CN110404533A - A kind of noble silver supported nano zinc oxide raw powder's production technology - Google Patents
A kind of noble silver supported nano zinc oxide raw powder's production technology Download PDFInfo
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- CN110404533A CN110404533A CN201810382933.XA CN201810382933A CN110404533A CN 110404533 A CN110404533 A CN 110404533A CN 201810382933 A CN201810382933 A CN 201810382933A CN 110404533 A CN110404533 A CN 110404533A
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- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 38
- 239000004332 silver Substances 0.000 title claims abstract description 38
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 title claims abstract description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 229920002401 polyacrylamide Polymers 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004108 freeze drying Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 9
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- LIQCCNRSMIHEBU-UHFFFAOYSA-N [Ag+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ag+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O LIQCCNRSMIHEBU-UHFFFAOYSA-N 0.000 description 5
- 229910007568 Zn—Ag Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- HAVWOKPVGYZVKQ-UHFFFAOYSA-N [Zn+2].[N+](=O)([O-])[O-].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [Zn+2].[N+](=O)([O-])[O-].[Ag+].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] HAVWOKPVGYZVKQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of noble silver supported nano zinc oxide raw powder's production technologies.The method, by simply hybrid reaction, is configured to certain density gel solution using water-soluble polymer and zinc nitrate hexahydrate, silver nitrate as raw material.Brown foam intermediate is obtained by freeze-drying, is finally calcined, obtains silver-ZnO target product.The hydroxyl of hydrophilic radical and particle surface generates stronger hydrogen bond association on the entropic effect and chain generated by water-soluble polymer chain conformation abundant, promote the dispersion of zinc oxide and Nano silver grain in aqueous polymer solution, obtains the zinc oxide of the nano-Ag particles load of polymolecularity.The preparation process flow is simple, and the powder dispersity of preparation is good, and particle hard aggregation is few, obtains the zinc oxide of the nano-Ag particles load of high usage, polymolecularity, reduces the dosage of silver, and raw material is cheap and easy to get, green non-pollution, be suitable for industrialized production.
Description
Technical field
The invention belongs to the materials synthesis fields of photochemical catalyst nano zine oxide, and in particular to noble silver loads nano oxygen
Change the preparation method of zinc.
Background technique
In recent years, water treatment problems are always the focus of international community's growing interest.Dying industrial wastewater is environment emphasis
One of pollution sources, the outstanding problem of processing are the removals of coloration and hardly degraded organic substance.It is current that there are many physics, chemistry, biologies
Method is used equally for the decolored degradation of waste water from dyestuff to handle, but is limited by waste water treatment efficiency and processing cost, treatment effect
It is all less desirable.
Heterogeneous photocatalysis technology not only can effective pollutants such as degradation of dye, phenols, hydro carbons, itrogenous organic substance, and
And can satisfy the technique requirement of sustainable development when using solar energy, therefore by favor.Due to zinc oxide semi-conductor light
Catalyst physical, chemical property are stablized, and oxidability is strong, and low energy consumption, reaction condition is mild, easy to operate, without secondary pollution, therefore
Often it is used as catalysis material.But zinc oxide nano-powder greater band gap, it is only capable of showing ultraviolet light photoresponse, and the earth
Can the ultraviolet light on surface only accounts for the 1%-5% of sunlight, be effectively to improve zinc oxide photocatalysis using solar energy therefore
The key of efficiency.
Liquid phase method is to prepare the most common method of nano particle, and liquid phase method includes the precipitation method, hydro-thermal method, sol-gel again
Method, microemulsion method etc., but at present these methods all have the shortcomings that it is respective.The Chinese patent of publication number CN105797704A
Application discloses a kind of preparation method of nano zine oxide, and the method is easy to operate, and raw material is cheap and easy to get, the nanoparticle point of preparation
It is preferable to dissipate uniformity, but single Zinc oxide nanoparticle made from the method is under ultraviolet light to the degradation efficiency of organic dyestuff one
As.
Noble metal has attracted extensive attention the modification of semiconductor material in Heterogeneous photocatalysis.The load of noble silver
Can make zinc oxide product to the photocatalytic degradation of organic dyestuff be improved significantly.Under ultraviolet light, zinc oxide and your gold
The interface for belonging to silver forms Xiao Jite potential barrier, and Nano silver grain serves as Electron absorption hydrazine, captures light induced electron, and make photohole shape
At hydroxyl radical free radical, the separative efficiency of light induced electron, hole is increased.In addition, under visible light illumination, utilizing nano-noble metal
The plasma resonance effect on surface, can be improved the visible light photocatalysis performance of nano zine oxide.
It is more that the Chinese patent of publication number CN107583654A discloses a kind of nanometer with adsorption photochemical catalysis synergistic effect
The preparation method of hole microballoon, be made Ag doped with nano TiO 2 kernel, hollow gap, porous nano silica shell it is micro-
Ball has the characteristics that large specific surface area, photocatalysis are strong.The Chinese patent of publication number CN106423162A discloses a kind of work
For the preparation method of the tin silver co-doped nano zinc oxide of photochemical catalyst, dropped while improving nano zinc oxide photocatalysis activity
Low production cost.The Chinese patent of publication number CN107497429A is closed using silver nitrate as silver-doped source using one step of solid phase method
At Ag doping WO out3Photochemical catalyst, with undoped WO3It compares, the degradation rate of rhodamine B is significantly improved.Although the above method
All prepare the nano particle of silver load, but preparation process complexity, severe reaction conditions, organic solvent be using more, while hot
Easy to reunite when processing, the pattern of particle not can be effectively controlled.
Summary of the invention
The purpose of the present invention is: overcome the deficiencies in the prior art, using relatively simple experiment flow, by the light of zinc oxide
Absorption region is expanded in visible-range by ultraviolet light, improves the photocatalytic degradation efficiency of nano zine oxide.Meanwhile it improving
The utilization rate in silver-colored source is improved in the dispersibility of nano oxidized zinc product in silver-colored source, improving, nano zinc oxide photocatalysis is active
Production cost is reduced simultaneously.
A kind of noble silver supported nano zinc oxide raw powder's production technology of the present invention, processing step are as follows:
(1) polyvinyl alcohol of certain mass or polyacrylamide are dissolved in deionized water and are stirred, obtained
Colorless and transparent colloidal sol；
(2) zinc nitrate hexahydrate and silver nitrate are added according to a certain percentage, reaction is sufficiently stirred, obtains water-soluble polymeric
Object-zinc nitrate-silver nitrate solution；
(3) above-mentioned solution is put into abundant pre-freeze in refrigerator, being subsequently placed in condenser temperature is -55 DEG C, and operating pressure is
It is freeze-dried in the freeze drier of 10Pa, obtains brown foam intermediate；
(4) the foam-like intermediate being dried to obtain is put into Muffle furnace, calcination temperature is 550 DEG C, and the heating-up time is
2h, soaking time are that 6h is calcined, and obtain the nanometer Zinc oxide powder of silver load.
The polyvinyl alcohol or polyacrylamide are water-soluble polymer, the preferred 20mg/mL-30mg/mL of mass concentration.
Wherein, polyvinyl alcohol needs 75 DEG C of heating water bath dissolutions, and zinc salt and silver salt is added by certain mass ratio after natural cooling.It is poly-
Acrylamide dissolves at normal temperature.The preferred 4:1-6:1 of the mass ratio of the zinc nitrate hexahydrate and water-soluble polymer.The nitre
The mass concentration of sour silver is 4mg/mL-16mg/mL.
Beneficial achievement of the invention:
First, above-mentioned preparation method use Vacuum Freezing & Drying Technology, solvent directly pass through distillation removal, avoid due to
The zinc oxide of the interparticle hard aggregation of surface tension of liquid bring, the silver load of preparation has higher crystallinity, crystal grain ruler
Very little distribution is more uniform, and hard aggregation is few；Second, improving nano silver using the water-soluble polymer that can generate abundant chain conformation
Particle size and chemical uniformity in aqueous polymer solution obtain the zinc oxide of the nano-Ag particles load of polymolecularity,
The dosage for reducing silver, reduces production cost；Third, organic solvent is not used, green non-pollution, raw material is cheap and easy to get, can
For industrialized production.
Detailed description of the invention
Fig. 1 is the SEM picture of the zinc oxide nano-powder of load silver prepared by embodiment 1；
Fig. 2 is the XRD diagram piece of the zinc oxide nano-powder of embodiment 1 and the preparation load silver of embodiment 2；
Fig. 3 is the DRS picture of the zinc oxide nano-powder of load silver prepared by embodiment 1 and embodiment 2；
Fig. 4 is the SEM picture of the zinc oxide nano-powder of load silver prepared by embodiment 3.
Specific embodiment
It is done below by preparation method of the embodiment to noble silver supported nano zinc oxide photocatalysis agent of the present invention
It further illustrates.
Embodiment 1
1.0g polyvinyl alcohol (PVA) is weighed in 100mL flask, 50mL deionized water is added, 75 DEG C of oil baths of flask are added
Thermal agitation 30min obtains the colorless and transparent colloidal sol of PVA that mass concentration is 20mg/mL.PVA aqueous solution is cooled to room temperature, is added
4.0g zinc nitrate hexahydrate [Zn (NO3)2·6H2O] and 400mg silver nitrate, 30min is stirred, polyvinyl alcohol-zinc nitrate-nitre is obtained
Sour silver solution.Above-mentioned solution is put into abundant pre-freeze in refrigerator, being subsequently placed in condenser temperature is -55 DEG C, operating pressure 10Pa
Freeze drier in be freeze-dried, obtain polyvinyl alcohol-zinc nitrate-silver nitrate (PVA-Zn-Ag) brown foam solid.It takes suitable
It measures above-mentioned solid to be put into crucible, is placed in 550 DEG C of heating 2h heat preservation 6h calcinings in Muffle furnace and obtains the nano oxidized of load silver
Zinc powder body.
The SEM figure of the nanometer Zinc oxide powder of load silver prepared by this example is shown in Fig. 1.From figure 1 it appears that it is brilliant
Particle size is evenly distributed, and average grain diameter is about 80-100nm, and rounded bulbous structure is presented in particle.
Embodiment 2
1.5g polyvinyl alcohol (PVA) is weighed in 100mL flask, 50mL deionized water is added, 75 DEG C of oil baths of flask are added
Thermal agitation 30min obtains the colorless and transparent colloidal sol of PVA that mass concentration is 30mg/mL.PVA aqueous solution is cooled to room temperature, is added
6.0g zinc nitrate hexahydrate [Zn (NO3)2·6H2O] and 600mg silver nitrate, 30min is stirred, polyvinyl alcohol-zinc nitrate-nitre is obtained
Sour silver solution.Above-mentioned solution is put into abundant pre-freeze in refrigerator, being subsequently placed in condenser temperature is -55 DEG C, operating pressure 10Pa
Freeze drier in be freeze-dried, obtain polyvinyl alcohol-zinc nitrate-silver nitrate (PVA-Zn-Ag) brown foam solid.It takes suitable
It measures above-mentioned solid to be put into crucible, is placed in 550 DEG C of heating 2h heat preservation 6h calcinings in Muffle furnace and obtains the nano oxidized of load silver
Zinc powder body.
Comparative example 1, example 2
Embodiment 1 is repeated, but is added without silver nitrate, obtains nano zine oxide I.
The nanometer Zinc oxide powder of load silver and the XRD diffraction pattern of nano zine oxide I prepared by example 1, example 2 are shown in figure
2, nano zine oxide I are typical hexagonal wurtzite structures, and for the sample of silver load, silver nano-grain is face-centered cubic knot
Structure observed the characteristic peak of apparent Ag；UV-vis DRS is as shown in figure 3, product prepared by example 1 and example 2
Occurs apparent absorption peak at 470nm.
Embodiment 3
1.0g polyacrylamide (PAM) is weighed in beaker, 50mL deionized water is added, 30min is stirred, it is dense to obtain quality
Degree is the colorless and transparent colloidal sol of PAM of 20mg/mL.4.0g zinc nitrate hexahydrate [Zn (NO is added3)2·6H2O] and 400mg nitric acid
Silver stirs 30min, obtains polyacrylamide-zinc nitrate-silver nitrate solution.Above-mentioned solution is put into abundant pre-freeze in refrigerator, so
Being placed on condenser temperature is -55 DEG C, is freeze-dried in the freeze drier that operating pressure is 10Pa, obtains polyacrylamide-nitre
Sour zinc-silver nitrate (PAM-Zn-Ag) brown foam solid.It takes appropriate above-mentioned solid to be put into crucible, is placed in Muffle furnace 550 DEG C
Heating 2h heat preservation 6h calcining obtains the nanometer Zinc oxide powder of load silver.
The SEM figure of the nanometer Zinc oxide powder of load silver prepared by this example is shown in Fig. 4.Figure 4, it is seen that its
Rounded bulbous structure is presented in grain part, and elongated club shaped structure is partially presented, wherein and the length of nanometer rods is about 1.0-2.5 μm,
Diameter is about 50-100nm, and the biggish ratio of height to diameter of nanometer rods increases the specific surface area of zinc oxide.
Embodiment 4
1.5g polyacrylamide (PAM) is weighed in beaker, 50mL deionized water is added, stirs 30min, it is saturating to obtain clarification
Bright mass concentration is the PAM aqueous solution of 30mg/mL.6.0g zinc nitrate hexahydrate [Zn (NO is added3)2·6H2O] and 600mg nitre
Sour silver, stirs 30min, obtains polyacrylamide-zinc nitrate-silver nitrate solution.Above-mentioned solution is put into abundant pre-freeze in refrigerator,
Being subsequently placed in condenser temperature is -55 DEG C, is freeze-dried in the freeze drier that operating pressure is 10Pa, obtains polyacrylamide -
Zinc nitrate-silver nitrate (PAM-Zn-Ag) brown foam solid.It takes appropriate above-mentioned solid to be put into crucible, is placed in 550 in Muffle furnace
DEG C heating 2h heat preservation 6h calcining i.e. obtain load silver nanometer Zinc oxide powder.
Claims (6)
1. a kind of noble silver supported nano zinc oxide raw powder's production technology, which comprises the steps of:
(1) polyvinyl alcohol of certain mass or polyacrylamide are dissolved in deionized water and stirred, obtained colourless
Bright colloidal sol；
(2) zinc nitrate hexahydrate and silver nitrate are added according to a certain percentage, reaction is sufficiently stirred, obtains water-soluble polymer-
Zinc nitrate-silver nitrate solution；
(3) it will be put into vacuum refrigerating machine and be dried after the abundant pre-freeze of sample described in step (2), obtain brown foam
Intermediate；
(4) the brown foam intermediate that step (3) is dried to obtain is put into crucible and is calcined in Muffle furnace, obtain silver
The nanometer Zinc oxide powder of load.
2. a kind of noble silver supported nano zinc oxide raw powder's production technology according to claim 1, which is characterized in that
Step (1) polyvinyl alcohol or polyacrylamide are water-soluble polymer, the preferred 20mg/mL-30mg/mL of mass concentration.
Wherein, polyvinyl alcohol needs 75 DEG C of heating water bath dissolutions, and zinc salt and silver salt is added by certain mass ratio after natural cooling.It is poly-
Acrylamide dissolves at normal temperature.
3. a kind of noble silver supported nano zinc oxide raw powder's production technology according to claim 1, which is characterized in that
The preferred 4:1-6:1 of mass ratio of step (2) zinc nitrate hexahydrate and water-soluble polymer.The quality of the silver nitrate of load is dense
Spend preferred 4mg/mL-16mg/mL.
4. a kind of noble silver supported nano zinc oxide raw powder's production technology according to claim 1, which is characterized in that
Step (3) dry technology uses Vacuum Freezing & Drying Technology.
5. a kind of noble silver supported nano zinc oxide raw powder's production technology according to claim 1, which is characterized in that
Step (4) calcination temperature is 550 DEG C, and the heating-up time is 2h, soaking time 6h.
6. a kind of load nano oxygen by the rounded bulbous of claim 1 to 5 the method preparation or the noble silver of club shaped structure
Change zinc powder body, which is characterized in that the diameter of the rounded bulbous structure silver supported nano zinc oxide powder is about 80-100nm, institute
The length for stating slender rod shaped structure silver supported nano zinc oxide powder is about 1.0-2.5 μm, and diameter is about 50-100nm；Silver nanoparticle
Particle successfully enters the lattice sites of zinc oxide, and the Zinc oxide powder of preparation is typical hexagonal wurtzite structure, silver nanoparticle
Particle is face-centred cubic structure.
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