CN102631873A - Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials - Google Patents
Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials Download PDFInfo
- Publication number
- CN102631873A CN102631873A CN2012101013156A CN201210101315A CN102631873A CN 102631873 A CN102631873 A CN 102631873A CN 2012101013156 A CN2012101013156 A CN 2012101013156A CN 201210101315 A CN201210101315 A CN 201210101315A CN 102631873 A CN102631873 A CN 102631873A
- Authority
- CN
- China
- Prior art keywords
- copper chloride
- preparation
- micro
- low
- materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of preparation of micro/nano structural materials and particularly relates to a low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials. In the low-cost preparation method, an inorganic dispersion sol-gel method is adopted, i.e., various micro/nano structural copper chloride hydroxide aerogel materials are prepared through a sol-gel process combined with a drying technology, by taking cheap copper chloride solution as precursor, polyacrylic acid as dispersing agent and template agent, and epoxide as a gel accelerator. The low-cost preparation method has the characteristics of cheap and easily-obtained materials, simple reaction process, short reaction period, low total cost and the like; the materials obtained by the method have multilevel micrometer and nanometer microstructures and also integrate high activity and high stability, and the properties of the materials also can be improved by the complexation of polyacrylic acid; and the micro/nano structural copper chloride hydroxide aerogel materials can be used in the fields of agricultural bactericide, feed additive, catalyst, pigment and the like.
Description
Technical field
The invention belongs to little/micro-nano structure technical field of material, be specifically related to a kind of low-cost preparation method that possibly be applied to the polyacrylic acid complexing basic copper chloride aeroge class material of directions such as high-performance agricultural bacteriocide, feed addictive, catalyst and pigment.
Background technology
Basic copper chloride (Cu
2(OH)
3Cl, or name copper oxychloride) be widely used in directions such as agricultural bacteriocide, feed addictive, catalyst and pigments.Usually, commercial basic copper chloride refines through mineral or the chemical precipitation method preparation, is generally the above closely knit powder of crystalline state of tens μ m.And aeroge is a kind of the gathering each other by nanometer scale ultrafine dust or high-polymer molecular to constitute the nanoporous network, and in hole, is full of a kind of high dispersive solid-state material of gaseous state decentralized medium.Its typical structure is the multistage fractal net work skeleton of nanometer scale, and this structure is not in self-supporting, can have ultrahigh activity in the dry linting.If can micro-structural type of the being regulated to aeroge structure of basic copper chloride will be improved its sterilizing rate, feed absorptivity, catalytic performance and colorability.
At present, adopt metal alkoxide to realize gelation (traditional sol-gal process) and combine drying process to prepare SiO as presoma, adjusting pH value
2, Al
2O
3And TiO
2Etc. multiple aeroge.Yet, a lot of metal alkoxides, costing an arm and a leg even extremely being difficult to obtains.Bivalent metal oxide (like the oxides, divalent of elements such as copper, nickel, cadmium, manganese, cobalt) is difficult to form three-dimensional net structure, makes that more the preparation of its aeroge is very difficult.Seminar such as the A. E. Gash of the U.S. and L. J. Hope-Weeks and domestic Gan Lihua, Zhang Lin, appoint people such as big waves to report the new technology that adopts inorganic salt solution and the multiple aeroge of organic epoxide prepared in reaction, expanded the preparation scope (epoxides method) of aeroge.It is dispersant and template that people such as applicant Du Ai, Zhou Bin adopt polyacrylic acid; The coupling collar conventional ceramic technique; Solved the preparation problem of many families multicycle oxide-base aerogel material; Further expanded aeroge the preparation scope (" preparation method of transition metal base aeroge, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel ", ZL200810033022.2).Applicant and Zhang Lin, a big waves seminar adopt this method to synthesize nanoporous basic copper chloride aeroge, and L. J. Hoop-Weeks also adopts the epoxides method to synthesize nanoporous basic copper chloride aeroge.
Yet above-mentioned basic copper chloride aeroge needs to consume a large amount of organic solvents in the preparation process, and needs to adopt the supercritical drying drying process of low temperature or high temperature bond high pressure, and cost is high.At present also Shang Weijian has document and patent report to need not the method that a large amount of organic solvents and supercritical drying mode are synthesized basic copper chloride aeroge class material.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, reaction time is short, applied widely, the low-cost preparation method of little/micro-nano structure basic copper chloride aeroge class material of maybe industry amplifying.Its basic ideas are when nanostructured keeps greater activity; Adopt water to reduce cost of material as solvent; Utilize with the big stress (avoiding adopting expensive supercritical fluid drying technology) in the micron dimension structure opposing normal pressure natural drying process of basic copper chloride aeroge, significantly reduce its synthetic cost.Obviously, described in claims, production cost method higher, that structural behaviour is more excellent (adopts organic or mixed solvent, adopt other more drying mode of costliness) also belongs to protection scope of the present invention.Particular content is following:
The low-cost preparation method of a kind of little/micro-nano structure basic copper chloride aeroge class material that the present invention proposes, concrete steps are following:
(1) copper chloride is dissolved in organic solvent/water mixed solution or directly soluble in water, is mixed with copper chloride solution;
(2) in the solution of step (1) gained, add polyacrylic acid and epoxides successively, stir, obtain gel after leaving standstill; Wherein, the adding proportion of copper chloride, organic solvent, deionized water, polyacrylic acid, epoxides is 6mmol:0 ~ 60ml:0.5 ~ 30ml:0.5-5ml:1-10ml;
(3) the aging at normal temperatures back of step (2) gained gel is dry, promptly obtain required little/micro-nano structure polyacrylic acid complexing basic copper chloride aeroge class material.
Among the present invention, the organic solvent in step (1) and the step (2) be in methyl alcohol, ethanol or the acetone and other organic solvent any.
Among the present invention, the epoxides in the step (2) is that expoxy propane, oxirane or epoxychloropropane etc. have in the compound of epoxide group any.
Among the present invention, drying means described in the step (3) be in the modes such as supercritical fluid drying, freeze drying, heat de-airing drying or normal pressure air dry any.
The basic copper chloride aeroge class material of the present invention's preparation has the characteristics of micron and nano-scale structures concurrently, and higher in constitutionally stable while activity, the low cost that has successfully solved basic copper chloride aeroge class material prepares a difficult problem.In addition, polyacrylic complexing also helps the further raising of its performance.Its raw material is easy to get, with low cost, all have great importance for fields such as agricultural bacteriocide, feed addictive, catalyst and pigments.
Description of drawings
The x x ray diffraction collection of illustrative plates of Fig. 1 embodiment 4 samples.
The FFIR figure of Fig. 2 embodiment 4 samples.
The electron scanning micrograph of Fig. 3 embodiment 4 samples.
The transmission electron microscope photo of Fig. 4 embodiment 4 samples.Wherein: (a), (b) be the high-amplification-factor photo for low multiplication factor photo.
The nitrogen adsorption desorption graph of pore diameter distribution of Fig. 5 embodiment 4 samples.
The electron scanning micrograph of Fig. 6 embodiment 5 samples.
The transmission electron microscope photo of Fig. 7 embodiment 6 samples.Wherein: (a), (b) be the high-amplification-factor photo for low multiplication factor photo.
The transmission electron microscope photo of Fig. 8 embodiment 7 samples.Wherein: (a), (b) be the high-amplification-factor photo for low multiplication factor photo.
The specific embodiment
Below further specify the present invention through embodiment and accompanying drawing.(each raw material is marketable material, does not have the purity of special instruction and is chemical pure or analyzes pure grade)
Embodiment 1: the normal pressure air dry of basic copper chloride aeroge sill preparation under the pure water solvent condition
Ratio with copper chloride, deionized water, polyacrylic acid and expoxy propane is 6 mmol:15 ml:1 ml:1 ml (organic solvent is 0 ml), under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel directly places the air dry of air normal pressure not have obvious reduction until quality, can obtain block basic copper chloride aeroge sill.
Embodiment 2: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, methyl alcohol, deionized water, polyacrylic acid and oxirane is 6 mmol:60 ml:0.5 ml:0.5 ml:1 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel carries out supercritical fluid drying after replacing three times through methyl alcohol, finally can obtain block basic copper chloride aeroge sill.
Embodiment 3: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, acetone, deionized water, polyacrylic acid and epoxychloropropane is 6 mmol:10 ml:30 ml:5 ml:10 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Carry out freeze drying after washing of gel process and the solvent replacing, obtain chunky shape or powdery basic copper chloride aeroge sill at last.
Embodiment 4: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6 mmol:10 ml:0.65 ml:0.77 ml:1.26 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel directly places the air dry of air normal pressure not have obvious reduction until quality, can obtain block basic copper chloride aeroge sill.
As shown in Figure 1, the x x ray diffraction spectrum of sample and 78-0372 standard card coincide, and the main component that this material is described is that (or be called copper oxychloride, molecular formula is Cu for the orthorhombic system basic copper chloride of low-crystallinity
2(OH)
3Cl).And shown in Figure 2, the FFIR of sample shows that then the bridge-type complexing has taken place for basic copper chloride and polyacrylic acid.Electron scanning micrograph among Fig. 3 and the transmission electron microscope among Fig. 4 then show, that this material has is little/receive the multilevel hierarchy of yardstick (several microns and tens nanometer).The nitrogen adsorption desorption graph of pore diameter distribution of Fig. 5 proves further that then this material also has the fine structure about 4 nm.Integration test is the result show, this material is little for having/receive low-crystallinity basic copper chloride multilevel hierarchy (at least three grades), the polyacrylic acid complexing.
Embodiment 5: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6 mmol:10 ml:0.65 ml:0.77 ml:1.26 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel can obtain chunky shape basic copper chloride aeroge sill after through 50 ℃ of heat de-airing dryings (vacuum drying).Its micro-structural is shown in the electron scanning micrograph among Fig. 6.
Embodiment 6: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6 mmol:10 ml:0.65 ml:0.385 ml:1.26 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel carries out supercritical fluid drying after overaging, solvent replacing and ethanol replacement, finally can obtain block basic copper chloride aeroge sill.Its micro-structural is shown in the transmission electron microscope photo among Fig. 7.
Embodiment 7: the preparation of basic copper chloride aeroge sill
Ratio with copper chloride, ethanol, deionized water, polyacrylic acid and expoxy propane is 6 mmol:10 ml:0.65 ml:1.155 ml:1.26 ml, under well-beaten situation, adds each reactant successively, obtains gel after leaving standstill.Gel carries out supercritical fluid drying after overaging, solvent replacing and ethanol replacement, finally can obtain block basic copper chloride aeroge sill.Its micro-structural is shown in the transmission electron microscope photo among Fig. 8.
Above-described embodiment has been merely explanation technological thought of the present invention and characteristics; Its purpose is to make those of ordinary skill in the art can understand content of the present invention and implements according to this; The scope of this patent also not only is confined to above-mentioned specific embodiment; Be all equal variation or modifications of doing according to disclosed spirit, still be encompassed in protection scope of the present invention.
Claims (4)
1. the low-cost preparation method of little/micro-nano structure basic copper chloride aeroge class material is characterized in that adopting inorganic dispersion sol-gal process, and concrete steps are following:
(1) copper chloride is dissolved in organic solvent/water mixed solution or directly soluble in water, is mixed with copper chloride solution;
(2) in the solution of step (1) gained, add polyacrylic acid and epoxides successively, stir, obtain gel after leaving standstill; Wherein, the adding proportion of copper chloride, organic solvent, deionized water, polyacrylic acid, epoxides is 6mmol:0 ~ 60ml:0.5 ~ 30ml:0.5-5ml:1-10ml;
(3) the aging at normal temperatures back of step (2) gained gel is dry, promptly obtain required little/micro-nano structure polyacrylic acid complexing basic copper chloride aeroge class material.
2. preparation method according to claim 1 is characterized in that organic solvent in step (1) and the step (2) is in methyl alcohol, ethanol or the acetone any.
3. preparation method according to claim 1, it is characterized in that epoxides in the step (2) be in expoxy propane, oxirane or the epoxychloropropane any.
4. preparation method according to claim 1, it is characterized in that drying means described in the step (3) be in supercritical fluid drying, freeze drying, heat de-airing drying or the normal pressure air dry any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101013156A CN102631873A (en) | 2012-04-10 | 2012-04-10 | Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101013156A CN102631873A (en) | 2012-04-10 | 2012-04-10 | Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102631873A true CN102631873A (en) | 2012-08-15 |
Family
ID=46616555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101013156A Pending CN102631873A (en) | 2012-04-10 | 2012-04-10 | Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102631873A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435325A (en) * | 2013-08-20 | 2013-12-11 | 南京工业大学 | Preparation method for calcium-based aerogel material |
| CN105350104A (en) * | 2015-12-01 | 2016-02-24 | 东华大学 | Method for preparing mesoporous zirconium phosphate supported copper oxide antibacterial polyvinyl alcohol fibers |
| CN110280191A (en) * | 2019-05-24 | 2019-09-27 | 江苏大学 | The manganese dioxide nanowire aeroge and its preparation method and application of acid and alkali-resistance self assembly laminated construction |
| CN111642633A (en) * | 2020-07-07 | 2020-09-11 | 武汉轻工大学 | Basic copper chloride microspheres, preparation method thereof and feed additive |
| CN112588276A (en) * | 2020-12-30 | 2021-04-02 | 南京中设石化工程有限公司 | Absorbent for absorbing ethylene in methanol-to-olefin reaction product and process thereof |
| CN115646430A (en) * | 2022-10-20 | 2023-01-31 | 淮阴工学院 | Preparation method of copper-based aerogel for iodide adsorption |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
| KR20080078101A (en) * | 2007-02-22 | 2008-08-27 | (주)분자와 사람들 | Synthesis of colloidal solution of ultrafine metal oxide for a thin film using a solvothermal method |
-
2012
- 2012-04-10 CN CN2012101013156A patent/CN102631873A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080078101A (en) * | 2007-02-22 | 2008-08-27 | (주)분자와 사람들 | Synthesis of colloidal solution of ultrafine metal oxide for a thin film using a solvothermal method |
| CN101219360A (en) * | 2008-01-24 | 2008-07-16 | 同济大学 | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel |
Non-Patent Citations (2)
| Title |
|---|
| 《原子能科学技术》 20080930 杜艾等 "ICF用铜基低密度气凝胶靶材料研制" 第794页至第798页 1-4 第42卷, 第9期 * |
| 杜艾等: ""ICF用铜基低密度气凝胶靶材料研制"", 《原子能科学技术》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435325A (en) * | 2013-08-20 | 2013-12-11 | 南京工业大学 | Preparation method for calcium-based aerogel material |
| CN105350104A (en) * | 2015-12-01 | 2016-02-24 | 东华大学 | Method for preparing mesoporous zirconium phosphate supported copper oxide antibacterial polyvinyl alcohol fibers |
| CN105350104B (en) * | 2015-12-01 | 2017-10-27 | 东华大学 | A kind of preparation method of Mesoporous zirconium phosphate loaded copper oxide antibacterial polyethylene alcohol fiber |
| CN110280191A (en) * | 2019-05-24 | 2019-09-27 | 江苏大学 | The manganese dioxide nanowire aeroge and its preparation method and application of acid and alkali-resistance self assembly laminated construction |
| CN110280191B (en) * | 2019-05-24 | 2022-02-15 | 江苏大学 | Manganese dioxide nanowire aerogel with acid-base-resistant self-assembled laminated structure and preparation method and application thereof |
| CN111642633A (en) * | 2020-07-07 | 2020-09-11 | 武汉轻工大学 | Basic copper chloride microspheres, preparation method thereof and feed additive |
| CN111642633B (en) * | 2020-07-07 | 2023-01-06 | 武汉轻工大学 | Basic copper chloride microspheres, preparation method thereof and feed additive |
| CN112588276A (en) * | 2020-12-30 | 2021-04-02 | 南京中设石化工程有限公司 | Absorbent for absorbing ethylene in methanol-to-olefin reaction product and process thereof |
| CN115646430A (en) * | 2022-10-20 | 2023-01-31 | 淮阴工学院 | Preparation method of copper-based aerogel for iodide adsorption |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102631873A (en) | Low-cost preparation method of micro/nano structural copper chloride hydroxide aerogel materials | |
| CN102642843B (en) | Method for simultaneously preparing multilevel-structure mesoporous silicon dioxide and carbon nano material | |
| CN101219360B (en) | Process for producing transition metal base silica aerogel, transition metal oxide silica aerogel, composite transition metal oxide silica aerogel | |
| CN100443223C (en) | Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel | |
| CN104211078B (en) | A kind of metal-doped mesoporous silicon based molecular sieve nanosphere and preparation method thereof | |
| CN102688732A (en) | Universal preparation method for rare earth oxide nanometer porous aerogel with high specific surface area | |
| CN102730770B (en) | Preparation method of spongy porous composite oxide nanoscale or microscale polyhedrons | |
| CN103447549B (en) | Preparation method of cobalt nanosphere | |
| CN104495908A (en) | Preparation method of cuprous sulfide powder, and cuprous sulfide powder | |
| CN101475161A (en) | Method for preparing BaTiO3 / multi-wall carbon nano-tube (MWCNTs) nano composite material | |
| CN105271405A (en) | Material based on bismuth oxycarbonate or bismuth oxide nano tube and preparation method thereof | |
| CN105502421A (en) | Preparation method of zinc silicate hollow micron ball | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN103387261A (en) | Anatase titanium dioxide nano-rods and preparation method thereof | |
| CN102139914A (en) | Method for preparing calcium titanate nanoparticles | |
| CN103303980B (en) | The method of sulfonated lignin template synthesis nano-sized iron oxide | |
| CN101805009B (en) | Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly | |
| CN101508468A (en) | Nano-superstructure polyporous material of ferrite and method of preparing the same | |
| CN105399418A (en) | Preparation method of high-performance sodium niobate dielectric ceramic powder | |
| CN105271374A (en) | Preparation method of stannic oxide microspheres of oriented connection microstructure | |
| CN102718255A (en) | Preparation method of titanium dioxide hollow nano structure | |
| Gholami et al. | Investigate the effect of silica on improvement electrochemical storage of hydrogen in ZnAl2O4 spinel | |
| CN108046340A (en) | A kind of method exempted from template and prepare cobaltosic oxide multi-layer hollow nanosphere | |
| CN108262051A (en) | A kind of method of mechanical ball mill heat treatment two-step method synthesis ceria-bismuthyl carbonate nano-complex | |
| CN102502871A (en) | Method for synthesizing three-dimensional porous ferric oxide nano rod cluster |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |