CN106185965A - The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide - Google Patents
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide Download PDFInfo
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- CN106185965A CN106185965A CN201610573298.4A CN201610573298A CN106185965A CN 106185965 A CN106185965 A CN 106185965A CN 201610573298 A CN201610573298 A CN 201610573298A CN 106185965 A CN106185965 A CN 106185965A
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- silicic acid
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- silicon dioxide
- microsphere
- acid nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of simple batch preparation preparing hollow silicic acid nickel microsphere with silicon dioxide for template.The method comprises the following steps: first by nano silicon ultrasonic disperse in deionized water, obtain white emulsion；It is subsequently adding carbamide and water soluble nickel salt, continues to be uniformly dispersed, obtain green emulsion；Then, the green emulsion obtained is transferred in there-necked flask, condensing reflux 1～24h under conditions of temperature is 80～120 DEG C；Finally, after alkali liquor etching 1～24h, it is dried to obtain hollow silicic acid nickel microsphere.Present invention process is simple, and easy and simple to handle, manufacturing cycle is short；Process is pollution-free, and cost of material used is relatively low, it is not necessary to specific response container, is suitable for mass production.
Description
Technical field
The present invention relates to a kind of field of inorganic material preparing technology with hollow-core construction, being specifically related to one with silicon dioxide is
Template prepares the method for hollow silicic acid nickel microsphere.
Background technology
Tiny balloon is to be developed by core/shell composite structure material, can be by regulating heterogeneous core shell compound particle
Structure, size and composition reach the controllable adjustment to its character, thus realize its optics, calorifics, electricity, magnetics and catalysis
The regulation and control on a large scale of character.Owing to the material of this class formation has low-density, high-ratio surface, high stability and Surface Permeability
Characteristic, and its hollow parts can accommodate substantial amounts of guest molecule or large-sized object, can produce some peculiar bases
The character of effect " is wrapped up " so that hollow microspheres is at catalyst, battery, medicine control, photoelectric material, sensor in microcosmic
Technical fields many with environmental science etc. have important effect (chemical industry is in progress, 2004,23 (6), 595-599).
The tradition preparation of hollow-core construction silicic acid nickel and composite inorganic membranes thereof is hydro-thermal method, owing to hydro-thermal reaction used by needs
Still, so real time reaction situation cannot be observed.Meanwhile, the control of actual temperature also Relative Fuzzy in reactor.Mould plate technique is
At present the most effective and practical in synthesis hollow-core construction technology, template is as the most frequently used a kind of nano-hollow ball of preparing
Method is widely used in the preparation of various nano material, the existing phase of its application in prepared by polymer nanocomposite hollow ball
Close research report, and technology relative maturity.Deposit or reaction at template surface by controlling presoma, form Surface coating
Layer；Then with dissolving, heating or the method such as chemical reaction remove template, i.e. can get hollow-core construction (material Leader B: a research piece,
2015,28(5),86-88；Patent CN 103252237A；Patent CN 104624126A).
Owing to high-pressure hydrothermal reaction kettle preparation condition is harsh, yield is few, and cost is high, and the present invention provides under a kind of condition of normal pressure
The method being prepared on a large scale, has important value to industrialized mass production.Further, had not yet to see at ambient pressure, with dioxy
SiClx is the method report that template is prepared on a large scale hollow-core construction silicic acid nickel microsphere.
Summary of the invention
[solving the technical problem that]
Present invention aim to address above-mentioned prior art problem, it is provided that one prepares hollow silicon with silicon dioxide for template
The method of acid nickel microsphere.The method reaction condition is gentle, overcomes conventional autoclave condition harshness, complex process and difficulty
With shortcomings such as large-scale production, the method can produce hollow silicic acid nickel microsphere at ambient pressure in enormous quantities.
[technical scheme]
In order to reach above-mentioned technique effect, the present invention takes techniques below scheme:
A kind of method preparing hollow silicic acid nickel microsphere for template with silicon dioxide, the method comprises the following steps: first
By nano silicon ultrasonic disperse in deionized water, white emulsion is obtained；It is subsequently adding carbamide and water soluble nickel salt, stirring
It is uniformly dispersed, obtains green emulsion；Then, the green emulsion obtained is transferred in there-necked flask, be 80～120 DEG C in temperature
Under conditions of condensing reflux 1～24h；Finally, after alkali liquor etching 1～24h, it is dried to obtain hollow silicic acid nickel microsphere.
The present invention further technical scheme, described water soluble nickel salt is nickel nitrate, Nickel dichloride., nickel sulfate, nickel acetate,
And the mixture of one or more in hydrate.
Alkali liquor described in the present invention further technical scheme is sodium hydroxide, potassium hydroxide, Lithium hydrate, hydroxide
The mixture of one or more in rubidium, Cesium hydrate., barium hydroxide.
The present invention further technical scheme, the addition matter between described water soluble nickel salt, nano silicon, carbamide
Amount ratio is 1:1:5～1:1.5:8.
The present invention further technical scheme, the time of described ultrasonic disperse is 0.5～4h, described dispersed with stirring time
Between be 0.1～2h, the time of described ultrasonic disperse is longer than the time of dispersed with stirring；Twice scattered condition is and at room temperature enters
OK.
The present invention further technical scheme, transfers in there-necked flask by the green emulsion obtained, and is 90 in temperature
～condensing reflux 10～15h under conditions of 100 DEG C.
The present invention further technical scheme, described concentration of lye is 0.1～5mol/L, the time of described alkali liquor etching
It is 5～16h.
The present invention further technical scheme, described dry refers to vacuum lyophilization.
Will be described in detail the present invention below.
In the present invention, the use of carbamide is to provide a weakly alkaline environment to reaction, it is therefore an objective to allow nickel salt such as nitric acid
Interface between nickel aqueous solution and the silica nanosphere of activation reacts so that nisiloy hydrochlorate energy uniform deposition and around
Silicic acid nickel shell on silica template, needed for formation.The purpose processed with supersonic generator before reaction is to allow raw material divide
Dissipating uniformly, this is also for advantageously promoting silica nanosphere and nickel nitrate reacts.
Hydrothermal reaction kettle is changed into there-necked flask, reaction condition milder by the present invention, and we can be directly to reaction
The actual temp of container measures, so that temperature controls more convenient and easy, overcomes conventional autoclave temperature control difficulty
Shortcoming.Meanwhile, there-necked flask can also increase magnetic agitation, allow solution keep stable homogeneous at any time, be conducive to bigger rule
Prepared by mould, these advantages are all that autoclave cannot meet.
Additionally, the present invention uses alkali liquor to be angle from health to corrode silicon dioxide, it is commonly known that
Silicon dioxide belongs to acidic oxide, can react with the alkali such as Fluohydric acid. and sodium hydroxide.Although Fluohydric acid. etching effect
Preferably, but it has bigger harm to health, easily causes osteoporosis.So, for safety, we use alkali liquor to enter
Row corrosion.Also there are strict requirements the time to alkali liquor etching of the present invention, and etch period is too short, can not remove dioxy completely
SiClx template, overlong time the most easily affects the quality of product.The most only process under suitable etch period and just can obtain
The hollow silicic acid nickel microsphere of good quality.
Due to vacuum lyophilization be carry out under low temperature, low pressure be dried, its moisture directly distils, and is dehydrated more thorough
The end, and the product of drying is stable, it is simple to long time stored.In the present invention, dry due to material is the completeest
Becoming, compared with other drying meanss, physical arrangement and the molecule structure change of material are minimum, its organizational structure and mode of appearance quilt
Preferably preserve.During vacuum lyophilization, there is not Surface hardened layer problem in material, and it is internally formed the sponge of porous
Shape, thus there is the rehydration of excellence, the state before being dried can be recovered at short notice.
[beneficial effect]
The present invention compared with prior art, has a following beneficial effect:
Present invention process is simple, and easy and simple to handle, manufacturing cycle is short；Process is pollution-free, and cost of material used is relatively low, it is not necessary to
Specific response container；And the preparation method mild condition of the present invention, mass production easily operated, applicable.
Accompanying drawing explanation
Fig. 1 is the SEM figure of nano silicon；
Fig. 2 is the SEM figure of the hollow silicic acid nickel microsphere that the embodiment of the present invention 2 prepares；
Fig. 3 is the TEM figure of nano silicon；
Fig. 4 is the TEM figure of the hollow silicic acid nickel microsphere that the embodiment of the present invention 2 prepares.
Detailed description of the invention
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
0.2g nano silicon is dispersed in 40mL deionized water, ultrasonic disperse 1h so that it is dispersed, is formed white
Color emulsion.Then in finely dispersed nanosilica solution, add 1g carbamide and 0.18g nickel nitrate, continue dispersed with stirring
30min, obtains green emulsion.Subsequently green emulsion is transferred in there-necked flask, under the reaction temperature of 100 DEG C, keep condensation
Backflow 12h.By product filtering and washing, lyophilization, obtain silicic acid nickel/silicon dioxide microsphere.With the 1mol/L's of 50mL preparation
Sodium hydroxide solution processes dried silicic acid nickel/silicon dioxide microsphere, and the time is 16h.Subsequently by product washing, sucking filtration, true
Vacuum freecing-dry, obtains absinthe-green pressed powder, is required hollow silicic acid nickel microsphere.Products therefrom pattern and structure are led to
Cross SEM and TEM to characterize.
Embodiment 2:
2g nano silicon as shown in figures 1 and 3 is dispersed in 400mL deionized water, ultrasonic disperse 1h so that it is
Dispersed, form white emulsion.Then in finely dispersed nanosilica solution, add 10g carbamide and 1.8g nitric acid
Nickel, continues dispersed with stirring 30min, obtains green emulsion.Subsequently green emulsion is transferred in there-necked flask, the reaction of 95 DEG C
At a temperature of keep condensing reflux 24h.By product filtering and washing, vacuum drying obtains silicic acid nickel/silicon dioxide microsphere.Use 500mL
The sodium hydroxide solution of the 1.5mol/L of preparation processes dried silicic acid nickel/silicon dioxide microsphere, and the time is 16h.Subsequently will
Product washing, sucking filtration, vacuum lyophilization, obtain absinthe-green pressed powder, is required hollow silicic acid nickel microsphere.Gained
Product morphology and structure are characterized by SEM and TEM, and as shown in Figure 2 and Figure 4, as seen from the figure, the present invention is successful for concrete structure
Prepare hollow silicic acid nickel microsphere.
Embodiment 3:
0.2g silica nanosphere is dispersed in 40mL deionized water, ultrasonic disperse 1h so that it is dispersed, is formed
White emulsion.Then in finely dispersed nanosilica solution, add 1g carbamide and 0.2g nickel acetate, continue stirring point
Dissipate 30min, obtain green emulsion.Subsequently green emulsion is transferred in there-necked flask, under the reaction temperature of 85 DEG C, keep cold
Solidifying backflow 24h.By product filtering and washing, vacuum drying obtains silicic acid nickel/silicon dioxide microsphere.1.2mol/L with 50mL preparation
Potassium hydroxide solution process dried silicic acid nickel/silicon dioxide microsphere, the time is 14h.Subsequently by product washing, sucking filtration,
Vacuum lyophilization, obtains absinthe-green pressed powder, is required hollow silicic acid nickel microsphere.
Although reference be made herein to invention has been described for the explanatory embodiment of the present invention, and above-described embodiment is only this
Bright preferably embodiment, embodiments of the present invention are also not restricted to the described embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other amendments and embodiment, and these amendments and embodiment will fall in principle disclosed in the present application
Within scope and spirit.
Claims (9)
1. the method preparing hollow silicic acid nickel microsphere for template with silicon dioxide, it is characterised in that the method includes following step
Rapid: first by nano silicon ultrasonic disperse in deionized water, to obtain white emulsion；It is subsequently adding carbamide and water solublity nickel
Salt, dispersed with stirring is uniform, obtains green emulsion；Then the green emulsion obtained is transferred in there-necked flask, be 80 in temperature
～condensing reflux 1～24h under conditions of 120 DEG C；Finally, after alkali liquor etching 1～24h, it is dried to obtain hollow silicic acid nickel microsphere.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
Described water soluble nickel salt is the mixture of one or more in nickel nitrate, Nickel dichloride., nickel sulfate, nickel acetate, and hydrate.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
Described alkali liquor is one or more in sodium hydroxide, potassium hydroxide, Lithium hydrate, rubidium hydroxide, Cesium hydrate., barium hydroxide
Mixture.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
Addition mass ratio between described water soluble nickel salt, nano silicon, carbamide is 1:1:5～1:1.5:8, adding of deionized water
Entering amount is 30～500mL.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
The time of described ultrasonic disperse is 0.5～4h, and the time of described dispersed with stirring is 0.1～2h, the time ratio of described ultrasonic disperse
The time of dispersed with stirring is long；Twice scattered condition is and at room temperature carries out.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
The green emulsion obtained is transferred in there-necked flask, condensing reflux 10～15h under conditions of temperature is 90～100 DEG C.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
The concentration of described alkali liquor is 0.1～5mol/L.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
The time of described alkali liquor etching is 5～16h.
The method preparing hollow silicic acid nickel microsphere for template with silicon dioxide the most according to claim 1, it is characterised in that
Described dry be vacuum lyophilization.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108238605A (en) * | 2018-04-08 | 2018-07-03 | 吉林大学 | A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof |
| CN109847765A (en) * | 2019-03-08 | 2019-06-07 | 西北师范大学 | The preparation and the application in evolving hydrogen reaction of CdSNRs@NiSilicate ultrathin nanometer piece composite material |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
| CN111659339A (en) * | 2020-06-23 | 2020-09-15 | 华东交通大学 | Preparation method and application of LDHs-loaded layered nano hollow microsphere NiSiO @ NiAlFe adsorbent |
| CN114480883A (en) * | 2021-12-16 | 2022-05-13 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by synergistically removing silicon and chromium in vanadium solution through nickel ions |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659417A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Porous silicate nanometer hollow granule and preparation method thereof |
| CN101767205A (en) * | 2008-12-29 | 2010-07-07 | 宁波大学 | Preparation method of hollow nickel nanosphere |
| US20130028824A1 (en) * | 2010-04-27 | 2013-01-31 | Ocean's King Lighting Science & Technology Co., Ltd. | Preparation method of zinc manganese silicate |
| CN105129809A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Sea-urchin-shaped nanometer nickel silicate hollow sphere and preparation method thereof |
-
2016
- 2016-07-19 CN CN201610573298.4A patent/CN106185965A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101659417A (en) * | 2008-08-28 | 2010-03-03 | 中国科学院合肥物质科学研究院 | Porous silicate nanometer hollow granule and preparation method thereof |
| CN101767205A (en) * | 2008-12-29 | 2010-07-07 | 宁波大学 | Preparation method of hollow nickel nanosphere |
| US20130028824A1 (en) * | 2010-04-27 | 2013-01-31 | Ocean's King Lighting Science & Technology Co., Ltd. | Preparation method of zinc manganese silicate |
| CN105129809A (en) * | 2015-10-12 | 2015-12-09 | 上海第二工业大学 | Sea-urchin-shaped nanometer nickel silicate hollow sphere and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 江顺等: "《高中化学实验报告集锦 供高中学生使用》", 31 May 2015, 同济大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108238605A (en) * | 2018-04-08 | 2018-07-03 | 吉林大学 | A kind of three-dimensional flower-shaped alkali formula silicic acid nickel microballoon and preparation method thereof |
| CN109847765A (en) * | 2019-03-08 | 2019-06-07 | 西北师范大学 | The preparation and the application in evolving hydrogen reaction of CdSNRs@NiSilicate ultrathin nanometer piece composite material |
| CN109847765B (en) * | 2019-03-08 | 2021-06-08 | 西北师范大学 | Preparation of CdSNRs @ NiSilicate ultrathin nanosheet composite material and application of composite material in hydrogen evolution reaction |
| CN110240169A (en) * | 2019-07-03 | 2019-09-17 | 山东科技大学 | A kind of three-dimensional petal-shaped alkali formula silicic acid nickel and preparation method thereof |
| CN111659339A (en) * | 2020-06-23 | 2020-09-15 | 华东交通大学 | Preparation method and application of LDHs-loaded layered nano hollow microsphere NiSiO @ NiAlFe adsorbent |
| CN111659339B (en) * | 2020-06-23 | 2022-10-21 | 华东交通大学 | Preparation method and application of LDHs-loaded layered nano hollow microsphere NiSiO @ NiAlFe adsorbent |
| CN114480883A (en) * | 2021-12-16 | 2022-05-13 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by synergistically removing silicon and chromium in vanadium solution through nickel ions |
| CN114480883B (en) * | 2021-12-16 | 2023-11-21 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing high-purity vanadium pentoxide by removing silicon and chromium in vanadium solution through nickel ion cooperation |
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