CN106268805A - A kind of silver wolframic acid nano silver wire and preparation method thereof - Google Patents
A kind of silver wolframic acid nano silver wire and preparation method thereof Download PDFInfo
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- CN106268805A CN106268805A CN201610679930.3A CN201610679930A CN106268805A CN 106268805 A CN106268805 A CN 106268805A CN 201610679930 A CN201610679930 A CN 201610679930A CN 106268805 A CN106268805 A CN 106268805A
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- wolframic acid
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002253 acid Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 title abstract description 14
- 239000004332 silver Substances 0.000 title abstract description 14
- 239000002070 nanowire Substances 0.000 claims abstract description 41
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 29
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 16
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 10
- 238000013019 agitation Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000428 dust Substances 0.000 claims description 5
- 229950000845 politef Drugs 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000010894 electron beam technology Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 27
- 239000002105 nanoparticle Substances 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001311547 Patina Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
A kind of silver wolframic acid nano silver wire and preparation method thereof, belongs to semiconductor visible light catalysis material and technical field of nano material.The invention solves the problems that the electron beam utilizing transmission electron microscope or field emission scanning electron microscope to produce carrys out irradiation wolframic acid silver, method is cumbersome, it is impossible to the technical problem being prepared on a large scale.Nano wire of the present invention be with sodium tungstate and silver nitrate for primary raw material elder generation hydrothermal synthesis method synthesis wolframic acid nano silver wire after, more prepared with sodium borohydride chemical reduction method.Method: one, while stirring silver nitrate solution is dropwise added drop-wise in sodium tungstate solution, adjust pH value to 2.5 3, hydrothermal synthesis reaction, take deposit, successively with deionized water and dehydrated alcohol ultrasonic cleaning, vacuum drying；Two, Ag2WO4Nano wire adds in deionized water, ultrasonic disperse, magnetic agitation limit, limit dropping sodium borohydride solution；Three, then with washes of absolute alcohol, vacuum drying.The present invention is for the Photocatalytic Activity for Degradation of the environmental organic pollutants such as organic dyestuff.
Description
Technical field
The invention belongs to semiconductor visible light catalysis material and technical field of nano material；It is specifically related to one and there is height
Silver-wolframic acid nano silver wire of effect visible light photocatalysis characteristic and preparation method thereof.
Background technology
At present, energy crisis and environmental pollution become countries in the world problem demanding prompt solution, Photocatalitic Technique of Semiconductor
Develop into this two big world property difficult problem of solution and open a new path.Due to tradition catalysis material TiO2Absorb just
Ultraviolet light, and sunlight medium ultraviolet light only accounts for 5%, therefore exploitation novel visible catalysis material becomes research emphasis.Scientist
Deposited by noble metal nano particles, to build the approach such as heterojunction structure and doping modified to wide band gap semiconducter, develop simultaneously
New catalysis material is in order to improve further quasiconductor to the energy conversion efficiency of visible ray and utilization rate.
Xinhui Liu et al. is Ag under visible light exposure2WO4There is Ag on/AgCl surface+It is reduced into Ag nanoparticle, due to surface etc.
Gas ions resonance effect enhances Ag2WO4Visible light photocatalytic degradation rhodamine B (RhB) performance of/AgCl nano material
[Materials Letters,2013,91:129-132].Wolframic acid silver is a kind of semi-conducting material, and its optical band gap is 3.2eV,
There is stronger UV Absorption and catalysis characteristics.The at present research for wolframic acid ag material is concentrated mainly on micron particle, micro-
Rice stub and the preparation of nanometer stub and characterize on.Some documents report electron beam irradiation method at Ag at present2WO4Nanometer
Rod surface in situ growth Ag nanoparticle [J.Phys.Chem.C, 2014,118:1229-1239；Physical Chemistry
Chemical Physics,2015,17(7):5352-5359；Chemical Physics Letters,2016,644:68-
72].In these are reported, Ag2WO4Nanometer rods is smaller due to horizontal and vertical size, easily produces photocatalyst and reclaims tired
The problems such as difficulty, and the electron beam utilizing transmission electron microscope or field emission scanning electron microscope to produce carrys out irradiation wolframic acid silver, and method compares
Trouble, it is impossible to be prepared on a large scale.
Summary of the invention
The invention solves the problems that the electron beam utilizing transmission electron microscope or field emission scanning electron microscope to produce comes irradiation wolframic acid silver, side
Method is cumbersome, it is impossible to the technical problem being prepared on a large scale；And provide a kind of silver-wolframic acid nano silver wire and preparation method thereof.
This patent is on the basis of wolframic acid nano silver wire preparation technology before, with sodium borohydride chemical reduction method, in room temperature
Under conditions of and aqueous solution in, on nano wire, directly restore Ag0Nano-particle, has prepared what surface plasma strengthened
Ag/Ag2WO4Visible-light photocatalyst.
In the present invention, silver-wolframic acid nano silver wire is to synthesize tungsten with sodium tungstate and silver nitrate for primary raw material elder generation hydrothermal synthesis method
After acid nano silver wire more prepared with sodium borohydride chemical reduction method；Concrete preparation method is completed by following step:
Step one, being dropwise added drop-wise in sodium tungstate solution by silver nitrate solution while stirring, then dust technology adjusts pH value extremely
2.5-3, it is airtight in politef reactor for being subsequently placed in liner, drives reactor, takes deposit, depend on after hydrothermal synthesis reaction
Secondary deionized water and dehydrated alcohol ultrasonic cleaning, obtain wolframic acid nano silver wire after vacuum drying；
The Ag of step 2, step one preparation2WO4Nano wire adds in deionized water, ultrasonic disperse, then limit magnetic agitation
Limit dropping sodium borohydride solution；
Step 3, then with washes of absolute alcohol, vacuum drying, obtain silver-wolframic acid nano silver wire.
Silver nitrate solution is dropwise added drop-wise in sodium tungstate solution by step one while stirring, in above-mentioned sodium tungstate solution
Sodium tungstate is 1:2 with the mol ratio of the silver nitrate in silver nitrate solution, and then dust technology adjusts pH value to 2.5-3, is subsequently placed in interior
Lining is airtight in politef reactor, and hydrothermal synthesis reaction 12h under the conditions of 120～180 DEG C drives reactor, takes deposition
Thing, successively with deionized water and dehydrated alcohol ultrasonic cleaning, then obtains wolframic acid silver nanoparticle after vacuum drying 2h under the conditions of 60 DEG C
Line.
Ultrasonic cleaning described in step one is carried out in the steps below: step 1, by clear for deposit deionized water
Wash, then ultrasonic cleaning 3～5min, more centrifugal 5min under the conditions of 15000r/min；Step 2, repetition step 1 operate 1～2
Secondary；Step 3, finally with dehydrated alcohol eccentric cleaning once.
In step 2, sodium borohydride solution preparation method is that the NaOH solution of pH=12 is placed in ice bath (temperature 0～4 DEG C)
In, magnetic agitation, it is slowly added to NaBH4To being completely dissolved, obtain sodium borohydride solution.
By 0.15g Ag in step 22WO4Nano wire adds 50mL deionized water, and sodium borohydride solution consumption is (60-
1000) μ L, sodium borohydride solution is with 25mLNaOH solution and 12mg NaBH4Preparation.
In step 2, the ultrasonic disperse time is 2～3min.
Step 2 carries out magnetic agitation with 700～800r/min rotating speeds.
Step 2 drips sodium borohydride solution with liquid-transfering gun.
With dehydrated alcohol eccentric cleaning twice under the conditions of 16000r/min, 5min in step 3；Under the conditions of 60 DEG C very
Empty dry 2h.
The present invention uses simple hydro-thermal one-step synthesis, prepares nano wire with sodium tungstate and silver nitrate for raw material, then adopts
Use NaBH4Reducing process is reduced directly out Ag nano-particle in nanowire surface, the Ag nano particle in situ of generation at Ag2WO4Receive
Nanowire surface grows, and generates Ag/Ag2WO4Nano wire.
The present invention uses simple hydrothermal synthesis method and chemical reduction method synthesis to have the new of efficient visible light catalytic effect
Type silver-wolframic acid nano silver wire, has production technology simple, can be prepared on a large scale, and production cost is low, nano wire pattern is excellent, can
See that light absorbs and catalytic efficiency advantages of higher, have in the Photocatalytic Activity for Degradation of the environmental organic pollutants such as organic dyestuff
Important actual application value and using value.
Accompanying drawing explanation
Fig. 1 is prepared Ag/Ag2WO4Scanning electron microscopy (SEM) photo of nano wire sample；
Fig. 2 is Ag2WO4Nano wire and Ag/Ag2WO4The C1s orbital electron of nano wire combines can high-resolution x-ray photoelectron
Power spectrum；
Fig. 3 is Ag2WO4Nano wire and Ag/Ag2WO4The Ag3d orbital electron of nano wire combines can high-resolution X-ray photoelectricity
Sub-power spectrum；
Fig. 4 is Ag2WO4Nano wire and Ag/Ag2WO4The W4f orbital electron of nano wire combines can high-resolution x-ray photoelectron
Power spectrum；
Fig. 5 is Ag2WO4Nano wire and Ag/Ag2WO4The O1s orbital electron of nano wire combines can high-resolution x-ray photoelectron
Power spectrum；
Fig. 6 is the solid ultraviolet-visible absorption spectroscopy of the silver-wolframic acid nano silver wire of different silver reduction；
Fig. 7 is Ag2WO4And Ag/Ag2WO4Nano wire catalytic performance comparison diagram under visible light illumination.
Detailed description of the invention
Detailed description of the invention one: a kind of silver-wolframic acid nano silver wire and preparation method thereof in present embodiment, it is characterised in that
This preparation method is completed by following step:
Step one, it is that to be dropwise added drop-wise to 50ml concentration be 0.005M to 0.01M silver nitrate solution by 50ml concentration while stirring
In sodium tungstate solution (time is 15-20 minute), the sodium tungstate in described sodium tungstate solution and the silver nitrate in silver nitrate solution
Mol ratio be 1:2, then dust technology (mass percent concentration is 2%) adjust pH value to 2.5, being subsequently placed in liner is polytetrafluoro
In ethylene (PTFE) reactor (still material is chrome-nickel (304II)), tighten reactor with bench vice, put into electric heating forced air drying
In case, under the conditions of design temperature is 150 DEG C, carry out hydrothermal synthesis reaction 12h；Hydro-thermal reaction cools down after terminating, and drives reactor,
Supernatant in reactor inner bag is removed, takes deposit, clean, obtain wolframic acid silver after being vacuum dried 2h under the conditions of 60 DEG C and receive
Rice noodle.
Wherein, the cleaning described in step one is carried out in the steps below:
Step 1, by deposit with deionized water clean, then ultrasonic cleaning 5min, then under the conditions of 15000r/min from
Heart 5min；
Step 2, repetition step 1 operate 2 times；
Step 3, finally with dehydrated alcohol eccentric cleaning once.
The Ag of step 2,0.15g step one preparation2WO4Nano wire adds in 50mL deionized water, in ultrasonic cleaner
Ultrasonic disperse 2min, then with 700r/min rotating speed magnetic agitation, with liquid-transfering gun to Ag2WO4Nanowire dispersion drips 200 μ L
Sodium borohydride solution；
Sodium borohydride solution preparation method described in step 2 is that water is placed in refrigerator freezing 2h, obtains ice bath, by 25mL
The NaOH solution of pH=12 is placed in ice bath (temperature 0～4 DEG C), with 700r/min rotating speed magnetic agitation, is slowly added to 12mg
NaBH4To being completely dissolved, obtain sodium borohydride solution.
Step 3, then with dehydrated alcohol eccentric cleaning twice under the conditions of 16000r/min, 5min, under the conditions of 60 DEG C
Vacuum drying 2h, obtains silver-wolframic acid nano silver wire.
Silver-wolframic acid the nano silver wire preparing present embodiment method detects, and result is as shown in figs. 1-7.
Fig. 1 is the Ag/Ag obtained according to above-mentioned preparation method2WO4Scanning electron microscopy (SEM) photo of nano wire sample.
Can be seen that nanowire surface has obvious nano-particle to adhere to, these nano-particle are exactly by NaBH4Revert to nano wire table
The Ag nanoparticle in face, surface has the sample of Ag nanoparticle to remain in that the pattern of nanometer rods simultaneously, and a small amount of reduction is described
Agent NaBH4Do not destroy the structure of original wolframic acid nano silver wire.
Fig. 2-5 is Ag2WO4Nano wire and Ag/Ag2WO4C1s, Ag3d, W4f and O1s orbital electron of nano wire combines
Can high-resolution x-ray photoelectron power spectrum.In Ag3d electronics high-resolution x-ray photoelectron power spectrum from Fig. 2-5 it can be seen that
Ag2WO4In nano wire sample, Ag3d5/2And Ag3d3/2Electron binding energy is respectively 368.0eV and 374.2eV, two Ag3d peak energy
Amount difference is 6.2eV, and the Ag/Ag after patina2WO4In nano wire sample, Ag3d5/2And Ag3d3/2Electron binding energy is respectively
368.2eV and 374.3eV, two Ag3d peak energy differences are 6.1eV.This result indicates sodium borohydride at Ag2WO4Nano wire
Surface in situ has restored Ag0Granule.Comparing Ag3d electron binding energy, the peak position of W4f and O1s electron binding energy is before patina
After all keep constant, indicate the quantivalence of W and O element in sample and do not change, respectively with+6 valencys and the-form of divalent
Exist.
Table 1 is Ag2WO4And Ag/Ag2WO4The XPS elemental composition table of nano wire, according to the Ag3d of x-ray photoelectron power spectrum,
W4f, O1s peak area, after deduction C1s, tri-kinds of element percentages of the W/Ag/O being converted into are as shown in table 1.Result of calculation table
Bright through NaBH4The Ag of reduction2WO4Nano wire, surface silver element atomic percent increases to 24.7% from 20.4%, indicates
Surface silver content increases, and can speculate Ag the most further0Exist.
Table 1
Fig. 6 is the solid ultraviolet-visible absorption spectroscopy of the silver-wolframic acid nano silver wire of different silver reduction.Can from absorption spectrum
To find out, along with the increase of surface silver also commercial weight, the nano wire light in visible region absorbs and is obviously enhanced.This light absorption effect
It is due to surface metal Ag0The surface plasmon resonance effect of nano-particle causes.
Fig. 7 is Ag2WO4And Ag/Ag2WO4Nano wire catalytic performance under visible light illumination compares.Can from Fig. 7
Go out, prepared Ag2WO4Nano wire under visible light illumination, the methylene blue solution of photocatalysis 10mg/L, urge by 60 minute time
The degradation efficiency changing degradation of methylene blue solution reaches 63%.And the Ag/Ag after patina2WO4Nano wire is for methylene blue solution
Photocatalytic degradation efficiency reached 91% when 60 minutes.As can be seen here, the Ag/Ag prepared by this patent2WO4Nano wire due to
The Ag on surface0The surface plasma resonance effect that nano-particle produces, enhances the visible absorption performance of wolframic acid nano silver wire,
Thus improve photocatalysis performance.Ag/Ag after patina2WO4Nano wire photocatalysis efficiency under visible light is not than through silver
The Ag changed2WO4The photocatalysis efficiency of nano wire improves 44.4%.
Claims (10)
1. silver-wolframic acid nano silver wire, it is characterised in that silver-wolframic acid nano silver wire is with sodium tungstate and silver nitrate for the most former
After material first hydrothermal synthesis method synthesis wolframic acid nano silver wire more prepared with sodium borohydride chemical reduction method.
The preparation method of a kind of silver-wolframic acid nano silver wire the most as claimed in claim 1, it is characterised in that this preparation method is logical
Cross what following step completed:
Step one, being dropwise added drop-wise in sodium tungstate solution by silver nitrate solution while stirring, then dust technology adjusts pH value to 2.5-
3, it is airtight in politef reactor for being placed in liner, and then hydrothermal synthesis reaction is driven reactor, taken deposit, uses successively
Deionized water and dehydrated alcohol ultrasonic cleaning, obtain wolframic acid nano silver wire after vacuum drying；
The Ag of step 2, step one preparation2WO4Nano wire adds in deionized water, and ultrasonic disperse, then magnetic agitation limit in limit is dripped
Add sodium borohydride solution；
Step 3, then with washes of absolute alcohol, vacuum drying, obtain silver-wolframic acid nano silver wire.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that in step one, limit is stirred
Mix limit to be dropwise added drop-wise in sodium tungstate solution by silver nitrate solution, in the sodium tungstate in above-mentioned sodium tungstate solution and silver nitrate solution
The mol ratio of silver nitrate be 1:2, then dust technology adjusts pH value to 2.5～3, and being subsequently placed in liner is politef reactor
In airtight, under the conditions of 120～180 DEG C, hydrothermal synthesis reaction 12h, drives reactor, takes deposit, successively by deionized water and nothing
Water-ethanol ultrasonic cleaning, then obtain wolframic acid nano silver wire after vacuum drying 2h under the conditions of 60 DEG C.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 3, it is characterised in that described in step one
Ultrasonic cleaning carry out in the steps below:
Step 1, deposit deionized water is cleaned, then ultrasonic cleaning 3～5min, more centrifugal under the conditions of 15000r/min
5min；
Step 2, repetition step 1 operate 1～2 time；
Step 3, finally with dehydrated alcohol eccentric cleaning once.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that boron hydrogen in step 2
Changing sodium solution preparation method is in the ice bath that the NaOH solution of pH=12 is placed in temperature 0～4 DEG C, and magnetic agitation is slowly added to
NaBH4To being completely dissolved, obtain sodium borohydride solution.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that will in step 2
0.15g Ag2WO4Nano wire adds 50mL deionized water, and sodium borohydride solution consumption is (60-1000) μ L, sodium borohydride solution
It is with 25mLNaOH solution and 12mg NaBH4Preparation.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that ultrasonic in step 2
Jitter time is 2～3min.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that in step 2 with
700-800r/min rotating speed carries out magnetic agitation.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that with moving in step 2
Liquid rifle dropping sodium borohydride solution.
The preparation method of a kind of silver-wolframic acid nano silver wire the most according to claim 2, it is characterised in that use in step 3
Dehydrated alcohol is eccentric cleaning twice under the conditions of 16000r/min, 5min；2h it is vacuum dried under the conditions of 60 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107096549A (en) * | 2017-03-30 | 2017-08-29 | 常州大学 | A kind of preparation method of the compound silver bromide photochemical catalyst of wolframic acid silver |
| CN108435172A (en) * | 2018-04-19 | 2018-08-24 | 上海泽铭环境科技有限公司 | A kind of ultraviolet optical drive nano-composite catalyst |
| CN110560100A (en) * | 2019-08-16 | 2019-12-13 | 南京理工大学 | Z-Scheme AgBr/Ag8W4O16Method for synthesizing photocatalyst |
| CN110802903A (en) * | 2019-11-21 | 2020-02-18 | 哈尔滨工业大学 | Preparation method of stretchable flexible transparent electrochromic film |
| CN112076797A (en) * | 2020-09-18 | 2020-12-15 | 苏州讯罡智能设备有限公司 | Preparation method of visible light driven composite photocatalyst |
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| CN103638929A (en) * | 2013-12-13 | 2014-03-19 | 江苏大学 | Graphene-silver tungstate composite photocatalytic material as well as preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107096549A (en) * | 2017-03-30 | 2017-08-29 | 常州大学 | A kind of preparation method of the compound silver bromide photochemical catalyst of wolframic acid silver |
| CN108435172A (en) * | 2018-04-19 | 2018-08-24 | 上海泽铭环境科技有限公司 | A kind of ultraviolet optical drive nano-composite catalyst |
| CN110560100A (en) * | 2019-08-16 | 2019-12-13 | 南京理工大学 | Z-Scheme AgBr/Ag8W4O16Method for synthesizing photocatalyst |
| CN110560100B (en) * | 2019-08-16 | 2022-11-18 | 南京理工大学 | Z-Scheme AgBr/Ag 8 W 4 O 16 Method for synthesizing photocatalyst |
| CN110802903A (en) * | 2019-11-21 | 2020-02-18 | 哈尔滨工业大学 | Preparation method of stretchable flexible transparent electrochromic film |
| CN112076797A (en) * | 2020-09-18 | 2020-12-15 | 苏州讯罡智能设备有限公司 | Preparation method of visible light driven composite photocatalyst |
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