CN105980055A - Process for manufacturing supported nanocolloidal particles, and supported nanocolloidal particles - Google Patents
Process for manufacturing supported nanocolloidal particles, and supported nanocolloidal particles Download PDFInfo
- Publication number
- CN105980055A CN105980055A CN201580007258.7A CN201580007258A CN105980055A CN 105980055 A CN105980055 A CN 105980055A CN 201580007258 A CN201580007258 A CN 201580007258A CN 105980055 A CN105980055 A CN 105980055A
- Authority
- CN
- China
- Prior art keywords
- nanometer colloid
- granule
- nanometer
- particulate load
- manufacture method
- Prior art date
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- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 38
- 239000002245 particle Substances 0.000 title abstract description 26
- 150000004676 glycans Chemical class 0.000 claims abstract description 39
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 39
- 239000005017 polysaccharide Substances 0.000 claims abstract description 39
- 239000004094 surface-active agent Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims description 98
- 239000008187 granular material Substances 0.000 claims description 54
- 229920002521 macromolecule Polymers 0.000 claims description 31
- 229920002678 cellulose Polymers 0.000 claims description 24
- 239000001913 cellulose Substances 0.000 claims description 24
- 239000003292 glue Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 210000001124 body fluid Anatomy 0.000 claims description 8
- 239000010839 body fluid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 229920002101 Chitin Polymers 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000002612 dispersion medium Substances 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 3
- 238000005054 agglomeration Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 48
- 239000007788 liquid Substances 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- -1 tetrachloro gold (III) Chemical compound 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229920000936 Agarose Polymers 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001147468 Chondrus ocellatus Species 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000004503 fine granule Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004531 microgranule Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/23—
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B01J35/393—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
Provided is a manufacturing process capable of manufacturing supported nanocolloidal particles which can yield a colloidal solution such that the concentration of the colloidal solution is enhanced by suppressing the agglomeration among nanocolloidal particles and which can keep the particle sizes even after long-term storage and be easily redispersed. Nanocolloidal particles supported on a polysaccharide-based polymer are obtained by a manufacturing process which comprises both a step for preparing a dissolved or swollen polysaccharide-based polymer in a surfactant solution and a step for mixing the dissolved or swollen polysaccharide-based polymer with a nanocolloidal fluid in which nanocolloidal particles are dispersed in a dispersion medium.
Description
Technical field
The manufacture method that the present invention relates to nanometer colloid particulate load thing and the nanometre glue obtained by this preparation method
Body particulate load thing.
Background technology
Using nanometer colloid granule such as the catalyst of fuel cell, waste gas purification use time, carry out
The base materials such as pottery, macromolecule be impregnated in metal nano colloid solution the method making it adsorb.Now,
The biggest catalytic action of specific surface area of nanometer colloid granule the most more improves, it is therefore desirable in colloid solution
The high concentration of nanometer colloid granule.But, on the other hand, during by granule high concentration, easily produce
The coarsening caused by granule gathering each other, it is also necessary to suppress this gathering.
In order to meet these contrary requirements, carry out following technology: add an intramolecular and have hydrophobic
Base and the dispersant of hydrophilic group, protective agent so that it is be adsorbed in the surface of nanometer colloid granule, comprise granule,
Thus suppression nanometer colloid granule gathering each other, improves dispersibility, obtains the nanometer colloid of high concentration
Grain dispersion liquid (such as, patent documentation 1).
But, thus by when comprising nanometer colloid granule with dispersant, there is nanometer colloid granule institute's phase
The problem that the catalytic action treated etc. are hindered by dispersant.
It addition, patent documentation 2 is recorded: utilize reducing agent, gold microgranule is made to be attached to polrvinyl chloride etc.
The high molecular surface of ethylene base system and obtain macromolecular material.And then, Patent Document 3 discloses: with
Cellulose be main constituent fiber in load containing platinum family element catalyst obtained by solid catalyst, note
Carrying, this solid catalyst such as can obtain as follows: make that above-mentioned fiber is impregnated in containing catalyst is molten
In liquid, then make it be dried thus obtain.But, in these methods described in patent documentation 2,3, deposit
In the problem being difficult to obtain the loaded article of high concentration.
It addition, Patent Document 4 discloses: have metal nano at cellulose nano-fibrous area load
The complex of granule.As its preparation method, describe, make metallic compound and surface have carboxyl or carboxylic acid
Cellulose nano-fibrous these groups of ester group combine, and are subsequently adding reducing agent etc., thus will above-mentioned and
The metallic compound that carboxyl etc. combine reduces and forms metal nanoparticle.But, this nanometer colloid granule
There is the nanometer colloid granule coarsening etc. loaded when loaded article is prepared in higher concentrations and be difficult to control to grain
The problem in footpath.
And then, Patent Document 5 discloses: microfibrillated cellulose is loaded with removing of argent colloid
Smelly paper, describes, and it is by cationic surfactant and composite metal hydride (reducing agent)
In the presence of by water-soluble silver compound reduction and obtain.But, in the method, utilize a large amount of use
Surfactant comprises metal colloid particles, therefore cannot be applied to the other fields such as catalyst.
Prior art literature
Patent documentation
Patent documentation 1: No. 4865772 publications of Japanese Patent No.
Patent documentation 2: No. 5114008 publications of Japanese Patent No.
Patent documentation 3: Japanese Unexamined Patent Publication 2011-98280 publication
Patent documentation 4: International Publication WO2010/095574 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2006-261709 publication
Summary of the invention
The problem that invention is to be solved
The present invention is in view of above-mentioned practical situation, it is therefore intended that, it is provided that: loaded article is loaded with nanometer colloid
The nanometer colloid particulate load thing of granule, and solve loaded article and its manufacture method of above-mentioned problem.That is,
Purpose is, it is provided that: owing to not producing the gathering each other of nanometer colloid granule therefore, it is possible to carry out colloid molten
The high concentration of liquid, long during storage can also keep particle size, nanometer colloid granule surface basic
Not by surfactant covering, redispersion easy nanometer colloid particulate load thing yet；With, can be with letter
Just means obtain the manufacture method of this loaded article.
For solving the scheme of problem
In order to solve above-mentioned problem, the manufacture method of the nanometer colloid particulate load thing of the present invention is such as lower section
Method, it possesses following operation: obtain dissolving in surfactant solution or swelling polysaccharide system high score
The operation of son；With, this dissolving or swelling polysaccharide system macromolecule are dispersed with nanometer in disperse medium
The operation of the nanometre glue body fluid mixing of colloidal solid, the method obtains in above-mentioned polysaccharide system macromolecule negative
It is loaded with the loaded article of nanometer colloid granule.
In above-mentioned manufacture method, as nanometer colloid granule, it is possible to use: selected from Au Ag Pt Pd,
One kind or two or more metal in ruthenium, rhodium, osmium, iridium and copper and/or the conjunction of above-mentioned one kind or two or more metal
The granule of gold.
It addition, as surfactant, it is possible to use: a kind in quaternary ammonium salt and carboxylate or 2 kinds
Above.
The consumption of above-mentioned surfactant is preferably 1～10 mass relative to nanometer colloid granule 100 mass parts
In the range of Fen.
As above-mentioned polysaccharide system macromolecule, it is possible to use many selected from cellulose, chitin and deacetylated shell
One kind or two or more in sugar.
The above-mentioned polysaccharide system preferred fiber diameter of macromolecule is in the range of 20～1000nm.
The nanometer colloid particulate load thing of the present invention is to be manufactured by the manufacture method of the invention described above, nanometer
Colloidal solid is carried on above-mentioned polysaccharide system macromolecule via above-mentioned surfactant.
The load capacity of above-mentioned nanometer colloid granule is set to relative to above-mentioned polysaccharide system macromolecule 100 mass parts
In the range of 1～15 mass parts.
The effect of invention
Manufacturing method according to the invention, can obtain that the gathering each other of nanometer colloid granule caused is thick
Bigization (Second Aggregation) is suppressed, when producing precipitation owing to taking care of during length, by being shaken gently for appearance
The operation of the simplicity such as device also is able to the nanometer colloid particulate load thing of redispersion.
In above-mentioned nanometer colloid particulate load thing, it is believed that via the surfactant nanometer colloid granule added
Being adsorbed in polysaccharide system macromolecule, this nanometer colloid granule is not comprised by surfactant, and except upper
Stating outside absorbed portion, the substantially all of part of particle surface is exposed, and the most also plays nanometer colloid granule
The most undiminished effect such as the catalytic action originally being had.
It addition, the high molecular kind of above-mentioned polysaccharide system used in the present invention is not particularly limited, logical
Crossing interpolation surfactant, nanometer colloid particulate load increases in the high molecular ratio of polysaccharide system, it addition,
During preservation, compared with the situation not using surfactant, also play particle diameter and go through effect steady in a long-term.
Additionally, carry out with the formation of nanometer colloid granule and the formation of nanometer colloid particulate load thing simultaneously
Prior art is different, form the operation (operation of modulation nanometre glue body fluid) of nanometer colloid granule with make through
The nanometre glue body fluid of ovennodulation and cellulose nano-fibrous dispersion liquid mix and form nanometer colloid granule
The operation of loaded article is independent, so can prepare nanometer colloid granule with independent technique, therefore may be used
More freely to control the composition of the nanometer colloid granule of load.Such as, conventional method is i.e. used
Reducing agent make the method difficulty that metal nano colloidal solid separates out at macromolecule surface, make solid solution, mixed
Brilliant nanometer colloid particulate load is also possibly realized in cellulose nano-fibrous.
It is independent technique like that it addition, above-mentioned, therefore, it can simplicity and synthesize nanometer colloid in large quantities
Granule, and then can be under room temperature, normal pressure, the technique few by carrying capacity of environment manufactures nanometre glue in large quantities
Body particulate load thing.
Detailed description of the invention
Hereinafter, embodiments of the present invention are illustrated, but the present invention is not limited to this.
The nanometer colloid particulate load thing of the present invention is loaded with as described above in polysaccharide system macromolecule
Nanometer colloid granule, can be obtained by the manufacture method including following operation: will be molten with surfactant
Liquid mixes and dissolves or be dispersed with nanometer colloid in swelling polysaccharide system macromolecule and disperse medium
The nanometre glue body fluid of granule mixes.
The granule that nanometer colloid granule is mean diameter 1～100nm used in the present invention, by way of example,
Can enumerate: the metallic particles of the platinum family etc. such as gold, silver, copper and platinum, palladium, ruthenium, rhodium, osmium, iridium.
Alternatively, it is also possible to be a kind of these metals or the granule comprising alloy of more than two kinds.Nanometre glue body fluid is point
Dispersion media is dispersed with the liquid of such nanometer colloid granule.
As the example of disperse medium, can enumerate: water, isopropanol (IPA), N-Methyl pyrrolidone
(NMP), methanol, ethanol, toluene etc., be not limited to these.Wherein, in terms of dispersion is easy
Set out, preferably water.
Above-mentioned nanometer colloid granule can be scattered in above-mentioned by utilizing known method by nanometre glue body fluid
Disperse medium manufactures, it is also possible to suitably utilize commercially available product.Its manufacture method is not particularly limited,
Such as, respectively, gold nano colloid is by by tetrachloro gold (III) acid (H [AuCl4]) in a liquid with also
The former dose of method carrying out reducing and obtain, nanoparticles is by entering silver nitrate with reducing agent in a liquid
Row reduction method and obtain.As reducing agent, it is possible to use sodium borohydride, sodium citrate, Vitamin C
Acid sodium etc..
Then, the polysaccharide system macromolecule used as loaded article in the present invention for combine 100 unit with
On the macromolecule of monosaccharide molecule.Polysaccharide system macromolecule is threadiness, and specific surface area is big, therefore,
By making nanometer colloid particulate load in the high molecular surface of such polysaccharide system, nanometre glue can be carried out
The high concentration of body granule.
As the high molecular disperse medium of polysaccharide system, if can by water or IPA, NMP, methanol,
The organic solvent such as ethanol, toluene dissolves or swelling is just not particularly limited, and is that hydrophilic is the easiest from base material
The aspects such as dispersion are set out, preferably water.
As the high molecular example of polysaccharide system, can enumerate: cellulose, acetylcellulose, carboxymethyl
Cellulose, chitin, chitosan, amylose, dextrin, glycogen, agarose, chondrus ocellatus Holmes
Glue etc., it is possible to use mixture of more than two kinds.
Wherein, native cellulose, chitin, chitosan are hydrophilic, use water as from can make
Aspect for disperse medium is set out as preferably.It addition, in terms of cheap and easy offer it is also preferred that.
Polysaccharide system macromolecule is preferably micropowder, and fiber diameter is preferably 20～1000nm, more excellent
Elect 20～200nm as.By using such fine granule, specific surface area can be increased further,
Nanometer colloid granule can be loaded in a large number.
Then, the surfactant used in the present invention is not particularly limited, it is possible to use anion system,
Cation system, nonionic system.As the example of anion system surfactant, can enumerate: single
Alkyl sulfate, alkyl polyoxyethylene sulfates, alkylbenzenesulfonate, MAP, carboxylate
Deng.As the example of cation system surfactant, can enumerate: alkyl trimethyl ammonium salt, dialkyl group
The quaternary ammonium salts such as dimethyl ammonium, alkyl benzyl dimethyl ammonium salt.Example as nonionic system surfactant
Son, can enumerate: polyoxyethylene alkyl ether, sorbitan fatty esters, alkyl polyglucoside,
The nonionic such as fatty diglycollic amide, alkyl monoglyceryl ether system activating agent etc..From nanometer colloid granule
The aspect that adsorption efficiency is high is set out, the most above-mentioned quaternary ammonium salt or carboxylate.As long as surfactant is not being disobeyed
The scope of back of the body the object of the invention can also be applied in combination two or more.
Surfactant be dissolved in the most in advance solvent formed after surfactant solution with above-mentioned polysaccharide
It it is macromolecule mixing.But it is also possible to use, polysaccharide system macromolecule is dissolved or molten the most in a solvent
The method being added thereto to surfactant after swollen, or can also use and put into polysaccharide the most simultaneously
Class system macromolecule and surfactant mixing make polysaccharide system macromolecule dissolution or swelling method.
As the example of the solvent that can use herein, can enumerate: water or IPA, NMP, methanol,
Ethanol, toluene etc., from aspects, preferably water such as the dissolving of surfactant are easy.
The consumption of surfactant also depends on its kind, relative to nanometer colloid in terms of solid constituent conversion
Granule 100 mass parts is preferably 1～10 mass parts, more preferably 1～5 mass parts.If 1 mass parts with
On, then the present invention easily carries out the high concentration of target nanometer colloid granule.On the other hand, if
Below 10 mass parts, then it is assumed that, surfactant is substantially only used for nanometer colloid granule to polysaccharide system
High molecular absorption, becomes ignoring and is not adsorbed in above-mentioned polysaccharide system macromolecule and dissociates in the solution
The degree of amount, the surface of nanometer colloid granule is contained substantially no by surfactant and keeps exposing.
Make polysaccharide system macromolecule dissolution in above-mentioned surfactant solution, or pass through surfactant solution
Make it swelling, the solution comprising this polysaccharide system macromolecule and surfactant is disperseed in disperse medium
The nanometre glue body fluid having above-mentioned nanometer colloid granule mixes, such that it is able to obtain polysaccharide system macromolecule
In be loaded with the loaded article of nanometer colloid granule.Nanometer colloid particulate load amount is relative in common purposes
In polysaccharide system, macromolecule 100 mass parts is set to more than 1 mass parts, it is also possible to as required, obtains 15 matter
The more than amount part loaded article of such high concentration.
To being not particularly limited for forming the concrete operation of loaded article and condition, after above-mentioned mixing, example
Nanometer colloid particulate load thing is formed immediately after at room temperature mixing.Gained loaded article is for centrifugal
Seperator, discards the disperse medium obtained with the isolated in form of supernatant, such that it is able to carry out high concentration,
Loaded article through high concentration can be shaken gently for and easily redispersion by adding water.
Embodiment
Below, it is shown that embodiments of the invention, but the present invention is not limited by below example.Need
Illustrating, middle compounding ratio etc. are set to quality criteria (mass parts, matter unless otherwise specified below
Amount %).
[embodiment 1]
(1) preparation of nanometer colloid particle dispersion
Adding the distilled water 868.5g of 5 DEG C in the glass beaker of 1L, carrying out cooling together with beaker will
Liquid temperature remains 5 DEG C, puts into the sodium borohydride aqueous solution 22.5mL of 40mM simultaneously, uses magnetic agitation
Device, with 800～900rpm stirring 15 minutes.Then, 10mM is dripped with the rate of addition of 16～20 seconds/1
Silver nitrate aqueous solution amount to 9mL, thus obtain nanoparticles particle dispersion.After completion of dropwise addition quiet
Put 1 day.
(2) preparation of cellulose aqueous dispersions
At cellulose nano-fibrous aqueous dispersions (SUGINO MACHINE LIMITED CO., LTD.
Manufacture, the industrial chopped fiber of BiNFi-s, 2wt%) 5.0g adds distilled water 95.0g, enter with Glass rod
After row is pre-dispersed, it is completely dispersed by ultrasonic Treatment.Gained dispersion liquid is stood until returning to
Room temperature, then drips 1wt% stearyl trimethyl ammonium chloride (STMAC) aqueous solution of total amount 10 μ L,
The most at room temperature, use magnetic stirring apparatus to carry out stirring in 1 hour with 150～350rpm, thus obtain fibre
Dimension element aqueous dispersions (dispersion liquid 1).
(3) preparation of nanometer colloid particulate load thing dispersion liquid
The nanoparticles particle dispersion 92.7g obtained in above-mentioned (1) is moved to glass beaker, uses
Magnetic stirring apparatus is stirred in advance with 350rpm, puts into the cellulose obtained in above-mentioned (2) wherein
Aqueous dispersions 22mL, carries out stirring in 10 minutes, thus obtains nanometer colloid particulate load thing dispersion liquid.
Take out stirrer from beaker, at room temperature stand 1 day.And then, in order to confirm long-time stability, in room
Temperature is lower stands 1000 hours.
Nanometer colloid particulate load thing dispersion liquid after above-mentioned standing removes supernatant, with rotating speed
2000rpm carries out centrifugation in 3 minutes, liquid phase is removed by gradient method, thus obtains nanometer colloid
The concentrate of particle loading thing aqueous dispersion.
[embodiment 2,3, comparative example 3]
Obtain nanoparticles particle dispersion in the same manner as above-described embodiment 1, after completion of dropwise addition, stand 1
My god.
Dropping 1wt% stearyl trimethyl ammonium chloride (STMAC) aqueous solution total amount 50 μ L, in addition,
Utilize the method identical with above-described embodiment 1, obtain cellulose aqueous dispersions 2.It addition, dropping STMAC
Aqueous solution total amount 100 μ L, in addition, utilizes the method identical with above-described embodiment 1, obtains cellulose
Aqueous dispersions 3.It addition, do not use STMAC aqueous solution, in addition, utilize and above-described embodiment 1
Identical method, obtains cellulose aqueous dispersions 4.
In gained polysaccharide system high molecular dispersion liquid, the most directly use material shown in table 2, except this it
Outward, prepare nanometer colloid particulate load thing dispersion liquid the most respectively, at room temperature stand 1
It, with after 1000 hours, is removed liquid phase similarly to Example 1, thus obtains nanometer colloid particulate load
The concentrate of thing aqueous dispersion.
[embodiment 4]
(1) preparation of nanometer colloid particle dispersion
Adding the distilled water 787.5g of 5 DEG C in the glass beaker of 1L, carrying out cooling together with beaker will
Liquid temperature remains 5 DEG C, puts into the sodium borohydride aqueous solution 22.5mL of 40mM simultaneously, uses magnetic agitation
Device, carries out stirring in 15 minutes with 800～900rpm.Then, drip with the rate of addition of 16～20 seconds/1
Tetrachloro gold (III) acid (H [AuCl4]) aqueous solution of 1mM amounts to 90mL, thus obtains gold nano colloid
Grain dispersion liquid.1 day is stood after completion of dropwise addition.
(2) preparation of cellulose aqueous dispersions
Dropping 1wt% stearyl trimethyl ammonium chloride (STMAC) aqueous solution total amount 50 μ L, in addition,
The method identical with above-described embodiment 1 is utilized to obtain cellulose aqueous dispersions 2.
(3) preparation of nanometer colloid particulate load thing dispersion liquid
Use in the gold nano colloidal solid dispersion liquid 50.8g obtained in above-mentioned (1) and above-mentioned (2) and obtain
Cellulose aqueous dispersions (dispersion liquid 2), in addition, be prepared as nanometer with above-described embodiment 1
Colloidal solid loaded article dispersion liquid, goes after at room temperature standing 1 day and 1000 hours similarly to Example 1
Except liquid phase, thus obtain the concentrate of nanometer colloid particulate load thing aqueous dispersion.
[embodiment 5]
(1) preparation of nanometer colloid particle dispersion
Adding the distilled water 859.5g of 5 DEG C in the glass beaker of 1L, carrying out cooling together with beaker will
Liquid temperature remains 5 DEG C, puts into the sodium borohydride aqueous solution 22.5mL of 40mM simultaneously, uses magnetic agitation
Device, carries out stirring in 15 minutes with 800～900rpm.Then, drip with the rate of addition of 16～20 seconds/1
The palladium chloride aqueous solution of 5mM amounts to 18mL, thus obtains palladium nanometer colloid particle dispersion.Dropping knot
1 day is stood after bundle.
(2) preparation of cellulose aqueous dispersions
Dropping 1wt% stearyl trimethyl ammonium chloride (STMAC) aqueous solution total amount 100 μ L, except this it
Outward, the method identical with above-described embodiment 1 is utilized to obtain cellulose aqueous dispersions 3.
(3) preparation of nanometer colloid particulate load thing dispersion liquid
Use in the palladium nanometer colloid particle dispersion 94.0g obtained in above-mentioned (1) and above-mentioned (2) and obtain
Cellulose aqueous dispersions (dispersion liquid 3), in addition, be prepared as nanometer with above-described embodiment 1
Colloidal solid loaded article dispersion liquid, goes after at room temperature standing 1 day and 1000 hours similarly to Example 1
Except liquid phase, thus obtain the concentrate of nanometer colloid particulate load thing aqueous dispersion.
[table 1]
※ is relative to silver-colored 100 mass parts (wherein, converting with solid constituent)
[comparative example 1]
Adding the distilled water 868.5g of 5 DEG C in the glass beaker of 1L, carrying out cooling together with beaker will
Liquid temperature remains 5 DEG C, puts into the sodium borohydride aqueous solution 22.5mL of 40mM simultaneously, uses magnetic agitation
Device, carries out stirring in 15 minutes with 800～900rpm.Then, drip with the rate of addition of 16～20 seconds/1
The silver nitrate aqueous solution of 10mM amounts to 9mL, obtains nanometer colloid particle dispersion, quiet after completion of dropwise addition
Put 1 day.After standing, nanometer colloid particle dispersion is also stable, but silver concentration substantially 10ppm.
[comparative example 2]
Adding the distilled water 868.5g of 5 DEG C in the glass beaker of 1L, carrying out cooling together with beaker will
Liquid temperature remains 5 DEG C, puts into the sodium borohydride aqueous solution 225mL of 40mM simultaneously, uses magnetic stirring apparatus,
Stirring in 15 minutes is carried out with 800～900rpm.Then, 10mM is dripped with the rate of addition of 16～20 seconds/1
Silver nitrate aqueous solution amount to 90mL.It is steady in dispersion liquid that dropping has just started rear nanoparticles granule
Surely exist, but when persistently dripping, nanometer colloid granule coarsening, immediately become suspension.
For the nanometer colloid particulate load thing obtained in above-described embodiment and comparative example and comparative sample, as
Hereinafter obtain converted score like that, it addition, carry out spectrum resolution, thus investigate colloidal particle size.By result
It is shown in table 2.
＜ converted score ＞
Use the volume of the nanometer colloid particulate load thing of the utensil measurement embodiments 3 such as graduated cylinder, it is assumed that same
Under one centrifugal condition, the cellulose nano-fibrous compression ratio of average basis weight is not changed in, basis at this
On, using the volume of embodiment 3 as benchmark, obtain corresponding with cellulose nano-fibrous input weight
Concentration.
＜ spectrum resolution ＞
Use ultraviolet-uisible spectrophotometer (Shimadzu Scisakusho Ltd's manufacture, UV-2600, integration
Ball ISR-2600 uses), measure absorbance spectrum under the following conditions.It should be noted that with glue
Premised in body particle diameter and absorbing wavelength, linear dependence is set up, the parsing of the difference between sample by compare by
Absorbance peak intensity standardization and spectral shape that equalization obtains are carried out.This analytic method is applied to tool
There is the absorbance spectrum of the shape close to Gauss distribution, specifically, the value of numeric data obtain extinction
Degree peak wavelength X p, full width at half maximum (FWHM) (FWHM) or half width at half maximum (HWHM), resolve and as raw material
Nanometer colloid particle dispersion equalization after the difference of absorbance peak, full width at half maximum (FWHM) or half width at half maximum
Different.Prior to analytically, select multiple standards sample and be diluted operation, in the range of absorbance 0.3～3
It is standardized, thus it is the most consistent to confirm peak.
Unit: polystyrol/Polystyrene REF 67.754 10x10x45mm SARSTEDT
AG&Co. make
Wave-length coverage: 350～800mm
Scanning speed: middling speed
Auto injection spacing: ON
Slit width: 1.0mm
S/R switching standards
Accumulated time: 1.0 seconds
[table 2]
Result as shown in Table 2 understand, as comparative example 1,2, non-loaded in macromolecule in the case of,
High concentration and stable nanometer colloid particle dispersion cannot be obtained, as comparative example 3, do not use table
In the case of the activating agent of face, it is impossible to formed loaded article, even if or formed loaded article be also difficult to highly concentrated
Degreeization.
Industrial applicability
The nanometer colloid particulate load thing of the present invention may be used for catalyst etc..
Claims (8)
1. the manufacture method of a nanometer colloid particulate load thing, it is characterised in that possess following operation:
Obtain dissolving or the swelling high molecular operation of polysaccharide system in surfactant solution；With,
This dissolving or swelling polysaccharide system macromolecule are dispersed with nanometer colloid granule in disperse medium
Nanometre glue body fluid mixing operation,
The method obtains being loaded with the load of described nanometer colloid granule in described polysaccharide system macromolecule
Thing.
The manufacture method of nanometer colloid particulate load thing the most according to claim 1, it is characterised in that
Described nanometer colloid granule is a kind or 2 in Au Ag Pt Pd, ruthenium, rhodium, osmium, iridium and copper
Plant the granule of the alloy of above metal and/or described one kind or two or more metal.
The manufacture method of nanometer colloid particulate load thing the most according to claim 1 and 2, its feature exists
It is one kind or two or more in quaternary ammonium salt and carboxylate in, described surfactant.
4. according to the manufacture method of the nanometer colloid particulate load thing according to any one of claims 1 to 3,
It is characterized in that, the consumption of described surfactant relative to described nanometer colloid granule 100 mass parts is
In the range of 1～10 mass parts.
5. according to the manufacture method of the nanometer colloid particulate load thing according to any one of Claims 1 to 4,
It is characterized in that, described polysaccharide system macromolecule is in cellulose, chitin and chitosan
One kind or two or more.
6. according to the manufacture method of the nanometer colloid particulate load thing according to any one of Claims 1 to 5,
It is characterized in that, described polysaccharide system macromolecule has the fiber diameter in the range of 20～1000nm.
7. a nanometer colloid particulate load thing, it is characterised in that it is by arbitrary in claim 1～6
Manufacture method described in Xiang manufactures, and is loaded with described nanometer colloid in described polysaccharide system macromolecule
Grain.
Nanometer colloid particulate load thing the most according to claim 7, it is characterised in that described nanometer
The load capacity of colloidal solid is relative to the model that described polysaccharide system macromolecule 100 mass parts is 1～15 mass parts
In enclosing.
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| CN110366460A (en) * | 2017-03-30 | 2019-10-22 | 拓自达电线株式会社 | Silver chlorate is coated particle |
| CN112739454A (en) * | 2018-09-20 | 2021-04-30 | 奇华顿股份有限公司 | Improvements in or relating to organic compounds |
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| CN113244268A (en) * | 2021-04-12 | 2021-08-13 | 青岛海洋生物医药研究院股份有限公司 | Bacteriostatic gel containing sulfated polysaccharide-nano silver complex and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440378B1 (en) * | 1997-12-22 | 2002-08-27 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases, a method of producing the same, and a method of purifying exhaust gases |
| CN1759962A (en) * | 2005-11-11 | 2006-04-19 | 华东理工大学 | Method for preparing Nano silver sol |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| US20110262646A1 (en) * | 2010-04-23 | 2011-10-27 | Purdue Research Foundation | Surfactant-Assisted Inorganic Nanoparticle Deposition on a Cellulose Nanocrystals |
| CN102228995A (en) * | 2011-06-30 | 2011-11-02 | 华南理工大学 | Polysaccharide-nano silver sol and preparation method thereof |
| CN102814502A (en) * | 2012-07-05 | 2012-12-12 | 南昌大学 | Preparation method of silver nanoparticle by using hemicellulose as stabilizer |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4865772A (en) | 1971-12-14 | 1973-09-10 | ||
| JPS5114008A (en) | 1974-07-25 | 1976-02-04 | Victor Company Of Japan | Jikiteepuno seidohoshiki |
| JP2005261709A (en) | 2004-03-19 | 2005-09-29 | National Institute Of Advanced Industrial & Technology | New deodorizing paper and manufacturing method thereof |
| JP3870282B2 (en) * | 2005-02-28 | 2007-01-17 | 株式会社 東北テクノアーチ | Dispersed and stabilized liquid containing catalyst nanoparticles |
| JP5131799B2 (en) * | 2005-04-07 | 2013-01-30 | 伯東株式会社 | Metal oxide fine particle dispersion and method for producing the same |
| JP5566368B2 (en) | 2009-02-18 | 2014-08-06 | 日本製紙株式会社 | Composite comprising cellulose nanofiber and metal nanoparticle, and production method thereof |
| JP5553402B2 (en) | 2009-11-05 | 2014-07-16 | 愛媛県 | Solid catalyst and method for producing the same |
| TW201138827A (en) * | 2010-05-11 | 2011-11-16 | Univ China Medical | Core-shell metal nanoparticles and method for manufacturing the same |
-
2015
- 2015-01-26 CN CN201580007258.7A patent/CN105980055B/en active Active
- 2015-01-26 WO PCT/JP2015/000330 patent/WO2015118831A1/en active Application Filing
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- 2015-01-26 JP JP2015561203A patent/JP6325009B2/en active Active
- 2015-02-03 TW TW104103559A patent/TWI617353B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6440378B1 (en) * | 1997-12-22 | 2002-08-27 | Toyota Jidosha Kabushiki Kaisha | Catalyst for purifying exhaust gases, a method of producing the same, and a method of purifying exhaust gases |
| CN1759962A (en) * | 2005-11-11 | 2006-04-19 | 华东理工大学 | Method for preparing Nano silver sol |
| CN1970143A (en) * | 2006-09-06 | 2007-05-30 | 大连理工大学 | Method for preparing high-activity hydrogenation catalyst nano Ru/C |
| US20110262646A1 (en) * | 2010-04-23 | 2011-10-27 | Purdue Research Foundation | Surfactant-Assisted Inorganic Nanoparticle Deposition on a Cellulose Nanocrystals |
| CN102228995A (en) * | 2011-06-30 | 2011-11-02 | 华南理工大学 | Polysaccharide-nano silver sol and preparation method thereof |
| CN102814502A (en) * | 2012-07-05 | 2012-12-12 | 南昌大学 | Preparation method of silver nanoparticle by using hemicellulose as stabilizer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110366460A (en) * | 2017-03-30 | 2019-10-22 | 拓自达电线株式会社 | Silver chlorate is coated particle |
| CN112739454A (en) * | 2018-09-20 | 2021-04-30 | 奇华顿股份有限公司 | Improvements in or relating to organic compounds |
| CN112739454B (en) * | 2018-09-20 | 2024-01-09 | 奇华顿股份有限公司 | Improvements in or relating to organic compounds |
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