CN103552988A - Layered double hydroxide based composite material with fiber hierarchical structure and preparation method thereof - Google Patents
Layered double hydroxide based composite material with fiber hierarchical structure and preparation method thereof Download PDFInfo
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- CN103552988A CN103552988A CN201310461301.XA CN201310461301A CN103552988A CN 103552988 A CN103552988 A CN 103552988A CN 201310461301 A CN201310461301 A CN 201310461301A CN 103552988 A CN103552988 A CN 103552988A
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Abstract
The invention relates to a layered double hydroxide based composite material with a fiber hierarchical structure and a preparation method thereof, the composite material is prepared by in-situ reaction of a bivalent metal salt and fiber-state alumina, the composite material comprises a primary structure and a secondary structure, the primary structure is a fiber-state alumina structure, the secondary structure is a sheet-shaped layered double hydroxide (LDHs) based structure, and the layered double hydroxide (LDHs) based composite material with the fiber hierarchical structure has potential application values in the fields of adsorption, catalysis, photics and the like. The preparation method has the characteristics of simple process, environmental friendliness, low cost and the like.
Description
Technical field
The present invention relates to layered double-hydroxide based composites of a kind of fiber classification structure and preparation method thereof, belong to technical field of function materials.
Background technology
Layered double-hydroxide (LDHs) compound that to be a class assembled layer by layer by interlayer anion and positively charged nanometer sheet, it is a kind of anion type laminated functional materials, the adjustable sex change of the two-dirnentional structure that it is unique and laminate element and interlayer anion, gets more and more people's extensive concerning.Positively charged laminate and electronegative interlayer anion, under very strong electrostatic attraction effect and under the effect of hydrogen bond, form orderly laminate structure.Distance between LDHs laminate only has about 0.5nm, and less interlamellar spacing and specific surface area have seriously limited the surface property of LDHs; Also make the molecule that some volumes are larger be difficult to be inserted into LDHs interlayer simultaneously.Therefore, control LDHs pattern, avoid the orderly stack between nanometer sheet, the LDHs for preparing hierarchy has important Research Significance.
The layered double-hydroxide LDHs of hierarchy, because its laminate is with permanent positive charge and have higher specific surface area, has important using value in catalysis and absorption.At present, although there is the LDHs preparation report of hierarchy, preparation process is comparatively complicated, poor controllability, and severe reaction conditions.1), prepare magnetic Fe_3O_4 particle as the preparation process of Fe3O4@SiO2@LDHs matrix material is:; 2), magnetic particle surface growth one deck SiO2; 3), at SiO2 surface growth one deck AlOOH; 4), take AlOOH as aluminium source, growth in situ LDHs nanometer sheet is prepared hierarchy core-shell particles.This preparation process is comparatively complicated, and every step all may be to environment, and in the material of preparation, has a kind of inoperative SiO2.
The present invention utilizes fibrous template to prepare the layered double-hydroxide LDHs based composites of hierarchy, can effectively control LDHs pattern and pore structure, and technique is simple, environmental protection.
Summary of the invention
Technical problem: the object of the invention is to provide layered double-hydroxide (LDHs) based composites of a kind of fiber classification structure and preparation method thereof, this material is to be formed by divalent metal M salt and fiber state aluminum oxide reaction in－situ, the structure of material comprises primary structure and secondary structure, its primary structure is fiber state aluminium oxide structure, and secondary structure is sheet LDHs structure.
Technical scheme: the present invention adopts the aluminum oxide of template synthesis fibre shape, then by situ synthesis in its surface growth one deck layered double-hydroxide LDHs nanometer sheet, obtain a kind of fiber classification structure layered double-hydroxide based composites.Concrete preparation process is:
This material is to be formed by divalent metal M salt and fiber state aluminum oxide reaction in－situ, the structure of material comprises primary structure and secondary structure, its primary structure is fiber state aluminium oxide structure, secondary structure is sheet layered double-hydroxide structure, and divalent metal M salt is one or more the combination in magnesium nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, sal epsom, zinc sulfate and magnesium chloride.
The preparation method of the layered double-hydroxide based composites of a kind of fiber classification structure of the present invention is:
Step a). with the hydrochloric acid of 0.5～1mol/L, regulating concentration is pH to 3～4 of 0.1～0.5mol/L aluminum saline solution, stirs 1～5h at 80 ℃, obtains aluminium colloidal sol; Under ultrasound condition, by 10～100g/L, the fibrous template of dried and clean is immersed in above-mentioned aluminium colloidal sol, ultrasonic 0.5～5h, filters, and distilled water wash is neutral to filtrate pH 1～3 time, dry 12～24h at 50～80 ℃, 400～800 ℃ of roasting 2～6h, obtain fiber state aluminum oxide;
Step b). press the mol ratio 1:1～1:6 of divalent metal M salt and precipitation agent, divalent metal M salt and precipitation agent are dissolved in distilled water, obtain the mixing solutions of 0.05～0.5mol/L divalent metal M salt/precipitation agent, this mixing solutions is added in the autoclave of inner liner polytetrafluoroethylene, press the mol ratio 1:4～4:1 of fiber state aluminum oxide and metal M, the fiber state aluminum oxide making in step a) is joined in above-mentioned mixing solutions, hydro-thermal reaction 1～15h at 80～140 ℃, cooling, filter, distilled water wash 3～5 times, dry 12～24h at 50～80 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
Wherein, the aluminium salt described in this preparation method's step a) is one or several combination of aluminum nitrate, Tai-Ace S 150 or aluminum chloride, and described fibrous template is one or several the combination in degreasing cotton fiber, bamboo fibers, lumber fibre or spider's thread fiber.
Precipitation agent described in this preparation method's step b) is urea or hexamethylene tetramine.
Layered double-hydroxide LDHs laminate metal consists of divalent metal M and trivalent metal aluminium, and wherein divalent metal can phase trans-substitution.Therefore, the aluminium salt described in above-mentioned preparation method is one or several the combination of aluminum nitrate, Tai-Ace S 150 and aluminum chloride; Described divalent metal M salt is one or several the arbitrary proportion combination in magnesium nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, sal epsom, zinc sulfate and magnesium chloride; Described precipitation agent is urea or hexamethylene tetramine.
Beneficial effect: binding fiber template of the present invention and in situ synthesis are prepared the layered double-hydroxide based composites of fiber classification structure, this material have unique micro-, receive hierarchy and higher specific surface area, there is to potential using value in the fields such as absorption, catalysis and optics.
Feature of the present invention is:
(1), the simple and environmental protection of the preparation technology of material.
(2), material presents unique texture within the scope of continuous micro-, nanoscale, its primary structure is fiber state aluminium oxide structure, secondary structure is sheet layered double-hydroxide LDHs structure.
(3), layered double-hydroxide LDHs forms macroporous structure at fiber state alumina surface, can make the molecule that some volumes are larger be inserted into layered double-hydroxide LDHs interlayer.
Embodiment
Embodiment 1:
Get 7.50g aluminum nitrate, add dehydrated alcohol 100mL, then to add appropriate distilled water to make the final volume of solution be 200mL, the aluminium colloidal sol of preparation 0.1mol/L; Get 0.4g absorbent cotton and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fiber state; Get 1mmol magnesium nitrate and 6mmol urea, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, getting 1mmol fibre shape aluminum oxide adds in reactor again, hydro-thermal 10h at 120 ℃, takes out sample, distilled water wash 3 times, at 80 ℃, be dried, obtain the layered double-hydroxide based composites of fiber classification structure.
Embodiment 2:
By the mol ratio of Tai-Ace S 150 and aluminum nitrate, be 1:2, the aluminium colloidal sol that preparation 200mL concentration is 0.1mol/L.Get 0.4g absorbent cotton and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fibre shape; Get 1mmol magnesium nitrate and 6mmol urea, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, getting 1mmol fibre shape aluminum oxide adds in reactor again, hydro-thermal 10h at 120 ℃, takes out sample, distilled water wash 3 times, at 80 ℃, be dried, obtain the layered double-hydroxide based composites of fiber classification structure.
Embodiment 3:
Get 7.50g aluminum nitrate, add dehydrated alcohol 100mL, then to add appropriate distilled water to make the final volume of solution be 200mL, the aluminium colloidal sol of preparation 0.1mol/L; Get 0.4g absorbent cotton and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fiber state.Get 0.5mmol magnesium nitrate, 0.5mmol zinc nitrate and 6mmol urea, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, get again 1mmol fibre shape aluminum oxide and add in reactor, then transfer in the reactor of 30mL, hydro-thermal 10h at 120 ℃, take out sample, distilled water wash 3 times, dry at 60 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
Embodiment 4:
Get 7.50g aluminum nitrate, add dehydrated alcohol 100mL, then to add appropriate distilled water to make the final volume of solution be 200mL, the aluminium colloidal sol of preparation 0.1mol/L; Get 0.4g absorbent cotton and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fiber state.Get 1mmol magnesium nitrate and 2mmol hexamethylene tetramine, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, get again 1mmol fibre shape aluminum oxide and add in reactor, then transfer in the reactor of 30mL, hydro-thermal 10h at 120 ℃, take out sample, distilled water wash 3 times, dry at 60 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
Embodiment 5:
Get 7.50g aluminum nitrate, add dehydrated alcohol 100mL, then to add appropriate distilled water to make the final volume of solution be 200mL, the aluminium colloidal sol of preparation 0.1mol/L; Get 0.4g bamboo fibers and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fiber state.Get 1mmol magnesium nitrate and 3mmol hexamethylene tetramine, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, get again 1mmol fibre shape aluminum oxide and add in reactor, then transfer in the reactor of 30mL, hydro-thermal 10h at 120 ℃, take out sample, distilled water wash 3 times, dry at 60 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
Embodiment 6:
Get 7.50g aluminum nitrate, add dehydrated alcohol 100mL, then to add appropriate distilled water to make the final volume of solution be 200mL, the aluminium colloidal sol of preparation 0.1mol/L; Get 0.2g bamboo fibers and 0.2g absorbent cotton and be immersed in above-mentioned aluminium colloidal sol, ultrasound condition is processed after 3h, takes out, distilled water wash number 2 times dry 12h at 80 ℃; By dried sample, at 600 ℃ of roasting 4h, obtain the aluminum oxide of fiber state.Get 1mmol magnesium nitrate and 3mmol hexamethylene tetramine, be dissolved in 20mL distilled water, then transfer in the reactor of 30mL, get again 1mmol fibre shape aluminum oxide and add in reactor, then transfer in the reactor of 30mL, hydro-thermal 10h at 120 ℃, take out sample, distilled water wash 3 times, dry at 60 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
Claims (4)
1. the layered double-hydroxide based composites of a fiber classification structure, it is characterized in that this material is to be formed by divalent metal M salt and fiber state aluminum oxide reaction in－situ, the structure of material comprises primary structure and secondary structure, its primary structure is fiber state aluminium oxide structure, secondary structure is sheet layered double-hydroxide structure, and divalent metal M salt is one or more the combination in magnesium nitrate, nickelous nitrate, zinc nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, sal epsom, zinc sulfate and magnesium chloride.
2. the preparation method of the layered double-hydroxide based composites of a kind of fiber classification structure according to claim 1, is characterized in that this preparation method is:
Step a). with the hydrochloric acid of 0.5～1mol/L, regulating concentration is pH to 3～4 of 0.1～0.5mol/L aluminum saline solution, stirs 1～5h at 80 ℃, obtains aluminium colloidal sol; Under ultrasound condition, by 10～100g/L, the fibrous template of dried and clean is immersed in above-mentioned aluminium colloidal sol, ultrasonic 0.5～5h, filters, and distilled water wash is neutral to filtrate pH 1～3 time, dry 12～24h at 50～80 ℃, 400～800 ℃ of roasting 2～6h, obtain fiber state aluminum oxide;
Step b). press the mol ratio 1:1～1:6 of divalent metal M salt and precipitation agent, divalent metal M salt and precipitation agent are dissolved in distilled water, obtain the mixing solutions of 0.05～0.5mol/L divalent metal M salt/precipitation agent, this mixing solutions is added in the autoclave of inner liner polytetrafluoroethylene, press the mol ratio 1:4～4:1 of fiber state aluminum oxide and metal M, the fiber state aluminum oxide making in step a) is joined in above-mentioned mixing solutions, hydro-thermal reaction 1～15h at 80～140 ℃, cooling, filter, distilled water wash 3～5 times, dry 12～24h at 50～80 ℃, obtain the layered double-hydroxide based composites of fiber classification structure.
3. the preparation method of a kind of fibre shape hierarchy stratiform double-hydroxide based composites according to claim 2, it is characterized in that aluminium salt described in this preparation method's step a) is one or several combination of aluminum nitrate, Tai-Ace S 150 or aluminum chloride, described fibrous template is one or several the combination in degreasing cotton fiber, bamboo fibers, lumber fibre or spider's thread fiber.
4. the preparation method of fibre shape hierarchy stratiform double-hydroxide base complex according to claim 2, is characterized in that the precipitation agent described in this preparation method's step b) is urea or hexamethylene tetramine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310449A (en) * | 2014-10-15 | 2015-01-28 | 上海应用技术学院 | Method for preparing layered double hydroxide nanorod |
| CN108276246A (en) * | 2018-02-08 | 2018-07-13 | 浙江博瑞电子科技有限公司 | A kind of method that hexachlorobutadiene is refined |
| CN112354513A (en) * | 2020-11-09 | 2021-02-12 | 榆林学院 | Zn2+-Al3+-CO32-LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling |
| CN113083216A (en) * | 2021-04-23 | 2021-07-09 | 江苏大学 | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application for removing phosphate radical |
| CN113184921A (en) * | 2021-04-23 | 2021-07-30 | 江苏大学 | LDH-based composite material based on nickel-containing sludge and preparation method thereof |
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| CN102876287A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material |
| CN103275408A (en) * | 2013-05-28 | 2013-09-04 | 河海大学 | Graphene/layered double hydroxide composite flame retardant and preparation method of polystyrene nanometer flame-retardant composite material |
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| CN102876287A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Self assembly laminated infrared film material and preparation method of self assembly laminated infrared film material |
| CN103275408A (en) * | 2013-05-28 | 2013-09-04 | 河海大学 | Graphene/layered double hydroxide composite flame retardant and preparation method of polystyrene nanometer flame-retardant composite material |
Non-Patent Citations (1)
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| TAO ZHANG ETAL: "Biomimetic fabrication of hierarchically structured LDHs/ZnO composites for the separation of bovine serum albumin", 《CHEMICAL ENGINEERING JOURNAL》, 11 January 2013 (2013-01-11) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104310449A (en) * | 2014-10-15 | 2015-01-28 | 上海应用技术学院 | Method for preparing layered double hydroxide nanorod |
| CN104310449B (en) * | 2014-10-15 | 2016-07-06 | 上海应用技术学院 | A kind of preparation method of laminated double hydroxide nanometer rod |
| CN108276246A (en) * | 2018-02-08 | 2018-07-13 | 浙江博瑞电子科技有限公司 | A kind of method that hexachlorobutadiene is refined |
| CN112354513A (en) * | 2020-11-09 | 2021-02-12 | 榆林学院 | Zn2+-Al3+-CO32-LDHs @ Al adsorbing material and application thereof in adsorbing fluorine ions by recycling |
| CN113083216A (en) * | 2021-04-23 | 2021-07-09 | 江苏大学 | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application for removing phosphate radical |
| CN113184921A (en) * | 2021-04-23 | 2021-07-30 | 江苏大学 | LDH-based composite material based on nickel-containing sludge and preparation method thereof |
| CN113184921B (en) * | 2021-04-23 | 2023-10-13 | 江苏大学 | LDH-based composite material based on nickel-containing sludge and preparation method thereof |
| CN113083216B (en) * | 2021-04-23 | 2023-11-10 | 江苏大学 | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application of adsorbent in removing phosphate radical |
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Application publication date: 20140205 |