CN105536869A - Nano-silver-supported hybrid microgel catalyst and preparation method and application thereof - Google Patents
Nano-silver-supported hybrid microgel catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 73
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical group OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 11
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000006185 dispersion Substances 0.000 claims description 28
- 238000011068 loading method Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 22
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 7
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 claims description 2
- 241000233803 Nypa Species 0.000 claims 5
- 235000005305 Nypa fruticans Nutrition 0.000 claims 5
- 239000002105 nanoparticle Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 238000009825 accumulation Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 239000002082 metal nanoparticle Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011557 critical solution Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000012447 hatching Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention provides a nano-silver-supported hybrid microgel catalyst and a preparation method and application thereof. Hybrid microgel uses nano-silver particles containing rich unsaturated carbon-carbon double bonds on the surface as a crosslinking agent, an initiator initiates soap-free emulsion polymerization of N-isopropyl acrylamide to prepare nano-silver particle supported temperature-sensitive type hybrid microgel, the particle size of nano-silver is 10-20 nm, and the diameter of the hybrid microgel is 150-250 nm. The double bonds are introduced into the surface of the nano-silver particles through esterification reaction between methacrylic acid 2-hydroxyl ethyl ester and the nano-silver with the surface modified with 3-thiohydracrylic acid, the double bond grafting ratio of the surfaces of the nano particles can be effectively controlled, and multiple nano-silver particles are contained in each microgel. Due to the fact that the nano-silver is chemically cross-linked in polymer gel, accumulation of the nano-silver particles can be effectively blocked, and the stability and catalytic activity of the nano-silver are improved. The prepared hybrid microgel has temperature sensibility and a good effect of catalytic reduction on the activity of 4-nitrophenol.
Description
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of loading nano silvery hybrid microgel Catalysts and its preparation method and application.
Background technology
Noble metal nano particles is because its size is little, specific area is large, make it have very high catalytic activity, become a kind of catalyst efficiently in catalytic field, but noble metal nano particles has higher specific surface energy, when there is no stabilizing agent or other functional groups stablize, easy gathering and instability, limit it and apply widely.Use polymer gel to be carrier loaded nano particle be one of most effective method at present, microgel is a kind of macromolecule with cross-linked network, can as the reactor of nanoparticle nucleation, not only can improve the specific area of nano particle, stabilized nanoscale particle and the effect preventing from assembling can also be played, and the passage of gel can be passed in and out as molecule, keep the catalytic efficiency of nano particle unaffected.But common microgel catalyst cannot control the catalytic efficiency of catalyst by simple method, application has significant limitation.
NIPA (PNIPAM) is the material that one has lowest critical solution temperature (LCST), namely when temperature is higher than LCST, PNIPAM there will be phase in version process, noble metal nano particles and PNIPAM microgel are compounded to form hybridized nanometer compound, can obtain and there is temperature sensitivity, catalytic activity and catalytic activity can with the temperature controlled composite with several functions.At present, be that carrier loaded Nano silver grain is prepared hybrid microgel and mainly contained three kinds of methods with microgel:
(1) noble metal nano particles prepared and intelligent microgel mix by hatching method, when utilizing the electrostatic force between them or change external environment, are spread by nano particle or penetrate into microgel inside.As P (NIPAM-co-AA) gel mixes at pH6 with gold nanorods (AuNRs), AuNRs by with the COO on polymer chain
-electrostatic interaction enters into gel inside, thus the obtained intelligent hybrid microgel with stimulating responsive.The deficiency of the method be nano particle and gel by physical action compound, under environmental stimulus, nano particle can diffuse out.
(2) local reduction way is the intelligent microgel synthesized is microreactor, presoma or precious metal ion are stable in intelligent microgel by the effect such as electrostatic, complexing, generate metal nanoparticle by in-situ reducing, thus obtain metal nanoparticle plural gel.This method is that synthesizing noble metal/intelligent microgel nano-complex at present comparatively conventional is also comparatively simple method.Its weak point is that nano particle is embedded in gel in the mode of assembling, and is formed and is similar to hud typed nano-complex.
(3) surface grafting polymerization method refers to the metal nanoparticle first prepared the material containing specific functional groups and modify, mix with monomer again, form gel by free radical polymerisation process, in polymerization process, nano particle is directly embedded in the network structure of gel.In recent years, by containing the functional group of double bond in nanoparticle surface modified formation, recycling emulsion polymerization forms core-shell type nano compound, double bond is incorporated into nanoparticle surface, then synthesizes core-shell type nano compound with emulsion polymerisation process.In preparation process, metal nanoparticle particle diameter is comparatively large, formation be core-shell type nano compound, the specific surface of nano particle is less, and shell thickness affects catalytic efficiency.
Summary of the invention
According to problems of the prior art, technical problem to be solved by this invention is the problem overcoming Nano Silver easily gathering in catalytic process, there is provided a kind of by Nano Silver chemical crosslinking on polymer chain, make Nano Silver stable dispersion in gel, avoid the reunion of Nano Silver, give the temperature sensitivity of catalyst, catalyst stability is good simultaneously.
The present invention adopts following technical scheme:
A kind of loading nano silvery hybrid microgel catalyst, the mass percent of described hybrid microgel consists of: Nano Silver (AgNPs) 5% ~ 10%, NIPA polymer gel 90% ~ 95%; Described Nano Silver particle diameter is 10 ~ 20nm, and hybrid microgel diameter is 150 ~ 250nm.
The application of described catalyst in the reaction of catalysis sodium borohydride reduction 4-nitrophenol.
A preparation method for loading nano silvery hybrid microgel catalyst, comprises the following steps:
The synthesis of the Nano Silver that A, 3-mercaptopropionic acid is stable: add 2mmol/L sodium borohydride aqueous solution in there-necked flask, and drip 1mmol/L silver nitrate aqueous solution, the ratio of described sodium borohydride and the amount of substance of silver nitrate is 2: 1 ~ 10: 1, logical nitrogen gas stirring 30min, generates nano silver dispersion; Joined by 3-mercaptopropionic acid in the nano silver dispersion of above-mentioned preparation fast, the ratio of described 3-mercaptopropionic acid and the amount of substance of silver nitrate is 1: 1 ~ 3: 1, reacts 30min under nitrogen atmosphere, the nano silver dispersion that obtained 3-mercaptopropionic acid is stable;
B, the synthesis of Nano Silver that 2-hydroxyethyl methacrylate is modified: 12mmol/L1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride aqueous solution is joined in the stable nano silver dispersion of 3-mercaptopropionic acid prepared by steps A, 10min is stirred in ice-water bath, add the 12mmol/LN-HOSu NHS aqueous solution, 30min is reacted under nitrogen atmosphere, add 2-hydroxyethyl methacrylate again, stirring reaction 12h under nitrogen atmosphere, described 3-mercaptopropionic acid, 2-hydroxyethyl methacrylate, the ratio of the amount of substance of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide is 1: 1.2: 1.4: 1.4, dialyse three times with the bag filter that molecular cut off is 8-14kDa, each dialysis time is 30-60min, the nano silver dispersion that obtained 2-hydroxyethyl methacrylate is modified,
C, preparation temperature sensitive loads Nano Silver hybrid microgel: NIPA is joined in the nano silver dispersion of 2-hydroxyethyl methacrylate modification prepared by step B, 30min is stirred under nitrogen atmosphere, the mass ratio 3: 100 ~ 10: 100 of described Nano Silver and NIPA, 5 ~ 10min is heated under 55 DEG C of conditions, add 16mmol/L ammonium persulfate aqueous solution and tetramethylethylenediamine, described NIPA, the ratio of the amount of substance of ammonium persulfate and tetramethylethylenediamine is 10: 1: 2, reaction 3-4h is continued under being transferred to room temperature after reaction 5min, with the bag filter dialysis 48h that molecular cut off is 8-14kDa, obtain a kind of loading nano silvery hybrid microgel catalyst.
In described steps A, silver nitrate aqueous solution dropwise joins in sodium borohydride aqueous solution.
Dripping silver nitrate aqueous solution in described steps A is adopt constant pressure funnel to drip.
In described steps A, the ratio of the amount of substance of sodium borohydride and silver nitrate is 6: 1.
In described steps A, the ratio of the amount of substance of 3-mercaptopropionic acid and silver nitrate is 2: 1.
The mass ratio 6: 100 of Nano Silver and NIPA in described step C.
In described step C, ammonium persulfate can use water soluble starter conventional in the field of polymer technology such as potassium peroxydisulfate, azo diisobutyl amidine hydrochloride to substitute.
In described step B, step C, dialysis can substitute by the method for high temperature centrifugal sedimentation.
Unsaturated carbon-carbon double bond is contained on described nano silver particles surface, using the Nano Silver of 2-hydroxyethyl methacrylate modification as crosslinking agent.
Beneficial effect of the present invention is: utilize the esterification between the Nano Silver of 2-hydroxyethyl methacrylate and finishing 3-mercaptopropionic acid that double bond is incorporated into nano grain of silver sub-surface, effectively can control the double bond percent grafting of nanoparticle surface, with the crosslinking agent that it is reaction, prepare hybridized nanometer microgel, nano silver particles containing multiple size tunable in each microgel, specific area significantly increases, and Nano Silver and polymer gel pass through chemical bonds, Nano Silver is scattered in gel, polymer chain can effectively stop Nano silver grain to be assembled, thus improve stability and the catalytic activity of Nano Silver, place 50 days catalytic effects at normal temperatures to remain unchanged.Add after tetramethylethylenediamine can make polymerisation cause and at room temperature react, when avoiding the temperature forming gel in high temperature emulsifier-free emulsion polymerization process to exceed the phase transition temperature of NIPA polymer, cause gel coagulation.Hybrid microgel has temperature sensitivity, and changing environment temperature can effectively control its catalytic efficiency.Particularly, namely by the change of ambient temperature, hybrid microgel is collapsed or swelling, thus control its catalytic efficiency further.The inventive method obtains hybrid microgel catalyst and has good catalytic reduction 4-nitrophenol activity.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of loading nano silvery hybrid microgel catalyst prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of loading nano silvery hybrid microgel catalyst prepared by embodiment 1.
Fig. 3 is that the loading nano silvery hybrid microgel catalyst of embodiment 1 preparation is to the observed rate constant (k of 4-nitrophenol catalytic reduction
app) variation with temperature curve.
Fig. 4 is that the loading nano silvery hybrid microgel catalyst of embodiment 1 preparation is to the observed rate constant (k of 4-nitrophenol catalytic reduction
app) with the change curve of gel strength.
Fig. 5 is that loading nano silvery hybrid microgel catalyst prepared by embodiment 1 places the ultraviolet-visible spectrum after 50 days and the concentration (ln (c in catalytic reduction reaction 4-nitrophenol
t/ c
0)) with the variation relation curve in reaction time (t).
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiments.
Embodiment 1
A kind of loading nano silvery hybrid microgel catalyst, the mass percent of described hybrid microgel consists of: Nano Silver 5%, NIPA polymer gel 95%; Described Nano Silver particle diameter is 10 ~ 20nm, and hybrid microgel diameter is 150 ~ 250nm.
By Fig. 1, a kind of preparation method of loading nano silvery hybrid microgel catalyst, comprises the following steps:
The synthesis of the Nano Silver that A, 3-mercaptopropionic acid (MPA) is stable: add in there-necked flask with 15mL, 2mmol/L sodium borohydride (NaBH
4) aqueous solution, drip with 5mL, 1mmol/L silver nitrate aqueous solution with constant pressure funnel, logical nitrogen gas stirring 30min, generates nano silver dispersion; 87 μ LMPA of dilution 100 times are joined in the nano silver dispersion of above-mentioned preparation fast, under nitrogen atmosphere, reacts 30min, the nano silver dispersion that obtained 3-mercaptopropionic acid is stable;
B, the synthesis of the Nano Silver that 2-hydroxyethyl methacrylate (HEMA) is stable: with 1mL, 12mmol/L1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) aqueous solution, join in the stable nano silver dispersion of 3-mercaptopropionic acid prepared by steps A, 10min is stirred in ice-water bath, add with 1mL, 12mmol/LN-HOSu NHS (NHS) aqueous solution, 30min is reacted under nitrogen atmosphere, add 145 μ L 2-hydroxyethyl methacrylates (HEMA) of dilution 100 times again, stirring reaction 12h under nitrogen atmosphere, dialyse three times with the bag filter that molecular cut off is 8-14kDa, each dialysis time is 30min, the nano silver dispersion that obtained 2-hydroxyethyl methacrylate is modified,
C, the hybrid microgel of preparation temperature sensitive loads Nano Silver: 0.4mmolN-N-isopropylacrylamide (NIPAM) is joined in the nano silver dispersion of 2-hydroxyethyl methacrylate modification prepared by step B, 30min is stirred under nitrogen atmosphere, then under 55 DEG C of conditions, 10min is heated, add with 3mL fast, the tetramethylethylenediamine (TEMED) of the APS aqueous solution that 16mmol/L ammonium persulfate (APS) configures and 15 μ L, be transferred to room temperature after reaction 5min and continue reaction 4h, be the 48h that dialyses in the bag filter of 8-14kDa with molecular cut off, obtain a kind of loading nano silvery hybrid microgel catalyst.
The results are shown in Figure 2, Nano Silver particle diameter is 10 ~ 20nm, and loading nano silvery hybrid microgel particle diameter is 150 ~ 250nm; It is 5% that thermogravimetric analyzer (SDTQ600) detects the load capacity obtaining Nano Silver.
Embodiment 2
A kind of loading nano silvery hybrid microgel catalyst, the mass percent of described hybrid microgel consists of: Nano Silver 5%, NIPA polymer gel 95%; Described Nano Silver particle diameter is 10 ~ 20nm, and hybrid microgel diameter is 150 ~ 250nm.
By Fig. 1, a kind of preparation method of loading nano silvery hybrid microgel catalyst, comprises the following steps:
The synthesis of the Nano Silver that A, 3-mercaptopropionic acid (MPA) is stable: add in there-necked flask with 15mL, 2mmol/L sodium borohydride (NaBH
4) aqueous solution, drip with 5mL, 1mmol/L silver nitrate aqueous solution with constant pressure funnel, logical nitrogen gas stirring 30min, generates nano silver dispersion; 87 μ LMPA of dilution 100 times are joined in the nano silver dispersion of above-mentioned preparation fast, under nitrogen atmosphere, reacts 30min, the nano silver dispersion that obtained 3-mercaptopropionic acid is stable;
B, the synthesis of the Nano Silver that 2-hydroxyethyl methacrylate (HEMA) is stable: with 1mL, 12mmol/L1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) aqueous solution, join in the stable nano silver dispersion of 3-mercaptopropionic acid prepared by steps A, 10min is stirred in ice-water bath, add with 1mL, 12mmol/LN-HOSu NHS (NHS) aqueous solution, 30min is reacted under nitrogen atmosphere, add 145 μ L 2-hydroxyethyl methacrylates (HEMA) of dilution 100 times again, stirring reaction 12h under nitrogen atmosphere, dialyse three times with the bag filter that molecular cut off is 8-14kDa, each dialysis time is 30min, the nano silver dispersion that obtained 2-hydroxyethyl methacrylate is modified,
C, the hybrid microgel of preparation temperature sensitive loads Nano Silver: 0.15mmolN-N-isopropylacrylamide (NIPAM) is joined in the nano silver dispersion of 2-hydroxyethyl methacrylate modification prepared by step B, 30min is stirred under nitrogen atmosphere, then under 55 DEG C of conditions, 10min is heated, add with 3mL fast, the tetramethylethylenediamine (TEMED) of the APS aqueous solution that 16mmol/L ammonium persulfate (APS) configures and 15 μ L, be transferred to room temperature after reaction 5min and continue reaction 4h, be the 48h that dialyses in the bag filter of 8-14kDa with molecular cut off, obtain a kind of loading nano silvery hybrid microgel catalyst.
In order to prove beneficial effect of the present invention, the hybrid microgel catalyst of what embodiment 1 was prepared by inventor have temperature sensitive loading nano silvery is used for catalysis sodium borohydride reduction 4-nitrophenol, and concrete test is as follows:
By 2mL36mMNaBH
4the 4-nitrophenol solution of solution and 1mL0.36mM mixes in the quartz colorimetric utensil of standard, and heating-up temperature is to 20,25,30,35,40 and 45 DEG C respectively, then adds 0.025mL1.4mgmL
-1catalyst dispersion of the present invention, adopt ultraviolet-visible spectrophotometer trace detection is carried out to its catalytic reduction process, the peak intensity that reaction rate is set to 398nm by peak position calculates over time.As seen from Figure 3, when temperature increases to 35 DEG C from 20 DEG C, the observed rate constant (k of catalytic reaction
app) strengthen gradually, but temperature higher than 35 DEG C time, observed rate constant starts to decline gradually, and when 45 DEG C, observed rate constant is close to zero, illustrates that catalytic reaction obviously shows temperature sensitivity.
By 2mL36mMNaBH
4the 4-nitrophenol solution of solution and 1mL0.36mM mixes in the quartz colorimetric utensil of standard, maintains the temperature at 25 DEG C, adds the 1.4mgmL of different volumes
-1catalyst dispersion of the present invention, catalyst concn scope is at 0 ~ 0.072mgmL
-1, adopt ultraviolet-visible spectrophotometer to carry out trace detection to its catalytic reduction process, the peak intensity that reaction rate is set to 398nm by peak position calculates over time.As seen from Figure 4, along with the increase of concentration, observed rate constant (kapp) increases gradually, but after its concentration reaches certain value, obvious change no longer occurs its rate of catalysis reaction constant.
In order to prove the stability of loading nano silvery hybrid gel of the present invention, after the microgel with temperature sensitive loading nano silvery that embodiment 1 is prepared by inventor places 50 days, characterize the situation of change of its ultravioletvisible absorption intensity and catalyst efficiency with ultraviolet-visible spectrophotometer.As seen from Figure 5, compared with the hybrid gel of fresh preparation, after catalyst places 50 days, the uv-visible absorption spectra of hybrid gel dispersion liquid does not become substantially, and the efficiency of catalytic reduction 4-nitrophenol is substantially identical.
Claims (8)
1. a loading nano silvery hybrid microgel catalyst, is characterized in that: the mass percent of described hybrid microgel consists of: Nano Silver 5% ~ 10%, NIPA polymer gel 90% ~ 95%; Described Nano Silver particle diameter is 10 ~ 20nm, and hybrid microgel diameter is 150 ~ 250nm.
2. the application of catalyst according to claim 1 in the reaction of catalysis sodium borohydride reduction 4-nitrophenol.
3. a preparation method for loading nano silvery hybrid microgel catalyst, is characterized in that, comprises the following steps:
The synthesis of the Nano Silver that A, 3-mercaptopropionic acid is stable: add 2mmol/L sodium borohydride aqueous solution in there-necked flask, and drip 1mmol/L silver nitrate aqueous solution, the ratio of described sodium borohydride and the amount of substance of silver nitrate is 2: 1 ~ 10: 1, logical nitrogen gas stirring 30min, generates nano silver dispersion; Joined by 3-mercaptopropionic acid in the nano silver dispersion of above-mentioned preparation fast, the ratio of described 3-mercaptopropionic acid and the amount of substance of silver nitrate is 1: 1 ~ 3: 1, reacts 30min under nitrogen atmosphere, the nano silver dispersion that obtained 3-mercaptopropionic acid is stable;
B, the synthesis of Nano Silver that 2-hydroxyethyl methacrylate is modified: 12mmol/L1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride aqueous solution is joined in the stable nano silver dispersion of 3-mercaptopropionic acid prepared by steps A, 10min is stirred in ice-water bath, add the 12mmol/LN-HOSu NHS aqueous solution, 30min is reacted under nitrogen atmosphere, add 2-hydroxyethyl methacrylate again, stirring reaction 12h under nitrogen atmosphere, described 3-mercaptopropionic acid, 2-hydroxyethyl methacrylate, the ratio of the amount of substance of 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxy-succinamide is 1: 1.2: 1.4: 1.4, dialyse three times with the bag filter that molecular cut off is 8-14kDa, each dialysis time is 30-60min, the nano silver dispersion that obtained 2-hydroxyethyl methacrylate is modified,
C, preparation temperature sensitive loads Nano Silver hybrid microgel: NIPA is joined in the nano silver dispersion of 2-hydroxyethyl methacrylate modification prepared by step B, 30min is stirred under nitrogen atmosphere, the mass ratio 3: 100 ~ 10: 100 of described Nano Silver and NIPA, 5 ~ 10min is heated under 55 DEG C of conditions, add 16mmol/L ammonium persulfate aqueous solution and tetramethylethylenediamine, described NIPA, the ratio of the amount of substance of ammonium persulfate and tetramethylethylenediamine is 10: 1: 2, reaction 3-4h is continued under being transferred to room temperature after reaction 5min, with the bag filter dialysis 48h that molecular cut off is 8-14kDa, obtain a kind of loading nano silvery hybrid microgel catalyst.
4. the preparation method of a kind of loading nano silvery hybrid microgel catalyst according to claim 3, is characterized in that: in described steps A, silver nitrate aqueous solution dropwise joins in sodium borohydride aqueous solution.
5. the preparation method of a kind of loading nano silvery hybrid microgel catalyst according to claim 3, is characterized in that: dripping silver nitrate aqueous solution in described steps A is adopt constant pressure funnel to drip.
6. the preparation method of a kind of loading nano silvery hybrid microgel catalyst according to claim 3, is characterized in that: in described steps A, the ratio of the amount of substance of sodium borohydride and silver nitrate is 6: 1.
7. the preparation method of a kind of loading nano silvery hybrid microgel catalyst according to claim 3, is characterized in that: in described steps A, the ratio of the amount of substance of 3-mercaptopropionic acid and silver nitrate is 2: 1.
8. the preparation method of a kind of loading nano silvery hybrid microgel catalyst according to claim 3, is characterized in that: the mass ratio 6: 100 of Nano Silver and NIPA in described step C.
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