CN105692700B - In high ion concentration plating solution can stable suspersion tungsten trioxide nano particle preparation method and application - Google Patents
In high ion concentration plating solution can stable suspersion tungsten trioxide nano particle preparation method and application Download PDFInfo
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- CN105692700B CN105692700B CN201610018894.6A CN201610018894A CN105692700B CN 105692700 B CN105692700 B CN 105692700B CN 201610018894 A CN201610018894 A CN 201610018894A CN 105692700 B CN105692700 B CN 105692700B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention disclose it is a kind of in high ion concentration plating solution can stable suspersion tungsten trioxide nano particle preparation method, with sodium tungstate as raw material, hydrochloric acid is precipitating reagent, and lauryl sodium sulfate and polyacrylic acid are coating material.Lauryl sodium sulfate is mixed with polypropylene uniform stirring, mixed solution is added to into Na2WO4In the aqueous solution, under agitation, dense HC1 solution is rapidly joined in the system, occur to yellow mercury oxide；Then by reaction system at room temperature, ultrasonic agitation reaction.After reaction terminates, by nanometer WO3Filter, wash, and be vacuum dried.The preparation process is simple, cycle is short, and product is easy to keeping, super quality and competitive price.
Description
Technical field
The present invention relates to field of nanometer technology, more particularly to a kind of WO with well suspended3Nano-particle, more
Body is to be related to a kind of WO suitable for composite plating3Nano-particle.
Background technology
The earliest application of composite plating will trace back to nineteen twenty-eight (Fink C G, Prince J D.Codeposition of
Copper and graphite [J] .Trans.Am.Electrochem.Soc., 1928,54：315-321), this method is used
To prepare the copper-graphite electrode composite deposite on car engine.From twentieth century beginning of the fifties the to the end of the sixties, with regard to this respect
Research increase gradually (Williams R V.Electrodeposited Composite Coatings [J]
.Electroplating and Metal Finishing, 1966,19 (3)：92-96.).The twentieth century seventies to 80 years
During this section, the focus of research is concentrated mainly on the mechanical strength of strengthening membrane, anti-corrosion, wear-resisting property.Until in 20 generation
Record the beginning of the nineties, Kunugi et al. takes the lead in preparing Ni+PTFE using composite plating, and uses it for electrocatalytic oxidation organic matter
(Kunugi Y, Fuchigami T, Nonaka T, Matsumura S.Electrolysis using composite-
plated electrodes：Part II.Electrooxidation of alcohols at a hydrophobic
nickel/poly(tetrafluoroethylene)composite-plated anode[J].Journal of
Electroanalytical Chemistry and Interfacial Electrochemistry, 1990,287：385-
388；Kunugi Y, Kumada R, Nonaka T, Chong T B, Watanabe N.Electrolysis using
composite-plated electrodes：Part III.Electroorganic reactions on a
hydrophobic Ni/PTFE composite-plated nickel electrode[J].Journal of
Electroanalytical Chemistry and Interfacial Electrochemistry, 1991,313：215-
225].Hereafter, the researcher such as Musiani M, Kawai, Yoneyama has carried out a series of researchs successively, is prepared using the method
Go out the composite functional material such as various catalysis, photosensitive, energy storage (Musiani M.Electrodeposition of Composites：
An Expanding Subject in Electrochemical Materials Science[J].Electrochimica
Acta, 2000,45 (20)：3397-3402；Musiani M, Furlanetto F, Bertoncello
R.Electrodeposited PbO2+RuO2：a composite anode for oxygen evolution from
Sulphuric acid solution [J] .Journal of Electroanalytical Chemistry, 1999,465：
160-167；Kawai K, Mihara N, Kuwabata S, Yoneyama H.Electrochemical Synthesis of
Polypyrrole Films Containing TiO2 Powder Particles[J].Journal of
Electrochemistry Society, 1990,137：1793-1796；Yoneyama H, Kishimoto A, Kuwabata
S.Charge-discharge properties of polypyrrole films containing manganese
Dioxide particles [J] .Journal of the Chemical Society, Chemical Communications,
1991,15：986-987；Kuwabata S, Kishimoto A, Tanaka T, Yoneyama H. Electrochemical
Synthesis of Composite Films of Manganese Dioxide and Polypyrrole and Their
Properties as an Active Material in Lithium Secondary Batteries[J].Journal of
Electrochemistry Society, 1994,141 (1)：10-15).
With the development of nanometer technology, composite plating is combined with nanometer technology, according to electrocrystallization theory and dispersion-strengtherning
Theory, by electrochemical method, makes one or more insoluble nano-solid particles occur altogether in electrode surface with metal ion
Deposition, nano-particle is wrapped in metal oxide matrix, so as to obtain composite function nano material.
The property that it is critical only that doping particle of composite plating --- the particle diameter of particle, density, electric conductivity, wetability and
Crystalline structure all can bring impact to deposition process.The particle diameter of particle is less, and the wettability of particle is better, is more advantageous in that suitable
Sharp is co-deposited with metal/metal oxide；The strong particle of conductive capability is more easily embedded in coating.So, prepare and be adapted to use
In the nano-particle of composite plating be the key of the technical field.
The content of the invention
Goal of the invention：To solve problems of the prior art, the present invention provides one kind in high ion concentration plating solution
Can stable suspersion tungsten trioxide nano particle preparation method, by choose coating material species and consumption, increased
WO3Nano-particle dispersed and suspension in the plating solution.
Technical scheme：To realize above-mentioned technical purpose, the present invention provide can in high ion concentration plating solution stable suspersion
WO3The preparation method of nano-particle comprises the steps：
(1) it is 3～5: 1～2 by mass percentage by 5～15wt% lauryl sodium sulfate and 2～6wt% polyacrylic acid
It is mixed and stirred for, is obtained surface modification liquid；
(2) in 95～100 DEG C of water-bath, the surface modification liquid is added to into 2～6wt%Na2WO4In the aqueous solution simultaneously
Stirring, wherein, surface modification liquid and Na2WO4The aqueous solution or amount ratio for 4: 1～3: 1；
(3) under agitation, 10 are added into system with the speed of 1s/ drops in the system for obtaining to step (2)～
30wt% hydrochloric acid solutions, occur to yellow mercury oxide；
(4) reaction system that step (3) is obtained is cooled down at room temperature, ultrasonic agitation；
(5) yellow product filtered, washed, after vacuum drying, obtain WO3Nano-particle.
Preferably, in step (1), stirring condition is 5～15min of magnetic agitation, and rotating speed is 200～400r/min.
In step (2), stirring condition is to be stirred under the conditions of rotating speed is 100～200r/min.
In step (3), rate of addition is 0.05～0.1ml/s.
Wherein, described high ion concentration plating solution is containing 0.5～0.2mol/L Pb2+Plating solution.
In one preferred embodiment, the concentration of sodium tungstate for 4wt%HCl solution concentration be 20wt%, 12
The concentration of sodium alkyl sulfate solution is 10wt%, and the concentration of polyacrylic acid solution is 4wt%.
The WO prepared by above-mentioned preparation method3Nano-particle is equally within the scope of the present invention.
Present invention further proposes WO3Application of the nano-particle in composite plating.
Beneficial effect：Compared with prior art, the present invention is by from properly mixed lauryl sodium sulfate and poly- third
, used as coating material, with sodium tungstate as raw material, hydrochloric acid is used as precipitating reagent, the WO of preparation for olefin(e) acid3Nano-particle is dense in macroion
(can be in the Pb containing 0.5～0.2mol/L with excellent suspension in the electroplate liquid of degree2+Plating solution in stable suspersion), it is this to receive
Rice corpuscles has good application in composite plating, and preparation method is simple, it is easy to keeping, super quality and competitive price.
Description of the drawings
Figure 1A is the stereoscan photograph of nano-particle prepared by embodiment 1, and nano-particle prepared by Figure 1B comparative examples 1
Stereoscan photograph；
Fig. 2 is the suspendability contrast in the plating solution of comparative example 1 and 1 product of embodiment；
Contrast photos of the Fig. 3 for comparative example 1 and 1 product of embodiment suspension situation in the plating solution, wherein, upper row is enforcement
Example 1, lower row are comparative example 1.
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.
Embodiment 1：It is a kind of can in high ion concentration plating solution stable suspersion WO3The preparation method of nano-particle.
First ensure that producing region and equipment clean and dry, by using vessel clean up and sterilize.
Specific implementation step is as follows：
(1) by 10% lauryl sodium sulfate of 20ml and 4% polyacrylic acid of 10ml by being mixed, and magnetic agitation
10min, rotating speed are 300r/min
(2) in 97 DEG C of water-bath, above-mentioned mixed solution is added to into 10mL 4%Na2WO4In the aqueous solution, in rotating speed it is
It is stirred under the conditions of 200r/min；
(3) under agitation, 20mL20% hydrochloric acid solutions are rapidly joined in the system, is occurred to yellow mercury oxide；
(4) reaction system is cooled down at room temperature, ultrasonic agitation is reacted 8 minutes, and supersonic frequency is 100Hz.
(5) yellow product filtered, washed, then 12h is vacuum dried under the conditions of 50 DEG C, obtains WO3Nano-particle.
Above-mentioned WO3Application of the nano-particle in composite plating：
The configuration of plating solution：
Prepare 100mL 0.2mol/L Pb (NO3)2, 0.1mol/L HNO3Solution.5mmol/L is added in the solution
WO3Nano-particle, ultrasonic agitation 10 minutes.Observe its suspension situation.
Suspension situation by product in above-mentioned plating solution, WO obtained in the present embodiment3Nanoparticle product is in height
In the plating solution of ion concentration, dispersiveness and suspension are good, and substantially sedimentation is had no in 1h, part occur and settle after 2h.
Embodiment 2：A kind of WO suitable for composite plating3The preparation method of nano-particle.
Guarantee producing region and equipment clean and dry, by using vessel clean up and sterilize.
Preparation process substantially with embodiment 1, except for the difference that：
Fill a prescription and be：20mL 4wt%Na2WO4The aqueous solution, the sodium dodecyl sulfate solution of 20mL 5wt%, 35mL
20wt%HCl solution.
Then according to prepared by method prepared by embodiment 1, and in being dispersed in plating solution described in embodiment 1, detect which hangs
Buoyancy energy.
Add the sodium dodecyl sulfate solution of 20mL 5% most suitable, but remain to see substantially sedimentation.Dodecyl
Sodium sulphate addition is excessive, WO3Yield is high substantially to be reduced, and suspension is general；Lauryl sodium sulfate addition is very few, WO3Easily
Reunite, suspension is poor.
Embodiment 3：A kind of WO suitable for composite plating3The preparation method of nano-particle.
Guarantee producing region and equipment clean and dry, by using vessel clean up and sterilize.
Preparation process substantially with embodiment 1, except for the difference that：
Fill a prescription and be：20mL 2%Na2WO4The aqueous solution, the polyacrylic acid solution of 20mL 2.5～30%, 35mL 20%HCl
Solution.
Then according to prepared by method prepared by embodiment 1, and in being dispersed in plating solution described in embodiment 1, detect which hangs
Buoyancy energy.
As a result show, when the polyacrylic acid solution of 20mL 4% is added in experiment, and suspension is good.Polyacrylic acid addition
When excessive, WO3It is difficult to be formed, yield is substantially reduced, reaction solution is in light yellow, and settles rapidly；Polyacrylic acid addition mistake
When few, WO3Can reunite rapidly and settle.
Embodiment 4：A kind of WO suitable for composite plating3The preparation method of nano-particle.
Guarantee producing region and equipment clean and dry, by using vessel clean up and sterilize.
Preparation process substantially with embodiment 1, except for the difference that：
Fill a prescription and be：20mL 2%Na2WO4The aqueous solution, the lauryl sodium sulfate of 10mL 10%, 1% polyacrylic acid of 10mL
Solution, 35mL 20%HCl solution.
Then according to prepared by method prepared by embodiment 1, and in being dispersed in plating solution described in embodiment 1, detect which hangs
Buoyancy energy.
As a result show, the lauryl sodium sulfate of addition is appropriate, and polyacrylic acid addition it is very few when, WO3Suspension one
As, it is not obviously improved.
Embodiment 5：A kind of WO suitable for composite plating3The preparation method of nano-particle.
Guarantee producing region and equipment clean and dry, by using vessel clean up and sterilize.
Preparation process substantially with embodiment 1, except for the difference that：
Fill a prescription and be：20mL 2%Na2WO4The aqueous solution, the lauryl sodium sulfate of 10mL 10%, 10mL30% polyacrylic acid
Solution, 35mL 20%HCl solution.
Then according to prepared by method prepared by embodiment 1, and in being dispersed in plating solution described in embodiment 1, detect which hangs
Buoyancy energy.
The lauryl sodium sulfate of addition is appropriate, and polyacrylic acid addition it is excessive when, WO3Particle is difficult to be formed, yield
Substantially reduce, reaction solution is in light yellow, and particle precipitation is very fast.
Comparative example 1：
In the case where any coating material is not added with, in 97 DEG C of water-bath, 40mL 2%Na2WO4In the aqueous solution,
Under stirring condition, 35mL 20%HCl solution is rapidly joined in the system, occurred to yellow mercury oxide；Then reaction system is existed
Under room temperature, ultrasonic agitation is reacted 8 minutes.After reaction terminates, product filtered, washed, be then vacuum dried under the conditions of 50 DEG C
Yellow WO is obtained after 12h3Nano-particle.
Comparative example 1 does not add any coating material, the product is dispersed in plating solution described in embodiment 1 and detects its suspension
Performance, its result and embodiment 1 contrast as shown in Figure 1, Figure 2 and Figure 3.
Figure 1A is 1 stereoscan photograph of embodiment, and the stereoscan photograph of Figure 1B comparative examples 1, can by Figure 1A, B contrast
Know, nanometer sheet of 1 product of embodiment for 100nm × 100nm × 10nm, and favorable dispersibility, and 1 product of comparative example is rolled into a ball completely
Poly-, prepared nanometer sheet is intersected with each other, defines blade inserting " particle cluster ".
From Fig. 2 and Fig. 3, the 1 product sinking speed of comparative example without any surface modification is very fast, almost reaches after 2h
To 100% sedimentation, and through surface modification 1 product of embodiment in the plating solution of high ion concentration can stable suspersion, in 1h not
See substantially sedimentation, occur part after 2h and settle.Illustrate that 1 product of embodiment has very big application prospect in composite plating.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of without departing from the technology of the present invention principle, some improvement and modification can also be made, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (6)
1. it is a kind of in high ion concentration plating solution can stable suspersion tungsten trioxide nano particle preparation method, its feature exists
In comprising the steps：
(1) 5～15wt% lauryl sodium sulfate and 2～6wt% polyacrylic acid are carried out for 3～5: 1～2 by mass percentage
It is mixed and stirred for, obtains surface modification liquid；
(2) in 95～100 DEG C of water-bath, the surface modification liquid is added to into 2～6wt%Na2WO4In the aqueous solution and stir,
Wherein, surface modification liquid and Na2WO4The mass ratio of the aqueous solution is 4: 1～3: 1；
(3) under agitation, 10～30wt% hydrochloric acid solutions are added dropwise into system in the system for obtaining to step (2), to Huang
Color precipitation occurs；
(4) reaction system that step (3) is obtained is cooled down at room temperature, ultrasonic agitation；
(5) yellow product filtered, washed, after vacuum drying, obtain WO3Nano-particle,
Wherein, described high ion concentration plating solution is containing 0.5～0.2mol/L Pb2+Plating solution.
2. preparation method according to claim 1, it is characterised in that in step (1), stirring condition be magnetic agitation 5～
15min, rotating speed are 200～400r/min.
3. preparation method according to claim 1, it is characterised in that in step (2), it is 100 in rotating speed that stirring condition is
It is stirred under the conditions of～200r/min.
4. preparation method according to claim 1, it is characterised in that the concentration of sodium tungstate is 4wt%HCl, solution it is dense
Spend for 20wt%, the concentration of sodium dodecyl sulfate solution is 10wt%, and the concentration of polyacrylic acid solution is 4wt%.
5. preparation method according to claim 1, it is characterised in that in step (3), rate of addition are 0.05～0.1ml/
s。
6. the tungsten trioxide nano particle that the preparation method described in any one of Claims 1 to 5 is prepared.
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| CN112103087B (en) * | 2020-09-17 | 2021-10-15 | 西北大学 | Method for preparing carbon quantum dot modified multistage tungsten trioxide-foamed nickel composite material and application thereof |
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| CN104962977B (en) * | 2015-06-03 | 2017-03-22 | 昆明理工大学 | Preparation method of rod-shaped bimetallic-based composite anode material |
| CN105154942A (en) * | 2015-10-09 | 2015-12-16 | 桂林理工大学 | Method for preparing Ni-P-WO3 nano-composite coating through pulse electrodeposition |
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