2019-05-07 | 东北林业大学 | A kind of hydro-thermal charcoal doping zinc-oxide photochemical catalyst |
| CN110398478A (en) * | 2018-04-25 | 2019-11-01 | 厦门量研新材料科技有限公司 | NDGCN synthetic method, aqueous solution method for detecting mercury content, cell developing method, conductive material and infrared transmitting device |
| CN108970629A (en) * | 2018-07-20 | 2018-12-11 | 河南师范大学 | A kind of preparation method of carbon doping BiOCl visible light responsible photocatalytic material |
| CN108927137A (en) * | 2018-07-20 | 2018-12-04 | 河南师范大学 | A kind of preparation method of carbon doping bismuth oxide catalysis material |
| CN108927137B (en) * | 2018-07-20 | 2021-08-13 | 河南师范大学 | Preparation method of carbon-doped bismuth oxide photocatalytic material |
| CN111137984A (en) * | 2019-12-30 | 2020-05-12 | 广东博源环保科技有限公司 | Thin-layer surface flow wastewater treatment carrier, wastewater treatment and thallus recovery system and method |
| CN111137984B (en) * | 2019-12-30 | 2022-05-06 | 广东博源环保科技有限公司 | Thin-layer surface flow wastewater treatment carrier, wastewater treatment and thallus recovery system and method |
| CN110975933A (en) * | 2019-12-31 | 2020-04-10 | 江苏理工学院 | Carbon/zinc oxide/polytriazine imine ternary composite visible light catalyst and preparation method and application thereof |
| CN110975933B (en) * | 2019-12-31 | 2023-02-28 | 江苏理工学院 | Carbon/zinc oxide/polytriazine imine ternary composite visible light catalyst and preparation method and application thereof |
| CN112844425A (en) * | 2021-01-30 | 2021-05-28 | 哈尔滨商业大学 | C/ZnO/BiOI ternary composite photocatalytic material |
| CN114272930A (en) * | 2021-11-24 | 2022-04-05 | 东莞理工学院 | Heterojunction photocatalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104148047B (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104148047B (en) | Macro preparation method for carbon doped zinc oxide-based visible-light catalyst | |
| CN104607216B (en) | The one-step method for synthesizing of phosphorus aluminum codope type conductive zinc oxide nanocatalyst | |
| CN104162681B (en) | A kind of preparation method of silver-ZnO nano composite structure | |
| CN105854863B (en) | A kind of C/ZnO/TiO2The preparation method of composite Nano catalysis material | |
| CN106542586B (en) | A kind of preparation method of wolframic acid cobalt nanorod | |
| CN106111108B (en) | A kind of preparation method of nanometer doped zinc oxide and its application in photocatalysis direction | |
| CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
| CN103663562B (en) | Method for low-temperature preparation of nano bismuth tungstate | |
| CN103055903B (en) | Preparation method of visible light catalytic material with adjustable BiOI-AgI spherical solid solution | |
| CN105728010A (en) | Preparation method of antibacterial silver molybdate and graphite-phase carbon nitride composite visible-light-induced photocatalyst | |
| CN104766963A (en) | Method for preparing metal oxide-carbon fiber nano composite material | |
| CN108579724B (en) | Bismuth vanadate nanotube crystal array growing on transparent conductive substrate in [010] direction and preparation and application thereof | |
| CN107983353B (en) | TiO 22-Fe2O3Preparation method and application of composite powder | |
| CN101302036A (en) | Preparation of doped titanium dioxide nano-tube | |
| CN103058265A (en) | Preparation method of mesoporous nano flake zinc oxide powder with high specific surface area | |
| CN104646003A (en) | Preparation and application of Nd<3-x>CoxNbO7-zincosilicate molecular sieve composite porous nanometer catalytic material | |
| CN102240540A (en) | Flaky gallium-containing nano photocatalyst and use thereof in light degradation of organic pollutants | |
| CN102553562B (en) | Multiple modified composite photocatalyst and preparation method thereof | |
| CN102580720B (en) | Visible light response nano zinc oxide-bismuth oxide composite photocatalyst and preparation method thereof | |
| CN102658209B (en) | Novel high-activity energy-saving thermal-insulating air purifying nonmaterial and preparation method thereof | |
| CN102602988B (en) | Method for preparing lithium titanate (Li4Ti5O12) with large specific area | |
| CN106315690A (en) | Porous cobalt tetroxide nanosheet and preparation method thereof | |
| CN108855170B (en) | A kind of preparation method and nanocomposite of the graphene-based bismuth system nanocomposite of carnation sample | |
| CN113443650B (en) | Method for preparing nano titanate by utilizing self-release of crystal water | |
| CN102389828B (en) | Preparation and application of high-dispersity ZnO/GaN solid solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Jinku Inventor after: Zhang Xiaoyan Inventor after: Wang Jiandong Inventor after: Zhang Hua Inventor after: Zhang Qi Inventor after: Yan Jie Inventor before: Liu Jinku Inventor before: Zhang Xiaoyan Inventor before: Wang Jiandong Inventor before: Zhang Hua Inventor before: Zhang Qi |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170201 Termination date: 20180831 |