CN104752069A - Preparation method of metallic oxide or metallic oxide composite material - Google Patents

Preparation method of metallic oxide or metallic oxide composite material Download PDF

Info

Publication number
CN104752069A
CN104752069A CN201310748663.7A CN201310748663A CN104752069A CN 104752069 A CN104752069 A CN 104752069A CN 201310748663 A CN201310748663 A CN 201310748663A CN 104752069 A CN104752069 A CN 104752069A
Authority
CN
China
Prior art keywords
metal oxide
chloride
nitrate
preparation
acid
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.)
Granted
Application number
CN201310748663.7A
Other languages
Chinese (zh)
Other versions
CN104752069B (en
Inventor
张立娟
付洋
崔成梅
党桃桃
谢钢
杨奇
陈三平
惠俊峰
步怀天
王尧宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwest University
Original Assignee
Northwest University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northwest University filed Critical Northwest University
Priority to CN201310748663.7A priority Critical patent/CN104752069B/en
Publication of CN104752069A publication Critical patent/CN104752069A/en
Application granted granted Critical
Publication of CN104752069B publication Critical patent/CN104752069B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacturing & Machinery (AREA)

Abstract

The invention discloses a preparation method of a metallic oxide or a metallic oxide composite material. The method specifically comprises the steps of dissolving water-soluble sugar composition and a water-soluble macromolecule into water in a closed container; adding organic acid or alkali; adding metallic salt; reacting at the temperature of 140 to 300 DEG C; drying and roasting to obtain the metallic oxide or the metallic oxide composite material. According to the preparation method, the metallic oxide or the metallic oxide composite material with high activity, high porosity and large electric chemical specific area is prepared by an one-step method; the prepared metallic oxide or metallic oxide composite material can be used as gas sensitive, magnetic, capacitive, electric conductive and catalytic active material and has a wide application prospect in the fields of information, energy, electronics, metallurgy, space navigation, chemicals, mechanisms, biologics and medicines.

Description

The preparation method of a kind of metal oxide or metal oxide composite
Technical field
The present invention relates to the preparation method of a kind of metal oxide or metal oxide composite.
Background technology
Carbon aerogels is a kind of novel light nanoporous carbon materials, and having the features such as high porosity, high-specific surface area, high conductivity and variable density scope are wide, is the ideal electrode material as double electric layer capacitor.Carbon aerogels (CA) is a kind of nano-porous materials of the three-dimensional net structure piled up by carbon nano-particles, it has the good characteristics such as controlled pore structure, higher specific area, good electronic conductivity, variable density scope be wide, and is widely used in the fields such as gas separaion adsorbent, catalyst, electrochemical capacitor, hydrogen storage material, template.Carbon aerogels is by the restriction of material with carbon element structure, and its electric double layer capacity formed is difficult to increase substantially.It is relatively little that carbon aerogels makes positive electrode specific capacity, and this will affect the overall performance of capacitor.Due to metal oxide active material reacts the faraday of Cathode/Solution Interface " fake capacitance " that produce will much larger than the double layer capacity of the material surfaces such as carbon aerogels, at present, many researchers are devoted in porous carbon materials, mix metal oxide, conducting polymer, and the heteroatomic mode of area load improves its chemical property.
Summary of the invention
The object of the invention is to provide that a kind of raw material is easy to get, technique is simple, condition is easily controlled, the preparation method of green non-poisonous metal oxide or metal oxide composite.
Implementation procedure of the present invention is as follows:
The preparation method of a kind of metal oxide or metal oxide composite: in closed container, by water-soluble sugar compounds and water soluble polymer water-soluble, add slaine, 140 ~ 300 DEG C of reactions, drying, calcining obtain metal oxide or metal oxide composite.
The preferred reaction temperature of above-mentioned reaction is 160 ~ 230 DEG C; Dry run adopts natural drying, freeze drying or CO 2 supercritical dry, be preferably freeze drying or CO 2 supercritical drying, the carbon aerogels that drying obtains further under an inert atmosphere 300 ~ 1200 DEG C of calcination processing obtain metal oxide composite, obtain metal oxide in 300 ~ 1200 DEG C of calcination processing in air atmosphere.Calcination process is conducive to opening inaccessible duct, and specific area is increased; The carbon aerogels elasticity prepared add organic acid or alkali in reaction system after better and compact.
Described saccharide compound is selected from monose, disaccharides, compound sugar, polysaccharide, described saccharide compound is selected from glucose, fructose, sucrose, maltose, lactose, stachyose, raffinose, isomaltoketose, milk ketose, FOS, xylo-oligosaccharide, galactooligosaccharide, oligoisomaltose, iMOS, oligomeric dragon gallbladder sugar, soyabean oligosaccharides, chitosan oligomer, cyclodextrin, starch, Acid modified starch, oxidized starch, white dextrin, yellow dextrin, faint yellow dextrin, acetoxylation starch, octyl group butanedioic acid sodium salt starch, hydroxypropyl starch ether, oxirane crosslinked starch, amylan, starch acetate glue, carboxy starch glue, water-fast amylan, cellulose, hemicellulose, glycogen, wood sugar, Arabic gum, mucopolysaccharide.
Described water soluble polymer is polyvinylpyrrolidone, polyacrylic acid, Sodium Polyacrylate, polyacrylamide, hydrolyzed polyacrylamide, acrylic acid and methacrylate polymer, PLA, poly, poly-aspartate, poly-epoxy succinic acid, chitin, polyvinyl alcohol.
Described slaine is selected from vanadium, manganese, iron, cobalt, nickel, zinc, cadmium, chromium, plumbous, zirconium, magnesium, calcium, strontium, barium, cerium, tungsten, bismuth, antimony, molybdenum, rare-earth salts, as iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, frerrous chloride, ironic citrate, ferric oxalate, ferrous oxalate, iron ammonium sulfate, cobaltous sulfate, cobaltic chloride, cobalt acetate, cobalt chloride, Hexammine cobaltic chloride, cobalt carbonate, cobalt nitrate, nickel nitrate, nickel acetate, nickel chloride, nickelous sulfate, zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, manganese carbonate, zirconium chloride, zirconyl nitrate, calcium chloride, calcium nitrate, calcium carbonate, calcium sulfate, strontium chloride, strontium nitrate, strontium bromide, strontium iodide, strontium hydroxide, butter of tin, stannous chloride, sodium tungstate, cerium chloride, cerous nitrate, magnesium chloride, magnesium hydroxide, yttrium chloride, yttrium nitrate, zinc nitrate, zinc chloride, zinc acetate, cadmium nitrate, cadmium acetate, nitric acid antimony, antimony chloride, bismuth nitrate, bismuth chloride, barium nitrate, barium chloride, lead acetate, ammonium vanadate, lanthanum nitrate, ammonium molybdate, lead acetate.
Add organic acid or alkali in reaction system, described organic acid or alkali are selected from acetic acid, formic acid, ethanedioic acid, acrylic acid, benzoic acid, ammoniacal liquor, pyridine, triethylamine, triethanolamine, monoethanolamine, Tetramethylammonium hydroxide, diisopropyl ethyl ammonia, diethylenetriamine, quinine.
The mass ratio of above-mentioned saccharide compound and water soluble polymer is 1:6 ~ 1:0.005, is preferably 1:1 ~ 1:0.05; The mass ratio of saccharide compound and water is 1:60 ~ 1:0.5, is preferably 1:30 ~ 1:1; The mass ratio of saccharide compound and slaine is 25:1 ~ 1:1.
The formation mechenism of carbon gel of the present invention is as follows: saccharide compound is containing polyhydroxy aldehyde, polyhydroxyketone and can be hydrolyzed and generates the organic compound of polyhydroxy aldehyde or polyhydroxyketone, water soluble polymer contains the high polymer of abundant carboxyl, hydroxyl or amino, acid or alkali catalysis under, can form crosslinked network structure through high-temperature water thermal response, final hydro-thermal charing obtains the carbon gel rubber material of porous.
Low raw-material cost of the present invention, manufacture craft is simple, green non-pollution, the metal oxide of preparation or metal oxide composite have active high, specific area is large, density is low, porosity is high, easily accomplish scale production.
Accompanying drawing explanation
Fig. 1 is the picture of the carbon aerogels that embodiment 1,2,3,6,11,12,14,20 prepares;
Fig. 2 is the powder diagram of iron oxide-carbon composite prepared by embodiment 1;
Fig. 3 is the powder diagram of zinc oxide-carbon composite prepared by embodiment 12;
Fig. 4 is the powder diagram of tin oxide-carbon composite prepared by embodiment 23.
Embodiment
Embodiment 1
10g glucose and 6g polyvinylpyrrolidone (K30) are dissolved in 60mL water, add 0.3g Fe(NO3)39H2O again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel after reaction terminates and see Fig. 1 (a), gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 3 hours, obtain iron oxide-carbon composite, its powder diagram is shown in Fig. 2, as can be seen from the figure has the peak of iron oxide (PDF No.40-1139).
Embodiment 2
5.5g sucrose and 0.5g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 20mL water, add 0.6g zirconyl nitrate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel and see Fig. 1 (b) after reaction terminates, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 2 hours, obtain zirconia-carbon composite.
Embodiment 3
5g lactose and 0.6g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 15mL water, add 10mL acetic acid, add 0.9g calcium chloride again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel and see Fig. 1 (c) after reaction terminates, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 4 hours, obtain calcium oxide-carbon composite.
Embodiment 4
7g stachyose and 1g Sodium Polyacrylate (Mw:5000000 ~ 7000000) are dissolved in 25mL water, add 7mL acetic acid, add 1.2g lanthanum nitrate again, mixed liquor is transferred in closed reactor, react 7 hours at 180 DEG C, obtain cylindric gel after reaction terminates, after CO 2 supercritical drying, 900 DEG C of calcinings obtain lanthana-carbon composite in 4 hours in a nitrogen atmosphere.
Embodiment 5
1g isomaltoketose and the poly-propionamide of 0.05g hydrolysis are dissolved in 5mL water, add 4mL acrylic acid, add 1.5g Fe(NO3)39H2O again, mixed liquor is transferred in closed reactor, react 6 hours at 190 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 900 DEG C of calcinings within 4 hours, obtain iron oxide-carbon composite.
Embodiment 6
5g raffinose and 0.7g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 15mL water, add 6mL glacial acetic acid, add 1.0g ironic citrate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel and see Fig. 1 (d) after reaction terminates, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 4 hours, obtain iron oxide-carbon composite.
Embodiment 7
5g potato starch and 0.8g acrylic acid and methacrylate polymer are dissolved in 30mL water, add 5mL concentrated ammonia liquor (concentration 28%), add 1.2g five oxalic acid hydrate iron again, mixed liquor is transferred in closed reactor, react 10 hours at 170 DEG C, obtain cylindric gel after reaction terminates, after freeze drying, 1000 DEG C of calcinings obtain iron oxide-carbon composite in 3 hours in a nitrogen atmosphere.
Embodiment 8
7g chitosan oligomer and 0.8g poly are dissolved in 15mL water, add 4mL concentrated ammonia liquor (concentration 28%), add 2.2g cobalt acetate again, mixed liquor is transferred in closed reactor, react 10 hours at 170 DEG C, reaction terminate after obtain cylindric gel, gel after CO 2 supercritical drying in a nitrogen atmosphere 1000 DEG C of calcinings within 2 hours, obtain cobalt oxide-carbon composite.
Embodiment 9
5g cyclodextrin and 1g poly are dissolved in 25mL water, add 3.5mL diethylenetriamine, add 2.4g cobalt carbonate again, mixed liquor is transferred in closed reactor, react 3.5 hours at 240 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying under air 800 DEG C of calcinings within 5 hours, obtain cobalt oxide-carbon composite.
Embodiment 10
4g cyclodextrin and 1.5g polyvinylpyrrolidone (K30) are dissolved in 25mL water, add 3.5mL concentrated ammonia liquor (concentration 28%), add 2.6g nickel acetate again, mixed liquor is transferred in closed reactor, react 4 hours at 230 DEG C, reaction terminate after obtain cylindric gel, gel after CO 2 supercritical drying in a nitrogen atmosphere 800 DEG C of calcinings within 5 hours, obtain nickel oxide-carbon composite.
Embodiment 11
3g white dextrin and 1.5g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 20mL water, add 3mL triethylamine, add 1.7g Nickelous nitrate hexahydrate again, mixed liquor is transferred in closed reactor, react 5.5 hours at 210 DEG C, obtain cylindric gel and see Fig. 1 (e) after reaction terminates, gel after freeze drying under air 800 DEG C of calcinings within 5 hours, obtain nickel oxide.
Embodiment 12
6g glucose and 1.0g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 19mL water, add 10mL formic acid, add 3.0g zinc nitrate hexahydrate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel after reaction terminates and see Fig. 1 (f), gel after freeze drying in a nitrogen atmosphere 700 DEG C of calcinings within 6 hours, obtain zinc oxide-carbon composite, its powder diagram is shown in Fig. 3, as can be seen from the figure has the peak of zinc oxide (PDF No.36-1451).
Embodiment 13
5g octyl group butanedioic acid sodium salt starch and 0.5g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 10mL water, add 9mL benzoic acid, add 3.2g zinc acetate again, mixed liquor is transferred in closed reactor, react 10 hours at 160 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in air atmosphere 800 DEG C of calcinings within 4 hours, obtain zinc oxide.
Embodiment 14
7g carboxy starch glue and 0.55g poly-aspartate are dissolved in 17mL water, add 7mL ethanedioic acid, add 3.4g manganese chloride again, mixed liquor is transferred in closed reactor, react 9 hours at 170 DEG C, obtain cylindric gel and see Fig. 1 (g) after reaction terminates, gel after freeze drying under air 1000 DEG C of calcinings within 2 hours, obtain manganese oxide-carbon composite.
Embodiment 15
4g hydroxypropyl starch ether and 0.6g poly-aspartate are dissolved in 6mL water, add 4mL quinine, add 3.6ml manganese nitrate again, mixed liquor is transferred in closed reactor, react 7 hours at 180 DEG C, obtain cylindric gel after reaction terminates, after freeze drying, 900 DEG C of calcinings obtain manganese oxide in 2 hours under air.
Embodiment 16
5.6g cellulose and 0.7g poly-epoxy succinic acid are dissolved in 13mL water, add 8mL acetic acid, add 5g zinc nitrate again, mixed liquor is transferred in closed reactor, react 9 hours at 170 DEG C, reaction terminate after obtain cylindric gel, gel after CO 2 supercritical drying in a nitrogen atmosphere 1000 DEG C of calcinings within 2 hours, obtain zinc oxide-carbon composite.
Embodiment 17
6.8g hemicellulose and 0.8g polyvinyl alcohol are dissolved in 15mL water, add 6mL acetic acid, add 1.8g zirconium chloride again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 500 DEG C of calcinings within 6 hours, obtain zirconia-carbon composite.
Embodiment 18
4.6g glycogen and 0.8g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 15mL water, add 10mL acetic acid, add 3.9g acetic acid zirconium again, mixed liquor is transferred in closed reactor, at 190 DEG C react 6 hours, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 2 hours, obtain zirconia-carbon composite.
Embodiment 19
6g wood sugar and 1g polyvinyl alcohol are dissolved in 30mL water, add 6mL concentrated ammonia liquor (concentration 28%), add 5g calcium chloride dihydrate again, mixed liquor is transferred in closed reactor, react 3 hours at 300 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 900 DEG C of calcinings within 2 hours, obtain calcium oxide-carbon composite.
Embodiment 20
7g Arabic gum and 5g Sodium Polyacrylate (Mw:5000000 ~ 7000000) are dissolved in 31mL water, add 7mL concentrated ammonia liquor (concentration 28%), add 1.5g calcium nitrate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, obtain cylindric gel and see Fig. 1 (h) after reaction terminates, gel after freeze drying in air atmosphere 900 DEG C of calcinings within 4 hours, obtain calcium oxide.
Embodiment 21
6.7g mucopolysaccharide and 1.2g polyvinylpyrrolidone (K30) are dissolved in 15mL water, add 6mL acrylic acid, add 1.6g strontium chloride again, mixed liquor is transferred in closed reactor, react 17 hours at 140 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 900 DEG C of calcinings within 5 hours, obtain strontium oxide strontia-carbon composite.
Embodiment 22
8g milk ketose and 1.0g polyvinylpyrrolidone (K30) are dissolved in 30mL water, add 7mL ethanedioic acid, add 2.0g zinc nitrate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 1 hour, obtain zinc oxide-carbon composite.
Embodiment 23
6g FOS and 1g poly are dissolved in 25mL water, add 7mL formic acid, add 3.5g butter of tin again, mixed liquor is transferred in closed reactor, at 170 DEG C react 9 hours, reaction terminate after obtain cylindric gel, gel after freeze drying under air 300 DEG C of calcinings within 7 hours, obtain tin oxide, its powder diagram is shown in Fig. 4, as can be seen from the figure has the peak of tin oxide (PDF No.13-0111).
Embodiment 24
2.7g xylo-oligosaccharide and 2.2g polyvinylpyrrolidone (K30) are dissolved in 16mL water, add 6mL acrylic acid, add 1.7g ammonium vanadate again, mixed liquor is transferred in closed reactor, react 7 hours at 180 DEG C, obtain cylindric gel after reaction terminates, after freeze drying, the lower 1000 DEG C of calcinings of air atmosphere obtain vanadic oxide in 1 hour.
Embodiment 25
4g galactooligosaccharide and 1.2g poly-epoxy succinic acid are dissolved in 25mL water, add 7mL benzoic acid, add 4.5g cadmium nitrate again, mixed liquor is transferred in closed reactor, react 4 hours at 230 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 1000 DEG C of calcinings within 2 hours, obtain cadmium oxide-carbon composite.
Embodiment 26
5.8g oligoisomaltose and 0.8g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 15mL water, add 6mL acrylic acid, add 0.8g lead acetate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 900 DEG C of calcinings within 3 hours, obtain lead oxide-carbon composite.
Embodiment 27
10g iMOS and 1.5g polyacrylamide (Mw:2000000 ~ 14000000) are dissolved in 45mL water, add 5mL benzoic acid, add 4.8g antimony chloride again, mixed liquor is transferred in closed reactor, react 9 hours at 170 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 800 DEG C of calcinings within 5 hours, obtain antimony oxide-carbon composite.
Embodiment 28
2.5g oligomeric dragon gallbladder sugar and 0.5g polyvinylpyrrolidone (K30) are dissolved in 10mL water, add 6mL acrylic acid, add 0.6g five nitric hydrate bismuth again, mixed liquor is transferred in closed reactor, react 7 hours at 180 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 700 DEG C of calcinings within 6 hours, obtain bismuth oxide-carbon composite.
Embodiment 29
5g glucose, 5g sucrose and 5.0g polyvinyl alcohol are dissolved in 60mL water, adding 15mL acetic acid, add 5g ammonium molybdate again, mixed liquor is transferred in closed reactor, react 5 hours at 200 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 600 DEG C of calcinings within 7 hours, obtain molybdenum oxide-carbon composite.
Embodiment 30
3g lactose, 3g cyclodextrin and 1g polyvinylpyrrolidone (K30) are dissolved in 10mL water, add 5mL acrylic acid, add 1.5g ammonium ceric nitrate again, mixed liquor is transferred in closed reactor, react 15 hours at 150 DEG C, reaction terminate after obtain cylindric gel, gel after freeze drying in a nitrogen atmosphere 1500 DEG C of calcinings within 2 hours, obtain cerium oxide-carbon composite.

Claims (10)

1. the preparation method of a metal oxide or metal oxide composite, it is characterized in that: in closed container, by water-soluble sugar compounds and water soluble polymer water-soluble, add slaine, 140 ~ 300 DEG C of reactions, drying, calcining obtain metal oxide or metal oxide composite.
2. the preparation method of metal oxide according to claim 1 or metal oxide composite, is characterized in that: described saccharide compound is selected from monose, disaccharides, compound sugar, polysaccharide.
3. the preparation method of metal oxide according to claim 2 or metal oxide composite, it is characterized in that: described saccharide compound is selected from glucose, fructose, sucrose, maltose, lactose, stachyose, raffinose, isomaltoketose, milk ketose, FOS, xylo-oligosaccharide, galactooligosaccharide, oligoisomaltose, iMOS, oligomeric dragon gallbladder sugar, soyabean oligosaccharides, chitosan oligomer, cyclodextrin, starch, Acid modified starch, oxidized starch, white dextrin, yellow dextrin, faint yellow dextrin, acetoxylation starch, octyl group butanedioic acid sodium salt starch, hydroxypropyl starch ether, oxirane crosslinked starch, amylan, starch acetate glue, carboxy starch glue, water-fast amylan, cellulose, hemicellulose, glycogen, wood sugar, Arabic gum, mucopolysaccharide.
4. the preparation method of metal oxide according to claim 1 or metal oxide composite, is characterized in that: described water soluble polymer is polyvinylpyrrolidone, polyacrylic acid, Sodium Polyacrylate, polyacrylamide, hydrolyzed polyacrylamide, acrylic acid and methacrylate polymer, PLA, poly, poly-aspartate, poly-epoxy succinic acid, chitin, polyvinyl alcohol.
5. the preparation method of metal oxide according to claim 1 or metal oxide composite, is characterized in that: described slaine is selected from vanadium, manganese, iron, cobalt, nickel, zinc, cadmium, chromium, lead, zirconium, magnesium, calcium, strontium, barium, cerium, tungsten, bismuth, antimony, molybdenum, rare-earth salts.
6. the preparation method of metal oxide according to claim 5 or metal oxide composite, is characterized in that: slaine is selected from iron chloride, ferric nitrate, ferric sulfate, ferrous sulfate, frerrous chloride, ironic citrate, ferric oxalate, ferrous oxalate, iron ammonium sulfate, cobaltous sulfate, cobaltic chloride, cobalt acetate, cobalt chloride, Hexammine cobaltic chloride, cobalt carbonate, cobalt nitrate, nickel nitrate, nickel acetate, nickel chloride, nickelous sulfate, zinc nitrate, zinc acetate, zinc chloride, zinc sulfate, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, manganese carbonate, zirconium chloride, zirconyl nitrate, calcium chloride, calcium nitrate, calcium carbonate, calcium sulfate, strontium chloride, strontium nitrate, strontium bromide, strontium iodide, strontium hydroxide, butter of tin, stannous chloride, sodium tungstate, cerium chloride, cerous nitrate, magnesium chloride, magnesium hydroxide, yttrium chloride, yttrium nitrate, zinc nitrate, zinc chloride, zinc acetate, cadmium nitrate, cadmium acetate, nitric acid antimony, antimony chloride, bismuth nitrate, bismuth chloride, barium nitrate, barium chloride, lead acetate, ammonium vanadate, lanthanum nitrate, ammonium molybdate.
7. the preparation method of metal oxide according to claim 1 or metal oxide composite, it is characterized in that: add organic acid or alkali in reaction system, described organic acid or alkali are selected from acetic acid, formic acid, ethanedioic acid, acrylic acid, benzoic acid, ammoniacal liquor, pyridine, triethylamine, triethanolamine, monoethanolamine, Tetramethylammonium hydroxide, diisopropyl ethyl ammonia, diethylenetriamine, quinine.
8. the preparation method of metal oxide according to claim 1 or metal oxide composite, is characterized in that: reaction temperature is 160 ~ 230 DEG C.
9. according to the preparation method of one of any described metal oxide of claim 1 to 8 or metal oxide composite, it is characterized in that: the mass ratio of saccharide compound and water soluble polymer is 1:6 ~ 1:0.005, the mass ratio of saccharide compound and water is 1:60 ~ 1:0.5, and the mass ratio of saccharide compound and slaine is 25:1 ~ 1:1.
10. according to the preparation method of one of any described metal oxide of claim 1 to 8 or metal oxide composite, it is characterized in that: 300 ~ 1200 DEG C of calcination processing obtain metal oxide composite under an inert atmosphere, obtain metal oxide in 300 ~ 1200 DEG C of calcination processing in air atmosphere.
CN201310748663.7A 2013-12-31 2013-12-31 A kind of preparation method of metal oxide or metal oxide composite Expired - Fee Related CN104752069B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310748663.7A CN104752069B (en) 2013-12-31 2013-12-31 A kind of preparation method of metal oxide or metal oxide composite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310748663.7A CN104752069B (en) 2013-12-31 2013-12-31 A kind of preparation method of metal oxide or metal oxide composite

Publications (2)

Publication Number Publication Date
CN104752069A true CN104752069A (en) 2015-07-01
CN104752069B CN104752069B (en) 2018-10-26

Family

ID=53591598

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310748663.7A Expired - Fee Related CN104752069B (en) 2013-12-31 2013-12-31 A kind of preparation method of metal oxide or metal oxide composite

Country Status (1)

Country Link
CN (1) CN104752069B (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845454A (en) * 2016-03-28 2016-08-10 西安科技大学 Method for preparing N-doped porous carbon/ferric oxide compound powder
CN106363166A (en) * 2016-09-12 2017-02-01 厦门理工学院 Composite powder formed by uniformly doping nano-La2O3 in nano-Mo and preparation method thereof
CN106693985A (en) * 2016-11-24 2017-05-24 上海交通大学 Preparation method of sheet spinel structure cobalt-manganese composite oxide
CN106987106A (en) * 2017-04-21 2017-07-28 戴琪 A kind of preparation method for removing ethene antibacterial and mouldproof fruit-vegetable plastic wrap
CN107237008A (en) * 2017-06-01 2017-10-10 赵云飞 Preparation method, electrode and the electrochemical sensor of porous nano-fibre
CN107337975A (en) * 2017-07-21 2017-11-10 南京理工大学 Infrared-reflection heat-insulation coating based on aluminium compound and preparation method thereof
CN107384072A (en) * 2017-07-21 2017-11-24 南京理工大学 Infrared-reflection heat-insulation coating based on bismuth molybdate compound and preparation method thereof
CN107670095A (en) * 2017-09-28 2018-02-09 广东景兴健康护理实业股份有限公司 A kind of bacteria resistance function powder and non-woven fabrics chip for amenities
CN107946090A (en) * 2017-11-20 2018-04-20 宝鸡文理学院 A kind of high power capacity cobalt ions intercalation porous oxidation manganese electrode material and preparation method thereof
CN108558102A (en) * 2018-02-12 2018-09-21 东华大学 A method of carbonization crystallization treatment high organic wastewater with high salt
CN108671924A (en) * 2018-05-24 2018-10-19 中南大学 A kind of nano metal/carbon composite and its preparation method and application
CN109464968A (en) * 2018-12-06 2019-03-15 西华大学 It is a kind of high at charcoal-aero gel and preparation method thereof, application
CN109786711A (en) * 2019-01-23 2019-05-21 电子科技大学 A kind of preparation method of porous carbon skeleton cladding tin combination electrode material
CN109801792A (en) * 2019-01-14 2019-05-24 中南林业科技大学 The preparation method and application of carbon coating iron oxide electrode material
CN109830380A (en) * 2019-02-18 2019-05-31 南阳理工学院 A kind of electrode material for super capacitor, preparation method and application
CN110436462A (en) * 2019-07-29 2019-11-12 华南理工大学 A kind of micro-pore carbon material and the preparation method and application thereof preparing highly selective separation propylene propane using starch
CN110770863A (en) * 2017-11-24 2020-02-07 株式会社Lg化学 Preparation method of negative electrode active material for pseudo capacitor
CN110922832A (en) * 2019-12-19 2020-03-27 和县卜集振兴标准件厂 Anti-slip thread rust-proof treatment process for bolt surface
CN110961107A (en) * 2019-12-10 2020-04-07 重庆工商大学 Nano iron oxide material, preparation method and application thereof
CN111135817A (en) * 2019-12-20 2020-05-12 桂林理工大学 Black oxygen-deficient bismuth oxide, rare earth metal-doped oxygen-deficient bismuth oxide photocatalytic material and preparation method thereof
CN112758923A (en) * 2021-01-05 2021-05-07 中国科学院青岛生物能源与过程研究所 Method for preparing magnetic activated carbon from sugar solution
CN113223870A (en) * 2021-04-15 2021-08-06 山东科技大学 Preparation and application of carbon electrode material derived based on waste mask
CN113800558A (en) * 2021-09-10 2021-12-17 华中科技大学 Method for preparing self-stabilizing nano zirconia sol by hydrothermal method

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456569A (en) * 2008-07-22 2009-06-17 绍兴纳诺气凝胶新材料研发中心有限公司 Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost
CN102227019A (en) * 2011-05-23 2011-10-26 南京大学 Method for preparing tin-carbon composite material for cathode of lithium ion battery
CN102417606A (en) * 2011-08-03 2012-04-18 武汉大学 Preparation method of chitin aerogel
CN103406096A (en) * 2013-07-17 2013-11-27 国家纳米科学中心 Nitrogen-doped porous carbon material, preparation method and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101456569A (en) * 2008-07-22 2009-06-17 绍兴纳诺气凝胶新材料研发中心有限公司 Method for quick-speed preparing aerogel by hydro-thermal synthesis at low cost
CN102227019A (en) * 2011-05-23 2011-10-26 南京大学 Method for preparing tin-carbon composite material for cathode of lithium ion battery
CN102417606A (en) * 2011-08-03 2012-04-18 武汉大学 Preparation method of chitin aerogel
CN103406096A (en) * 2013-07-17 2013-11-27 国家纳米科学中心 Nitrogen-doped porous carbon material, preparation method and use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ROBIN J. WHITE等: ""A sustainable synthesis of nitrogen-doped carbon aerogels"", 《GREEN CHEMISTRY》 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845454A (en) * 2016-03-28 2016-08-10 西安科技大学 Method for preparing N-doped porous carbon/ferric oxide compound powder
CN106363166B (en) * 2016-09-12 2019-03-01 厦门理工学院 A kind of nanometer of La2O3Uniform Doped nanometer molybdenum composite powder and preparation method thereof
CN106363166A (en) * 2016-09-12 2017-02-01 厦门理工学院 Composite powder formed by uniformly doping nano-La2O3 in nano-Mo and preparation method thereof
CN106693985A (en) * 2016-11-24 2017-05-24 上海交通大学 Preparation method of sheet spinel structure cobalt-manganese composite oxide
CN106693985B (en) * 2016-11-24 2020-08-18 上海交通大学 Preparation method of flaky spinel-structured cobalt-manganese composite oxide
CN106987106A (en) * 2017-04-21 2017-07-28 戴琪 A kind of preparation method for removing ethene antibacterial and mouldproof fruit-vegetable plastic wrap
CN107237008A (en) * 2017-06-01 2017-10-10 赵云飞 Preparation method, electrode and the electrochemical sensor of porous nano-fibre
CN107337975A (en) * 2017-07-21 2017-11-10 南京理工大学 Infrared-reflection heat-insulation coating based on aluminium compound and preparation method thereof
CN107384072A (en) * 2017-07-21 2017-11-24 南京理工大学 Infrared-reflection heat-insulation coating based on bismuth molybdate compound and preparation method thereof
CN107670095A (en) * 2017-09-28 2018-02-09 广东景兴健康护理实业股份有限公司 A kind of bacteria resistance function powder and non-woven fabrics chip for amenities
CN107946090A (en) * 2017-11-20 2018-04-20 宝鸡文理学院 A kind of high power capacity cobalt ions intercalation porous oxidation manganese electrode material and preparation method thereof
CN107946090B (en) * 2017-11-20 2019-07-02 宝鸡文理学院 A kind of high capacity cobalt ions intercalation porous manganese dioxide electrode material and preparation method thereof
CN110770863B (en) * 2017-11-24 2022-09-30 株式会社 Lg新能源 Preparation method of negative electrode active material for pseudo capacitor
US11276533B2 (en) 2017-11-24 2022-03-15 Lg Chem, Ltd. Process for preparing anode active material for pseudocapacitor
CN110770863A (en) * 2017-11-24 2020-02-07 株式会社Lg化学 Preparation method of negative electrode active material for pseudo capacitor
CN108558102A (en) * 2018-02-12 2018-09-21 东华大学 A method of carbonization crystallization treatment high organic wastewater with high salt
CN108671924A (en) * 2018-05-24 2018-10-19 中南大学 A kind of nano metal/carbon composite and its preparation method and application
CN108671924B (en) * 2018-05-24 2020-06-16 中南大学 Nano metal/carbon composite material and preparation method and application thereof
CN109464968A (en) * 2018-12-06 2019-03-15 西华大学 It is a kind of high at charcoal-aero gel and preparation method thereof, application
CN109801792A (en) * 2019-01-14 2019-05-24 中南林业科技大学 The preparation method and application of carbon coating iron oxide electrode material
CN109801792B (en) * 2019-01-14 2021-06-15 中南林业科技大学 Preparation method and application of carbon-coated iron oxide electrode material
CN109786711A (en) * 2019-01-23 2019-05-21 电子科技大学 A kind of preparation method of porous carbon skeleton cladding tin combination electrode material
CN109830380A (en) * 2019-02-18 2019-05-31 南阳理工学院 A kind of electrode material for super capacitor, preparation method and application
CN110436462A (en) * 2019-07-29 2019-11-12 华南理工大学 A kind of micro-pore carbon material and the preparation method and application thereof preparing highly selective separation propylene propane using starch
CN110961107A (en) * 2019-12-10 2020-04-07 重庆工商大学 Nano iron oxide material, preparation method and application thereof
CN110961107B (en) * 2019-12-10 2023-03-28 重庆工商大学 Nano iron oxide material, preparation method and application thereof
CN110922832A (en) * 2019-12-19 2020-03-27 和县卜集振兴标准件厂 Anti-slip thread rust-proof treatment process for bolt surface
CN111135817A (en) * 2019-12-20 2020-05-12 桂林理工大学 Black oxygen-deficient bismuth oxide, rare earth metal-doped oxygen-deficient bismuth oxide photocatalytic material and preparation method thereof
CN112758923A (en) * 2021-01-05 2021-05-07 中国科学院青岛生物能源与过程研究所 Method for preparing magnetic activated carbon from sugar solution
CN113223870A (en) * 2021-04-15 2021-08-06 山东科技大学 Preparation and application of carbon electrode material derived based on waste mask
CN113800558A (en) * 2021-09-10 2021-12-17 华中科技大学 Method for preparing self-stabilizing nano zirconia sol by hydrothermal method

Also Published As

Publication number Publication date
CN104752069B (en) 2018-10-26

Similar Documents

Publication Publication Date Title
CN104752069A (en) Preparation method of metallic oxide or metallic oxide composite material
Ghiyasiyan-Arani et al. Effect of Li2CoMn3O8 nanostructures synthesized by a combustion method on montmorillonite K10 as a potential hydrogen storage material
Gash et al. Use of epoxides in the sol− gel synthesis of porous iron (III) oxide monoliths from Fe (III) salts
CN100575251C (en) The preparation method of carbon nanotube supported magnetic ferroferric oxide nano-particles
CN104741046A (en) Method for preparing aluminum oxide/carbon aerogel composite material
CN103950969B (en) A kind of preparation method of multistage porous metal oxide nano material
CN109174155B (en) Preparation method and application of loose and porous silicon dioxide coated Co-N-C hollow nanotube material
CN101759146B (en) Method for preparing ZnO/ZnFe2O4 compound nano hollow sphere
Ching et al. Nonaqueous sol− gel syntheses of microporous manganese oxides
CN102557021B (en) Nanocomposite material preparation method based on graphene oxide autocatalysis
CN104743540A (en) Preparation method for nitrogen-doped carbon material
CN105923625B (en) A kind of preparation method of graphene-supported uniform single oxide quantum dot
CN104275173A (en) Carbon-coated metal-doped zinc oxide composite photocatalysis nano material and preparation method thereof
CN102161498B (en) Preparation method of uniformly dispersed nano lanthanum oxide
WO2012144532A1 (en) Solution of gold/hydroxoanion complex and process for producing substance loaded with gold nanoparticles
CN102886279A (en) Preparation method for coating metal nanoparticles on surface of nano-titania
CN103553140A (en) Method for preparing lanthanum ferrite nanodisk
CN109718823A (en) N-doped TiO2/ C composite and the preparation method and application thereof
WO2020119717A1 (en) Hollow ceric oxide preparation method
CN106315690A (en) Porous cobalt tetroxide nanosheet and preparation method thereof
CN102616850A (en) Preparation method for monodisperse vanadium pentoxide solid microspheres
CN108380197A (en) A kind of methane CO based on microwave activation2Preparing synthetic gas by reforming nucleocapsid catalyst and preparation method thereof
WO2024109834A1 (en) Ultra-small stable platinum-cobalt nanoparticle catalyst, and preparation method therefor and use thereof in selective hydrogenation
CN102583560A (en) Spherical gamma-MnO2 particle and preparation method thereof
CN101327952A (en) Preparation of Ce4Ti9O24 composite oxides

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181026

CF01 Termination of patent right due to non-payment of annual fee