CN1772375A - Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria - Google Patents
Nanometer doped zinc oxide and its prepn and application in photocatalysis to degrade organic matter and kill bacteria Download PDFInfo
- Publication number
- CN1772375A CN1772375A CN200510095053.7A CN200510095053A CN1772375A CN 1772375 A CN1772375 A CN 1772375A CN 200510095053 A CN200510095053 A CN 200510095053A CN 1772375 A CN1772375 A CN 1772375A
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- Prior art keywords
- zinc
- oxide
- zinc oxide
- silver
- rare earth
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- 239000011787 zinc oxide Substances 0.000 title claims abstract description 55
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000005416 organic matter Substances 0.000 title claims abstract description 26
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 21
- 241000894006 Bacteria Species 0.000 title abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 54
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- 229910052709 silver Inorganic materials 0.000 claims abstract description 39
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- 239000011701 zinc Substances 0.000 claims abstract description 28
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 23
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 10
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- 239000000243 solution Substances 0.000 claims description 18
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
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- 229940068475 zinc citrate Drugs 0.000 claims description 6
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- YHKRPJOUGGFYNB-UHFFFAOYSA-K sodium;zirconium(4+);phosphate Chemical compound [Na+].[Zr+4].[O-]P([O-])([O-])=O YHKRPJOUGGFYNB-UHFFFAOYSA-K 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to Ag and RE doped nanometer zinc oxide and its preparation process and application in photocatalysis to degrade organic matter and killing bacteria. Ag, RE metals La, Ce, Pr, Nd, Sm, etc. are doped into nanometer zinc oxide to raise its photocatalytic activity in degrading harmful chemical matter and resisting bacteria. Under lighting, the doped nanometer zinc oxide has higher photocatalytic activity and higher antibacterial capacity; and in case of no lighting, it has relatively high antibacterial effect owing to the antibacterial effect one Ag, Zn, RE and other antibacterial ions. The preparation process may be an organic matter complexing process or a sprying pyrolysis process. The doped nanometer zinc oxide may be used through mixing with other material, or used as additive added into plastic, ceramic, fiber, timber, rubber, glass, cement, metal and other material to form various kinds of photocatalytic antibacterial material and product.
Description
Technical field
The invention belongs to photocatalysis, environmental protection, technical field of inorganic material.The nano zine oxide and preparation method thereof and photocatalysis to degrade organic matter and antibiotic application that relate to silver-doped, rare earth metal.
Technical background
Morbid substance contained in the air produces serious harm to human body.As airborne CO, SO
2, NO
x, H
2S, NH
3, formaldehyde, acetaldehyde, benzene and homologue, TOVC (TVOC) etc., health is produced very big infringement.Formaldehyde (HCHO) is a kind of colourless easily molten irritative gas, and formaldehyde can absorb through respiratory tract, and its aqueous solution " formalin " can absorb through alimentary canal.Acetaldehyde is soluble in water, makes water quality generation chemical change, and it is very big to human body harmfulness to drink this water, injures the nervous system of drinking person especially easily and causes cancer.The people of long-term contact formaldehyde, acetaldehyde can cause nasal cavity, oral cavity, nasopharynx, throat, skin and gastral cancer.Benzene and homologue toluene thereof, dimethylbenzene, trimethylbenzene are the raw materials of important making various kinds of resin, are widely used as solvent (glue, paint, coating, waterproof material) when house ornamentation.Benzene is inflammable poisonous, can suppress the human body hematopoiesis function, can cause leucocyte, red blood cell and hematoblastic minimizing and causes multiple disease, and skin and mucous membrane are had local irritant effect, sucks or absorb through skin to cause poisoning.TVOC is divided into eight classes: alkanes, aromatic hydrocarbons, alkene class, halohydrocarbon, ester class, aldehydes, ketone and other.They all clear existing with trace and trace water, mainly come from: one, organic solution.As paint, aqueous coating, adhesive, cosmetics, washing agent, seam composition; Two, construction material: as wood-based plate, foam heat insulating material, plastic plate; Three, house decorative material: as wallpaper, other ornaments etc.; Four, fibrous material: as carpet, tapestry and synthetic fiber curtain; The imperfect combustion of domestic fuel and tobacco leaf, slop etc.TVOC can cause the immunity of organism off-leveling, influences central nervous system function, dizziness, headache, subjective symptoms such as drowsiness, unable, uncomfortable in chest occur; Also may influence digestive system, poor appetite occur, feel sick etc., but allergy etc. appears in liver injury and hemopoietic system when serious.
Often contain multiple harmful organic principles such as halogenated aliphatic hydrocarbon, halogenated aryl hydrocarbon, nitro-aromatic, polycyclic aromatic hydrocarbon, phenols, dyestuff, agricultural chemicals in the organic wastewater sewer, organic pollution has caused a large amount of aquatic environments pollutions, animal to poison in the water, cause certain destruction of river, river, lake, extra large ecological environment, and constitute serious threat health.
Show that according to interrelated data 60% of human diseases comes from air pollution, particularly comes from airborne pathogenic microorganisms such as bacterium, virus etc., the purification of air has crucial effect for human beings'health.Remove airborne pollutant with the method for filtering and adsorb in traditional air cleaning, perhaps adopt the method for spraying chemical agent to kill airborne bacterium, filtration and absorption often are subjected to the filter cloth obstruction or adsorb saturated restriction, and spraying agent will produce new pollution.It is the new air purification method that Recent study develops that application conductor photocatalysis technology purifies air.The photocatalyst-type nano material has extremely strong oxidability, can decomposing organic matter, and decomposing bacteria, fungi, CO, SO
2, NO
x, H
2S, NH
3, the organic matter in formaldehyde, acetaldehyde, benzene and homologue thereof, TOVC (TVOC), the organic wastewater etc., harmful substance is changed into innocuous substances such as carbon dioxide, water, inorganic oxide.
Photocatalysis technology is with semiconductor nano material titanium dioxide TiO
2Be representative, application technology technology is simple, with low cost, utilize natural daylight to get final product catalytic decomposition bacterium and pollutant, have characteristics such as high catalytic activity, good chemical stability and heat endurance, non-secondary pollution, nonirritant, safety non-toxic, and can be of value to the ecological natural environment for a long time, be one of environmental protection catalyst that has most DEVELOPMENT PROSPECT.Particularly in recent years, realized industrialization in many fields such as glass, metal, building, automobile, residential equipment, household electrical appliances, light industry, air cleaning, water treatment, air cleaning, coating.
At TiO
2The area load noble metal is beneficial to the ultra-voltage that separates and reduce reduction reaction (reduction of proton, the reduction of dissolved oxygen) in light induced electron and hole, thereby improves the activity of photochemical catalyst greatly.
Nano zine oxide ZnO is that photocatalysis performance is only second to titanium dioxide TiO
2Catalysis material.But nano zine oxide ZnO price is more cheap, and zinc oxide is a metal ion species dissolution type antiseptic, still has antibiotic performance under the condition of unglazed photograph.When unglazed the photograph, titanium dioxide TiO
2The surface has only load antimicrobial nano metallic (silver, copper etc.) that antibacterial ability is just arranged.Nano zine oxide is a kind of good photochemical catalyst, after water oxygen zinc is being subjected to photon irradiation greater than the energy gap energy, produces that electronics---the hole is right.Electronics and hole are at zinc oxide surface and water and water oxygen gas or very high OH hydroxyl free radical and the ultra-oxygen anion free radical O of airborne oxygen reaction generation oxidisability
2 -, can with CO, SO in the air
2, NO
x, H
2S, NH
3, formaldehyde, acetaldehyde, benzene and homologue, TOVC (TVOC) or the many bio-refractories of water the toxic organic compound reaction generate inorganic matter and other innocuous substances such as carbon dioxide and water.Harmful organic substances in the water such as organic chloride, agricultural chemicals, interfacial agent, pigment etc., it is difficult fully removing with present water technology, and zinc oxide can make organic matter decompose as photochemical catalyst.Studies show that, the reaction speed of nano zinc oxide particles is 100～1000 times of common zinc oxide particle, and compares with the common zinc oxide particle, and it causes scattering of light hardly, and big specific area and wide being with are arranged, therefore be considered to one of photochemical catalyst that has application prospect.Zinc oxide is one of traditional inorganic antibacterial material, when in unglazed environment, contacting with bacterium, zinc ion slowly releases, with the bacterium generation effect of inhaling on the surface, can combine with cell membrane and memebrane protein, destroy its structure, enter the enzyme that destroys electron transport system behind the cell, it is lost activity, reach antibiotic purpose.The antibiotic of nano zine oxide is the result of photocatalysis and two kinds of antibiotic mechanism effects of metal ion stripping.Nano zine oxide especially under the ultraviolet ray irradiation, can decomposite the electronegative electronics that moves freely voluntarily at sunlight, stay the hole of positively charged simultaneously, with airborne oxygen effect oxygen is become active oxygen, extremely strong chemism is arranged, thereby most germ and virus are killed.It is strong that nano zine oxide absorbs ultraviolet ability, and ((wavelength 280～320nm) all has shielding action for wavelength 320～400nm) and ultraviolet B radiation to long wave ultraviolet.At nano zine oxide area load argent, copper nano-particle, can obtain better bactericidal effect.Nano zine oxide is nontoxic, tasteless, and is non-stimulated to skin, do not decompose, never degenerates, good stability, and this is as white, can be in addition painted according to different objects, and low price.Nano zine oxide is the external used medicine of skin, and skin is had functions such as convergence, anti-inflammatory, wrinkle resistant and protection, and the sun-screening agent that can be used for cosmetics is to prevent ultraviolet injury.In fiber textile and dress ornament thereof, applying nano zinc oxide has the peculiar effect of antibiotic, mildew-resistant, deodorizing.Can be used for producing deodorization, antibiotic, anti-ultraviolet fiber or zinc oxide timber floor and carpet.Nano zine oxide is because the diffusion velocity that gas passes through than very fast, is again a kind of fabulous catalyst therefore.Nano zine oxide is little because of its size, specific area is big, surperficial key and granule interior different, the surface atom coordination is not congruent, cause the activity site on surface to increase, formed scraggly atomic steps, strengthened the reaction contact-making surface, the catalytic activity of nano zine oxide and selectivity are far longer than its traditional catalyst, are widely used in fields such as fiber, cosmetics, pottery, environmental project, glass and building materials.
According to the regulation in the Ministry of Public Health's " disinfection technology standard " that comes into effect in April, 2003 (version in 2002), an antibiotic speech strict definition is " antibiotic being meant adopted chemistry or physical method kill bacteria or handled breeding of overslaugh bacterial growth and active process thereof ".Antibacterial and general name bactericidal action is antibiotic.Antibacterial product generally is that antibacterial product is made in reprocessing, and anti-microbial property is achieved, and durable antibiotic by after adding one or more anti-biotic materials in the raw material.
The antiseptic of comparative maturity can be divided into two classes at present.One class is an inorganic antiseptic, and another kind of is organic antibacterial agent.Wherein organic antibacterial agent is various in style, and they are widely used in medical field and industrial circle.The main feature of organic antibacterial agent is that effect is fast and effect is obvious, but exists not enough at the aspects of using such as security, persistence, hear resistance and broad spectrum antibacterial.Compare with organic antibacterial agent, characteristics such as that inorganic antiseptic has is high temperature resistant, broad-spectrum antibacterial property, long-acting, safety, non-secondary pollution become the new research focus in antibiotic field just gradually.
Inorganic antibacterial material is divided into two kinds again according to antibiotic mechanism.First kind is the photocatalysis antifungal mechanism, be that nanometer semiconductor oxidation produces light induced electron and photohole under the activation of ultraviolet light, electronics separates and moves to the diverse location of particle surface with the hole, electronics and the O that is adsorbed on the nanometer semiconductor oxidation photocatalyst powder surface
2Generate ultra-oxygen anion free radical O
2 -, hole and H
2The O reaction generates the OH hydroxyl free radical, and nearly all organic matter is decomposed, thereby plays the effect of sterilization, mildew-resistant, air cleaning.Second kind of inorganic antiseptic is to utilize metal and the sterilization of ion or the class antiseptics that bacteriostasis makes such as silver, copper, zinc, be to utilize metal ion stripping sterilization mechanisms such as Ag, Cu, Zn, when the metal ion that promptly dissociates out contacts bacterial body, combine with protease in the bacterium and it to be lost activity and bacterium is killed, belong to ion stripping contact-type antiseptic, its antibacterial action is a passive type, has proved that its toxicity is less.Its activity of killing, suppressing pathogen is successively decreased in the following order: Ag＞Hg＞Cu＞Cd＞Cr＞Ni＞Pb＞Co＞Zn＞Fe, and best with the antibacterial effect of silver ion, and Hg, Cd, Cr, Pb metal itself have very strong toxicity to human body.
Silver ion has strong bactericidal action, carrying silver antimicrobials is that silver ion or fine silver particles are loaded on the different porous or sandwich material, as zeolite, silica, sodium zirconium phosphate, rectorite, fluor-apatite, hydroxyapatite, calcium carbonate, clay, calcium phosphate, alumino-silicate, basic zirconium phosphate, active carbon, silica gel, CaO, Al
2O
3Carrying silver antimicrobials has multiple advantages such as antibacterial ability height, Heat stability is good, safe and reliable, nonirritant.This inorganic antibacterial material can extensively be added in the various types of materials, as tame electrical article, commodity, stationery, toy, medical supplies etc., is applied in construction material, the fibre.
The Nano Silver product is a kind of high-efficiency antimicrobial medicine.Silver itself can not sterilization under metallic state, and what it leaned on is the silver-ion antibiotic that metal silver surface discharges.Because the stability of silver, its solubility in the medium beyond the nitric acid is extremely low, so the fungistatic effect of common metal silver is rather faint.But, after argent is processed into Nano Silver, its atomic arrangement shows as " Jie's attitude " between solid and molecule, and the extremely strong Nano Silver particulate of this activity possesses superpower antibacterial ability, can kill bacteria, pathogenic microorganisms such as fungi, mycoplasma, Chlamydia.
Since the twentieth century, the research in rare earth field is subjected to people's attention day by day, and rare earth salts and complex thereof are by constantly synthetic and be applied to all trades and professions.Especially at the rare earth biological chemical field, obtained challenging achievement.People find successively, some rare earth compounds and rare earth organic ligand complex have anti-inflammatory, antibiotic, anticoagulation, effect such as hypoglycemic, can be used for treating illnesss such as burn, thrombotic disease, skin disease, diabetes and eczema, gout, rheumatism, tuberculosis, leprosy, arthritis.Nearly research during the last ten years discloses, and rare earth salts and complex thereof also have significant inhibitory effect to cancer and tumour.
Rare-earth salts can the stripping rare earth element ion when running into water or malaria.The antibiotic property of rare earth element ion is strong, has a broad antifungal spectrum, only need very low concentration inhibitory action to be arranged to common gram-positive bacterium (as staphylococcus aureus) and gramnegative bacterium (as Escherichia coli), the gemma bacterium strong to various vitality also has stronger inhibitory action.
Domestic researcher synthesizes and has compared the bacteriostatic activity of humic acid cerium and two kinds of complex compounds of cerium citrate.The result shows that humic acid cerium solution have broad spectrum antibacterial, and cerium citrate solution but stimulates the growth of bacterial strain to the equal unrestraint effect of experimental strains such as Escherichia coli, staphylococcus aureus under the condition of physiological pH=6.45.This may reflect humic acid, citric acid and Ce
3+The difference of combination and chemistry of complex character.Humic acid and Ce
3+The complex compound instability that generates has bigger dissociation constant, and citric acid and Ce
3+The complex compound that generates has bigger stability constant.This shows bacteriostasis and free Ce
3+Concentration is relevant.Further research is relatively behind the antibacterial ability of rare earth compound cerous nitrate, lanthanum nitrate and silver ion antimicrobial agent, and its result shows that the antibacterial ability of cerous nitrate and lanthanum nitrate and silver ion antimicrobial agent are similar.Choose cerous nitrate and mix its antibiotic level of test in the celluar concrete, the result shows that the antibiotic level of celluar concrete is improved largely, and preliminary proof strengthens concrete antibiotic property with rare earth compound.To mix with ceric sulfate at zinc oxide nano-particle, the intensification heat treatment of oven dry back obtains mixing cerium Ce
4+Nano zine oxide, improved its anti-microbial property to Escherichia coli, staphylococcus aureus, bacillus subtilis.
Rare earth compound and complex are as antibiotic, anti-inflammation drugs, can be used for treating dermatitis such as contact, anaphylaxis, to its result of treatment of Acute and chronic dermatitis no less than the cortex hormone of aadrenaline medicine, have effects such as inflammation-resisting itch-stopping, difficult recurrence, and do not contain antibiotic and cortex hormone of aadrenaline and so in the medicine, so long-term use can not cause side effect.The rare earth bacteriostatic agent not only has purposes widely at field of medicaments, and has also shown wide application prospect in other industry.Studies show that, in the arrangement of synthetic fibers, behind the complex of use praseodymium Pr, make fabric produce stronger broad-spectrum antibacterial action.The complex of a kind of lanthanum La is added in the adhesive, and the antibacterial and mouldproof test shows that 5% lanthanum La complex makes adhesive extend to 30 days in the beginning mildew time by 3 days, and the mildew-resistant diseases prevention performance of product greatly improves.Relevant bibliographical information, rare earth can with cell membrane, cell membrane, enzyme, protein, DNA, RNA effect.The application of exploitation rare earth bacteriostatic agent is significant.
Preparation of nanomaterials mainly contains chemical preparation method, physics preparation method and Chemical Physics preparation method.Each components contents of chemical preparation method can accurately be controlled, and can realize molecule---and the even mixing on the atomic level can obtain even particle size distribution, the controlled nanoparticle material of shape by control of process condition.Chemical preparation method has certain advantage aspect the large-scale production of nano particle, be to prepare nano zine oxide at present to adopt maximum class methods.
CN200410017315.3 silver surface decorated nanometer zinc oxide and preparation method thereof, this method is interspersed or the clad nano silver oxide on the nano zine oxide surface, and the average grain diameter of silver surface decorated nanometer zinc oxide is at 10～100nm.This method is to add oxalic acid in soluble zinc salt such as its halogen, nitrate, sulfate, acetate solution, obtain zinc oxalate, pour soluble silver salt into lasting stirring the in the zinc oxalate suspension, oven dry after-baking, obtain silver surface decorated nanometer oxidized zinc products, be used for anti-biotic material.Wherein do not address and identical content of the present invention.
CN1631163 is a kind of dichloride in anatase type TiO
2Composite inorganic antimicrobial agent and preparation method thereof, this method is containing dichloride in anatase type TiO
2, AgNO
3And in rare earth (Ce, Pr, Nd, the La) mixed aqueous solution in reactor the constant temperature stirring reaction, filter, washing, roasting 3～5 hours makes rare earth ion and silver ion be fastened on TiO
2On, obtain nano-TiO
2Composite inorganic antimicrobial agent is not wherein addressed and identical content of the present invention.
Summary of the invention
The objective of the invention is: utilize the inorganic structure and the functional material of the excellent performance of zinc oxide, very extensive in rubber industry, coatings industry, electronics, pottery, piezo-resistance, cosmetics, catalyst, medicine, food, industry purposes such as antibiotic.For satisfying the requirement of different industries, improve the quality and the added value of product, development of new photocatalytic degradation harmful chemical and anti-biotic material to zinc oxide product.Under illumination, produce the photocatalytic activity higher, have degraded harmful chemical and self-cleaning function, improved antibacterial ability than common nano zine oxide; During unglazed the photograph or in dark surrounds, because the effect of antibiotic ions such as silver, zinc, rare earth metal still has strong antibacterial action.The present invention adopts organic matter complexometry, spray pyrolysis etc. that doping zinc-oxide is prepared into nanometer grade powder, can mix a kind of or mix several among silver-colored Ag, rare earth ion lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, the yttrium Y simultaneously, make the silver-colored Ag, rare earth ion lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, the yttrium Y that mix be distributed in the surface of nano zine oxide and inner.Be used for photocatalytic degradation harmful chemical and antibiotic.So far, do not see that correlative study and patent report are arranged.
The object of the present invention is achieved like this: nano zine oxide mixes silver or/and the composition of rare earth ion.Nano zine oxide mixes silver-colored Ag or/and several ions among thulium lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, the yttrium Y.
Its preparation method is to be zinc nitrate, zinc acetate, zinc tartrate, zinc citrate with material containing zinc, be that solvent is made into one or more material containing zincs and contains the zinc aqueous solution with the deionized water, adopt organic matter complexometry, spray pyrolysis etc. that doping zinc-oxide is prepared into nanometer grade powder, mix a kind of or mix several ions or rare earth oxide among silver-colored Ag, thulium lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, the yttrium Y simultaneously.One-step method prepares nanometer doped zinc oxide, and then through appropriate heat treatment, obtains to have simultaneously the material of photocatalytic degradation harmful chemical and antibacterial ability.
Particular content of the present invention is as follows:
1, by mixing silver in the nano zine oxide or/and rare earth ion etc., because silver, zinc, rare earth ion itself just have stronger antibacterial action, nano zine oxide can be used as well behaved anti-biotic material as carrier on the one hand; The ion that mixes on the other hand helps electronics---the separation in hole of generation in the photocatalyst of zinc oxide under the illumination, improves the photocatalytic activity of zinc oxide, and harmful chemical and antibiotic is used to degrade.Finally be implemented under the illumination the higher photocatalytic activity of nano zine oxide than common (mixing), be used to degrade harmful chemical and self-cleaning material improve antibacterial ability; During unglazed the photograph or in dark surrounds, because the effect of antibiotic ions such as silver, zinc, rare earth metal reaches strong antibacterial action.Mixing silver-colored Ag amount of metal is 0.01～10% of zinc oxide weight.Mixing rare earth metal is lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, yttrium Y, and mixing the rare earth metal amount is 0.05～10% of zinc oxide weight.Can mix a kind of or mix several ions among silver-colored Ag and the above-mentioned thulium Y simultaneously, adopt organic matter complexometry, spray pyrolysis etc. that doping zinc-oxide is prepared into nanometer grade powder.Obtain the silver-colored nano zine oxide of mixing of containing metal silver particles and silver ion simultaneously, silver-colored Ag, the rare earth ion that mixes is distributed in the surperficial and inner of nano zine oxide.Through appropriate heat treatment, silver ion can be moved to the surface of nano zine oxide morely.
2, with above-mentioned summary of the invention 1 described content and method, adopting the employed material containing zinc of organic matter complexometry is zinc nitrate, zinc acetate, zinc tartrate, zinc citrate; Organic matter with complexing power is tartaric acid, ethylenediamine tetra-acetic acid, malic acid, citric acid, ethylene glycol, glycerine, polyethylene glycol, oxalic acid, polyvinyl alcohol, ethylenediamine, triethanolamine, DBSA, glycine, lysine, alanine, stearic acid, acetylacetone,2,4-pentanedione.With a certain amount of deionized water is that solvent is made into one or more material containing zincs and organic matter and contains the zinc aqueous solution, and the mol ratio between zinc and the organic matter is 1: 0.1～1: 3, and the temperature of solution is 10～95 ℃.Doping ion material is its water miscible all cpds, is argent, rare earth oxide perhaps, and conduct contains the doping ion solution behind nitric acid dissolve.On request the doping solion is joined in the zinc-containing solution, heating concentrates this mixed solution under 60～260 ℃ of temperature, till concentrating the generation jelly.Change jelly over to heating furnace, heat treatment 60～360 minutes in the air obtains the nanometer doped zinc oxide powder under 200～900 ℃ of temperature.Or jelly is put into micro-wave oven handled 10～40 minutes, blowing air heat treatment 30～360 minutes under 300～800 ℃ of temperature again obtains nanometer doped zinc oxide powder (less than 100nm).
3, with above-mentioned summary of the invention 1 described content and method, adopting the employed material containing zinc of spray pyrolysis is zinc nitrate, zinc acetate, zinc tartrate, zinc citrate, is that solvent is made into one or more material containing zincs and contains the aqueous solution that zinc concentration is 0.05～6mol/L with the deionized water.Doping ion material is its water miscible all cpds, is argent, rare earth oxide perhaps, and conduct contains the doping ion solution behind nitric acid dissolve.On request the doping solion is joined in the zinc-containing solution, enter in the pyrolysis oven after spraying apparatus is handled, heat decomposition temperature is 400～1100 ℃, carries out thermal decomposition under the condition of bubbling air, collect product, be nanometer doped zinc oxide powder (less than 100nm).
4, with above-mentioned summary of the invention 1,2,3 described content and methods, obtain nanometer doped zinc oxide, can be directly and other material such as ZrO
2, SiO
2, Al
2O
3, TiO
2, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, You material etc. mix and use; Or as making various photocatalysis and antibacterial product in the materials such as additive adding plastics, pottery, glass, fiber, timber, rubber, cement.
Characteristics of the present invention are:
The technological process of production of the present invention is short, and operating condition is simple, the production process serialization, one step of preparation process of doping process and nano zine oxide finishes, and production cost is low, and composition is even, obtain hydrophilic, efficient, that performance is permanent photocatalysis and anti-biotic material, antibacterial ability is stronger.
The specific embodiment
Embodiment 1
Adopt the preparation of organic matter complexometry to mix silver-colored nano zine oxide and photocatalytic degradation aldehydes gas.Take by weighing 30.05g. zinc nitrate hexahydrate Zn (NO
3)
26H
2O pours in the evaporating dish of a 250ml, use the 100ml deionized water dissolving, then adding by argent concentration behind nitric acid dissolve is the liquor argenti nitratis ophthalmicus 19ml of 0.04mol/L, add citric acid 21.4g again, the heating evaporation ware evaporates the water on electric furnace, the solution thickness that becomes gradually moves in the inherent air atmosphere of chamber type electric resistance furnace in 500 ℃ of heat treatments 240 minutes, obtains little yellow puff.Measure through X-ray diffraction (XRD), this product is a wurtzite-type zinc oxide of mixing silver 1%; Observe through transmission electron microscope (TEM), the zinc oxide average grain diameter is about 60nm; Measuring silver through XPS, TEM SEAD SAED is present in the zinc oxide with silver ion Ag+ and Ag.The zinc oxide of silver is not mixed in the preparation that uses the same method, and granularity is about 70nm.Take by weighing 0.8g and should mix silver-colored nano zine oxide, be tiled in the culture dish, culture dish is put into the 500ml photo catalysis reactor, the about 4000ppm of acetaldehyde is injected inwards from an injection port in the sealing back, places 12 hours.With the xenon lamp of 300W as light source, with GC-14B detection reaction product.After 11 hours illumination, can not survey the concentration of acetaldehyde, and 95% acetaldehyde is become CO by mineralising
2, and the nano zine oxide of not mixing silver has only 50% acetaldehyde to be become CO by mineralising under same experimental condition
2, still can detect a certain amount of acetaldehyde and exist.The photocatalytic activity that shows the nano zine oxide of mixing silver does not reduce, and is improved on the contrary.
Adopt foregoing invention content 2 described other material containing zincs and organic one or more as raw material, add in the different rare earth ions one or more, can prepare the nano zine oxide of doping equally with above-mentioned organic matter complexometry, show the ability of higher photocatalytic degradation acetaldehyde.
The nano zine oxide and the ZrO of the above-mentioned silver-doped for preparing, rare earth ion
2, SiO
2, Al
2O
3, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, You material etc. mix when using, because the interception of these materials, the photocatalytic activity of nanometer doped zinc oxide decreases, but still has certain photocatalytic activity.
Embodiment 2
Adopt the spray pyrolysis preparation to mix cerium nano zine oxide and photocatalytic degradation formaldehyde gas.With zinc acetate and cerous nitrate is raw material, the acetate zinc concentration is 2mol/L, mix cerium ratio adding cerous nitrate in 2% and be made into the aqueous solution, the ultrasonic ultrasonic delay line memory of packing into, spray in the pyrolysis oven, heat decomposition temperature is set at 800 ℃, carries out thermal decomposition under the condition of bubbling air, per hour straying quatity is 300ml, collects product.Measure and transmission electron microscope (TEM) observation through X-ray diffraction (XRD), this product is a wurtzite-type zinc oxide, and the zinc oxide average particle size is about 81nm.The zinc oxide of cerium is not mixed in the preparation that uses the same method, and granularity is about 75nm.Take by weighing 0.8g and should mix the cerium nano zine oxide, be tiled in the culture dish, culture dish is put into the 500ml photo catalysis reactor, the about 800ppm of formaldehyde is injected inwards from an injection port in the sealing back, places 12 hours.With the xenon lamp of 300W as light source, with GC-14B detection reaction product.After 2.5 hours illumination, do not measure formaldehyde, the result shows that 93% formaldehyde is become CO by mineralising
2, and the nano zine oxide of not mixing cerium has only 70% acetaldehyde to be become CO by mineralising under same experimental condition
2, still can detect a small amount of formaldehyde and exist, illustrate that mixing the cerium nano zine oxide has higher photocatalytic activity.
Adopt foregoing invention content 3 described other material containing zincs and organic one or more as raw material, add in silver and the different rare earth ion one or more, can prepare the nano zine oxide of doping with above-mentioned spray pyrolysis, show the ability of higher photocatalytic degradation formaldehyde.
The nano zine oxide and the ZrO of the above-mentioned silver-doped for preparing, rare earth ion
2, SiO
2, Al
2O
3, TiO
2, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, You material etc. mix when using, and still have certain photocatalytic activity.
Embodiment 3
Adopt the preparation of organic matter complexometry to mix the nano zine oxide of silver and lanthanum and antibiotic.Take by weighing 15g zinc nitrate hexahydrate Zn (NO
3)
26H
2O pours in the evaporating dish of a 250ml, use the 30ml deionized water dissolving, take by weighing 99.95% lanthana 1g, in the volumetric flask of packing into behind the dilute nitric acid dissolution, add in the evaporating dish by 1.5% lanthanum incorporation with pipette, add liquor argenti nitratis ophthalmicus by 1% silver medal incorporation again, take by weighing the 6g glycine, pour in the evaporating dish and mix with solution.In baking oven,, obtain yellow thickness jelly, jelly is put into micro-wave oven handled 8 minutes, produce violent combustion-type reaction, collect product in 140 ℃ of dehydrations 300 minutes.Measure through X-ray diffraction (XRD), this product is a wurtzite-type zinc oxide; Observe through transmission electron microscope (TEM), the zinc oxide average particle size is about 23nm.Again in chamber type electric resistance furnace in air atmosphere in 500 ℃ of heat treatments 180 minutes, remove surplus carbon.The nano zine oxide of silver and lanthanum is not mixed in the preparation that uses the same method, and granularity is about 31nm.
Penetrate employing flat band method culture of bacteria mensuration photocatalysis sterilization efficient down in illumination.With above-mentioned preparation mix silver and the nano zine oxide A of lanthanum, pure (not mixing silver-colored and lanthanum) nano zine oxide B mixes in the aqueous solution with activated carbon respectively, the oven dry sample is AC, BC, other gets the pure activated carbon C of same weight as test specimen.Sample is packed in the photocatalysis post, opens ultraviolet light, feed room air in the drum, pass sample layer after, use the distilled water solution filtered air.Illumination was taked a certain amount of aqueous sample after 3 hours from filter distilled water, add nutrient solution, and culture dish is placed (37 ℃) cultivation 24h in the insulating box, the clump count in the record culture dish.η=(1-N by formula
Sample/ N
Empty) * 100% calculates photocatalysis sterilization efficient, wherein N
EmptyClump count when not adding any sample, N
SampleClump count during for adding AC, BC, C.The result shows, from the aqueous solution sampling cultivation of the nano zinc oxide photocatalysis test specimen AC that mixes silver and lanthanum, do not observe clump count, and the sample sterilizing efficiency is 100%; And the nano zine oxide sample BC photocatalysis sterilization efficient of not mixing silver and lanthanum is more than 95%, and the sterilizing efficiency of pure activated carbon C sample is 30～50%.
Penetrate down in illumination, mix the nano zine oxide and the ZrO of silver, rare earth ion with other
2, SiO
2, TiO
2, Al
2O
3, CaO, MgO, CaCO
3, mixing such as mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, You material, adopt said method to measure, photocatalysis sterilization efficient is 60～100%.
Unglazed according to the time, adopt inhibition zone method that the anti-microbial property of the nano zine oxide of mixing silver and lanthanum is estimated.The bacterial classification of anti-microbial property evaluation experimental adopts the mixed bacteria liquid of Escherichia coli and staphylococcus aureus.Suppress the diameter 12mm that forms and the wafer A of thickness 6mm with mixing the silver and the nano zine oxide powder of lanthanum.As a comparison, the silver and the nano zine oxide disk B of lanthanum are not mixed in the preparation that uses the same method.In 3 culture dishes, coat the culture medium that can solidify, again mixed bacteria liquid is evenly spread upon media surface.Place nano zine oxide cylinder A a slice on the culture medium in a culture dish, put into nano zine oxide disk B a slice in another culture dish, except that the culture medium mixed bacteria liquid, do not put into other material in the 3rd culture dish, as blank C.Then culture dish is placed (37 ℃) cultivation 24h in the insulating box, take out back slide measure working sample inhibition zone size on every side.A, B inhibition zone are respectively 21 and 11mm as a result.Blank C is then without any inhibition zone.
When unglazed the photograph, other mixes the nano zine oxide and the ZrO of silver, rare earth ion
2, SiO
2, TiO
2, Al
2O
3, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, You material etc. mix and use as anti-biotic material; Or, can record the inhibition zone size in 5～23mm scope as making various antibacterial products in the materials such as additive adding plastics, pottery, fiber, timber, rubber, cement.
Claims (7)
1, nanometer doped zinc oxide, it is characterized in that mixing silver in the nano zine oxide or/and the composition of rare earth ion or rare earth oxide, thulium or oxide are one or more among lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, the yttrium Y.Mixing silver-colored Ag amount of metal is 0.01～10% of zinc oxide weight.Mixing rare earth metal is lanthanum La, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, yttrium Y, and mixing the rare earth metal amount is 0.05～10% of zinc oxide weight.
2, the nanometer doped zinc oxide preparation method, it is characterized in that with material containing zinc be raw material, material containing zinc is a zinc nitrate, zinc acetate, zinc tartrate or zinc citrate, with the deionized water is solvent, be made into above-mentioned one or more material containing zincs and contain the zinc aqueous solution, adopt the organic matter complexometry, spray pyrolysis etc. are prepared into nanometer grade powder with doping zinc-oxide, mix silver-colored Ag and/or one or more thulium lanthanums La simultaneously, cerium Ce, praseodymium Pr, neodymium Nd, samarium Sm, europium Eu, gadolinium Gd, dysprosium Dy, erbium Er, several ions or rare earth oxide among the yttrium Y, one-step method prepares nanometer doped zinc oxide, and then, obtain to have simultaneously the material of photocatalytic degradation harmful chemical and antibacterial ability through appropriate heat treatment.
3, nanometer doped zinc oxide preparation method is characterized in that mixing a kind of or mixes several ions among silver-colored Ag and/or the above-mentioned thulium Y simultaneously, adopts organic matter complexometry, spray pyrolysis etc. that doping zinc-oxide is prepared into nanometer grade powder.Obtain the silver-colored nano zine oxide of mixing of containing metal silver particles and silver ion simultaneously, silver-colored Ag, the rare earth ion that mixes is distributed in the surperficial and inner of nano zine oxide.Through appropriate heat treatment, silver ion can be moved to the surface of nano zine oxide morely.
4, by the described nanometer doped zinc oxide preparation method of claim 2, it is characterized in that adopting the employed material containing zinc of organic matter complexometry is zinc nitrate, zinc acetate, zinc tartrate, zinc citrate; Organic matter with complexing power is tartaric acid, ethylenediamine tetra-acetic acid, malic acid, citric acid, ethylene glycol, glycerine, polyethylene glycol, oxalic acid, polyvinyl alcohol, ethylenediamine, triethanolamine, DBSA, glycine, lysine, alanine, stearic acid or acetylacetone,2,4-pentanedione; Be that solvent is made into one or more material containing zincs and organic matter and contains the zinc aqueous solution with the deionized water, the mol ratio between zinc and the organic matter is 1: 0.1～1: 3, and the temperature of solution is 10～95 ℃; Doping ion material is its water miscible all cpds, is argent, rare earth oxide perhaps, and conduct contains the doping ion solution behind nitric acid dissolve; On request the doping solion is joined in the zinc-containing solution, heating concentrates this mixed solution under 60～260 ℃ of temperature, till concentrating the generation jelly.Change jelly over to heating furnace, heat treatment 60～360 minutes in the air obtains the nanometer doped zinc oxide powder under 200～900 ℃ of temperature.Or jelly is put into micro-wave oven handled 10～40 minutes, blowing air heat treatment 30～360 minutes under 300～800 ℃ of temperature again obtains nanometer doped zinc oxide powder (less than 100nm).
5, by the described nanometer doped zinc oxide preparation method of claim 2, it is characterized in that adopting spray pyrolysis, employed material containing zinc is zinc nitrate, zinc acetate, zinc tartrate or zinc citrate, is that solvent is made into one or more material containing zincs and contains the aqueous solution that zinc concentration is 0.05～6mol/L with the deionized water.Doping ion material is its water miscible all cpds, is argent and/or rare earth oxide perhaps, and conduct contains the doping ion solution behind nitric acid dissolve.On request the doping solion is joined in the zinc-containing solution, enter in the pyrolysis oven after spraying apparatus is handled, heat decomposition temperature is 400～1100 ℃, carries out thermal decomposition under the condition of bubbling air, collect product, be nanometer doped zinc oxide powder (less than 100nm).
6, by the described nanometer doped zinc oxide preparation method of claim 2, it is characterized in that obtaining nanometer doped zinc oxide, can be directly and other material such as ZrO
2, SiO
2, Al
2O
3, TiO
2, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, glaze etc. mix and use; Or as making various photocatalysis and antibacterial product in the materials such as additive adding plastics, pottery, glass, fiber, timber, rubber, cement.
7, nanometer doped zinc oxide light is mixed at ZrO in catalytic degradation organic matter and antibiotic application
2, SiO
2, TiO
2, Al
2O
3, CaO, MgO, CaCO
3, mica, zeolite, active carbon, lithopone, resin, metal dust, organic particle, coating, glaze etc. mix and use as anti-biotic material; Or as making various antibacterial products in the materials such as additive adding plastics, pottery, fiber, timber, rubber, cement.
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