CN113797979B - Modified nano particle, preparation method and application thereof - Google Patents
Modified nano particle, preparation method and application thereof Download PDFInfo
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- CN113797979B CN113797979B CN202111079828.7A CN202111079828A CN113797979B CN 113797979 B CN113797979 B CN 113797979B CN 202111079828 A CN202111079828 A CN 202111079828A CN 113797979 B CN113797979 B CN 113797979B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000004954 Polyphthalamide Substances 0.000 claims abstract description 12
- 229920006375 polyphtalamide Polymers 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 102000004190 Enzymes Human genes 0.000 claims abstract description 6
- 108090000790 Enzymes Proteins 0.000 claims abstract description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007974 sodium acetate buffer Substances 0.000 claims description 11
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 11
- 229960003351 prussian blue Drugs 0.000 claims description 10
- 239000013225 prussian blue Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910003321 CoFe Inorganic materials 0.000 claims description 3
- 229910016507 CuCo Inorganic materials 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- -1 fe 3 O 4 Chemical compound 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical class O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
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Images
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention relates to the technical field of compounds, in particular to a modified nanoparticle, and a preparation method and application thereof. The modified nanoparticles include: inorganic nanoparticles; and a polyphthalamide layer coated on the surfaces of the inorganic nanoparticles. The applicants have creatively found that the modified nanoparticles can catalyze the reaction of oxygen and water under neutral conditions (pH 7.0) to produce hydrogen peroxide; can oxidize a substrate TMB (3, 3', 5' -tetramethyl benzidine), shows that an obvious absorption peak is generated at 658nm of an ultraviolet visible spectrum, and has the catalytic activity of unique redox type nano enzyme.
Description
Technical Field
The invention relates to the technical field of compounds, in particular to a modified nanoparticle, and a preparation method and application thereof.
Background
Aromatic polymers are one of the most commonly used semiconducting polymers, and their conjugated structure provides excellent conductivity and electrochemical activity, and its conductivity and dielectric properties can be adjusted by controlling proton doping state. The coupling of plasma with active dielectric is expected to develop and design multifunctional responsive intelligent materials, such as terahertz phase-modulated metamaterials. The surface of aromatic polymers (such as poly-o-phenylenediamine) has abundant amino and imine groups, so that the aromatic polymers are easy to functionalize and modify, and the application range of the aromatic polymers is expanded, for example, the aromatic polymers are applied to the fields of biosensing, metal ion adsorption, supercapacitors, catalysis, sensing, electrochromic devices and the like.
For the poly-o-phenylenediamine micro-nano material, the micro-assembly process is accurately regulated, a more ordered micro-nano structure is constructed, and the exploration and optimization of a large-scale controllable preparation method are very important for regulating and controlling the macroscopic performance and the practical production application of the material and still are important problems to be solved. In addition, the application of aromatic polymers as mimic enzymes is still to be developed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a modified nanoparticle, a preparation method and an application thereof, wherein the modified nanoparticle provided by the present invention has catalytic activity of redox nanoenzyme.
The present invention provides a modified nanoparticle comprising:
inorganic nanoparticles;
and a polyphthalamide layer coated on the surface of the inorganic nano-particle.
Preferably, the inorganic nanoparticles include at least one of a noble metal, a binary metal oxide, and a ternary transition metal oxide;
the particle size of the inorganic nano particles is 20-500 nm.
Preferably, the inorganic nanoparticles comprise gold, silver, platinum, palladium, fe 3 O 4 、CeO 2 Prussian blue, V 2 O 5 、ZnCo 2 O 4 、CoFe 2 O 4 And CuCo 2 O 4 At least one of;
the thickness of the poly-o-phenylenediamine layer is 10-40 nm.
The invention also provides a preparation method of the modified nano particles, which comprises the following steps:
a) Uniformly mixing the inorganic nanoparticle dispersion liquid, the aqueous solution of the surfactant, the aqueous solution of o-phenylenediamine and the hydrogen peroxide solution to obtain a mixed solution;
b) And adjusting the pH value of the mixed solution to 4-6, and reacting at 35-45 ℃ to obtain the modified nanoparticles.
Preferably, in the step a), the molar ratio of the inorganic nanoparticles to the surfactant is 1 to 10:10 to 500 parts;
the molar ratio of the o-phenylenediamine to the hydrogen peroxide to the surfactant is 2-50: 1 to 25:1 to 25;
the surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polystyrene sulfonate.
Preferably, in the step A), the uniform mixing is realized by ultrasonic and oscillation;
the equipment adopted by the ultrasound is a KQ-300DE type numerical control ultrasonic cleaner, the frequency of the ultrasound is 30-45 kHz, and the time is 10-20 min;
the adopted equipment for oscillation is a DT96-4 type oscillator, the temperature of the oscillation is room temperature, and the time is 15-35 min.
Preferably, in the step B), the reagent for adjusting the pH value of the mixed solution is an acetic acid-sodium acetate buffer solution;
the concentration of the acetic acid-sodium acetate buffer solution is 0.1-0.2 mol/L, and the pH value is 3.8-6.4.
Preferably, in the step B), the reaction temperature is 40 ℃, and the reaction time is 40 min-2 h.
Preferably, step B) further comprises, after the reaction:
centrifugal separation and water washing;
the rotation speed of the centrifugal separation is 12500-13500 rpm.
The invention also provides an application of the modified nano particle as redox type nano enzyme.
The present invention provides a modified nanoparticle comprising: inorganic nanoparticles; and a polyphthalamide layer coated on the surfaces of the inorganic nanoparticles. The applicants have creatively found that such modified nanoparticles are capable of catalyzing the reaction of oxygen and water under neutral conditions (pH 7.0) to produce hydrogen peroxide; can oxidize the substrate TMB (3, 3', 5' -tetramethyl benzidine), and has obvious absorption peak at 658nm of the ultraviolet visible spectrum and unique catalytic activity of the redox nano-enzyme.
Drawings
FIG. 1 is a TEM image of a modified nanoparticle of example 1 of the present invention;
FIG. 2 is a NMR spectrum of modified nanoparticles of example 1 of the present invention;
FIG. 3 is a FTIR plot of modified nanoparticles of example 1 of the present invention;
FIG. 4 is a TEM image of a modified nanoparticle of example 4 of the present invention;
FIG. 5 is a graph showing the color change of the experimental group and the control group after 30min reaction in example 5 of the present invention;
FIG. 6 is a graph showing the change of UV-visible absorption peak with time during the reaction in the experimental group of example 5 according to the present invention;
FIG. 7 is a graph showing the change of UV-visible absorption peak with time during the reaction in the control group of example 5 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides a modified nanoparticle comprising:
inorganic nanoparticles;
and a polyphthalamide layer coated on the surfaces of the inorganic nanoparticles.
In certain embodiments of the present invention, the inorganic nanoparticles comprise at least one of a noble metal, a binary metal oxide, and a ternary transition metal oxide.
In certain embodiments of the invention, the inorganic nanoparticles comprise gold, silver, platinum, palladium, fe 3 O 4 、CeO 2 Prussian blue, V 2 O 5 、ZnCo 2 O 4 、CoFe 2 O 4 And CuCo 2 O 4 At least one of (1).
In certain embodiments of the present invention, the inorganic nanoparticles have a particle size of 20 to 500nm. In certain embodiments, the inorganic nanoparticles have a particle size of 30 to 60nm, 300 to 500nm, 20 to 30nm, or 40 to 60nm.
In certain embodiments of the present invention, the thickness of the polyphthalamide layer is 10 to 40nm. In certain embodiments, the thickness of the polyphthalamide layer is 20 to 40nm or 10 to 30nm.
In the invention, the poly-o-phenylenediamine is coated on the inorganic nano particles, so that the specific surface area of the poly-o-phenylenediamine is increased, active sites are fully exposed, and the poly-o-phenylenediamine can be more fully contacted with reactants.
The invention also provides a preparation method of the modified nano-particle, which comprises the following steps:
a) Uniformly mixing the inorganic nanoparticle dispersion liquid, the aqueous solution of the surfactant, the aqueous solution of o-phenylenediamine and the hydrogen peroxide solution to obtain a mixed solution;
b) And adjusting the pH value of the mixed solution to 4-6, and reacting at 35-45 ℃ to obtain the modified nanoparticles.
The method comprises the steps of uniformly mixing inorganic nanoparticle dispersion liquid, aqueous solution of a surfactant, aqueous solution of o-phenylenediamine and hydrogen peroxide solution to obtain mixed solution.
The components of the inorganic nanoparticles are the same as above, and are not described in detail herein.
The preparation method of the inorganic nanoparticles is not particularly limited, and the inorganic nanoparticles can be generally commercially available or self-made.
In certain embodiments of the present invention, the inorganic nanoparticle dispersion has a concentration of 10 to 50mmol/L. In certain embodiments, the concentration of the inorganic nanoparticle dispersion is 10mmol/L, 15mmol/L. In certain embodiments of the present invention, the solvent in the inorganic nanoparticle dispersion is deionized water.
In certain embodiments of the present invention, the surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and polystyrene sulfonate. In certain embodiments of the invention, the concentration of the aqueous solution of the surfactant is 10 to 50mmol/L. In certain embodiments, the concentration of the aqueous solution of the surfactant is 10mmol/L. In certain embodiments of the present invention, the solvent in the aqueous solution of the surfactant is deionized water.
In certain embodiments of the present invention, the concentration of the aqueous solution of o-phenylenediamine is 0.1 to 0.3mol/L. In certain embodiments, the concentration of the aqueous solution of o-phenylenediamine is 0.2mol/L. In certain embodiments of the present invention, the solvent in the aqueous solution of o-phenylenediamine is deionized water.
In certain embodiments of the present invention, the hydrogen peroxide solution has a mass concentration of 25% to 35%. In certain embodiments, the hydrogen peroxide solution has a mass concentration of 30%. In certain embodiments, the solvent of the hydrogen peroxide solution is deionized water.
In certain embodiments of the present invention, the inorganic nanoparticles and the surfactant are present in a molar ratio of 1 to 10:10 to 500. In certain embodiments, the inorganic nanoparticles and surfactant are present in a molar ratio of 1:50 or 1:10.
in certain embodiments of the invention, the molar ratio of o-phenylenediamine, hydrogen peroxide, and surfactant is from 2 to 50:1 to 25:1 to 25. In certain embodiments, the molar ratio of o-phenylenediamine, hydrogen peroxide, and surfactant is 2:1:1.
in certain embodiments of the invention, the blending is achieved by sonication and oscillation.
In some embodiments of the invention, the ultrasonic wave is generated by a KQ-300DE type numerical control ultrasonic cleaner, the frequency of the ultrasonic wave is 30-45 kHz, and the time is 10-20 min. In certain embodiments, the ultrasound has a frequency of 30kHz. In certain embodiments, the time of the sonication is 10min or 15min.
In some embodiments of the invention, the equipment used for the oscillation is a DT96-4 type oscillator, and the temperature of the oscillation is room temperature and the time is 15-35 min. In certain embodiments, the time of oscillation is 15min.
In certain embodiments of the present invention, mixing the inorganic nanoparticle dispersion, the aqueous solution of a surfactant, the aqueous solution of o-phenylenediamine, and the hydrogen peroxide solution specifically comprises:
mixing the inorganic nanoparticle dispersion liquid and the aqueous solution of the surfactant, standing at 28-32 ℃ for 10-30 min, mixing with the aqueous solution of o-phenylenediamine and the hydrogen peroxide solution, and performing ultrasonic treatment and oscillation to obtain a mixed solution.
The ultrasonic and oscillation parameters are the same as above and are not described in detail here.
In certain embodiments of the invention, the temperature of the placing is 30 ℃. In certain embodiments, the time of the placing is 25min.
After the mixed solution is obtained, the pH value of the mixed solution is adjusted to 4-6, and then the mixed solution reacts at 35-45 ℃ to obtain the modified nano particles.
In some embodiments of the invention, the pH of the mixed solution is adjusted to 5 to 6.
In certain embodiments of the invention, the agent that adjusts the pH of the mixture is an acetic acid-sodium acetate buffer. In some embodiments of the invention, the concentration of the acetic acid-sodium acetate buffer solution is 0.1-0.2 mol/L, and the pH value is 3.8-6.4. In certain embodiments, the acetic acid-sodium acetate buffer has a concentration of 0.1mol/L and a pH of 4.5.
In certain embodiments of the invention, the temperature of the reaction is 40 ℃. In certain embodiments of the invention, the reaction time is between 40min and 2h. In certain embodiments, the reaction time is 1h. In certain embodiments of the invention, the reaction is carried out in a thermostated water bath.
In certain embodiments of the present invention, the reacting further comprises:
centrifugal separation and water washing.
In certain embodiments of the invention, the centrifugation is performed at 12500 to 13500rpm. In certain embodiments, the centrifugation is performed at 12000rpm or 15000rpm. In certain embodiments of the invention, the time for the centrifugation is 5 to 10min.
In certain embodiments of the present invention, the water wash is a deionized water wash. In certain embodiments of the invention, the number of water washes is 3.
The source of the above-mentioned raw materials is not particularly limited, and the raw materials may be generally commercially available.
The invention also provides an application of the modified nano particle as redox type nano enzyme. The applicant finds that the modified nanoparticles can catalyze the reaction of oxygen and water under a neutral condition (pH value is 7.0) to generate hydrogen peroxide; the substrate TMB (3, 3', 5' -tetramethylbenzidine) can be oxidized, as shown by the generation of a distinct absorption peak at 658nm in the UV-visible spectrum. Thus, the use of the modified nanoparticles as redox nanoenzymes is claimed.
In the modified nano particle provided by the invention, the surface coating layer poly-o-phenylenediamine greatly increases the specific surface area of the nano particle, and the surface has a large amount of active free amino and imine groups, so that the modified nano particle has more versatility and has great advantages in the aspect of later-stage functional modification; the nitrogen-rich active site is expected to embody the application value in the field of catalysis; at the same time, it helps to increase the affinity of the substrate; these properties broaden the range of applications of the functional nanoparticles. The applicants have creatively found that such modified nanoparticles are capable of catalyzing the reaction of oxygen and water under neutral conditions (pH 7.0) to produce hydrogen peroxide; can oxidize a substrate TMB (3, 3', 5' -tetramethyl benzidine), shows that an obvious absorption peak is generated at 658nm of an ultraviolet visible spectrum, and has the catalytic activity of unique redox type nano enzyme.
In the preparation method of the modified nanoparticles, the reaction conditions are mild and simple, the method is rapid and simple, the product has good uniformity and stability, large-scale preparation is facilitated, and the phenomena of uneven surface modification, poor stability and the like are overcome.
In order to further illustrate the present invention, the following examples are provided to describe the modified nanoparticles, the preparation method and the application thereof in detail, but the scope of the present invention should not be construed as being limited thereto.
Example 1
1. And (3) synthesizing prussian blue nanoparticles:
20mL of an aqueous solution of ferric chloride (1.0 mmol/L) and 20mL of an aqueous solution of potassium ferricyanide (1.0 mmol/L) were prepared in advance. After the aqueous potassium ferricyanide solution was left in an ice water bath for 30 minutes, 1mmol of citric acid was added thereto, and the mixture was shaken for 5 minutes to be mixed uniformly. A100 ml round bottom flask and magneton were prepared, and the aqueous solution of ferric chloride was poured into the flask and transferred to a 60 ℃ oil bath and allowed to stand for 10min. The potassium ferricyanide solution described above was added dropwise to the round bottom flask with vigorous stirring and the solution gradually turned bright blue. And stopping stirring after 20min, adding 40mL of acetone after the solution is cooled to room temperature, then centrifuging at 12000rpm for 15min to obtain a blue product, and washing with acetone for several times to obtain the Prussian blue nanoparticles. Finally, the obtained prussian blue nanoparticles were dispersed in 10mL of deionized water for storage.
2. Taking 50 mu L of Prussian blue nanoparticle dispersion liquid (the concentration is 10mmol/L, the particle size of the Prussian blue nanoparticles is 30-60 nm), adding 3mL of lauryl sodium sulfate aqueous solution (the concentration is 10 mmol/L), wherein the molar ratio of the Prussian blue nanoparticles to the lauryl sodium sulfate is 1:50, placing the mixture in a constant-temperature water bath kettle at the temperature of 30 ℃ for 25min, and then mixing the mixture with 0.3mL of o-phenylenediamine aqueous solution (0.2 mol/L) and 0.6mL of hydrogen peroxide solution (30 mass percent), wherein the molar ratio of the o-phenylenediamine to the hydrogen peroxide to the sodium dodecyl sulfate is 2:1:1, performing ultrasonic treatment for 10min at the frequency of 30kHz by adopting a KQ-300DE type numerical control ultrasonic cleaner, and oscillating for 15min at room temperature by adopting a DT96-4 type oscillator to obtain a mixed solution;
3. and mixing the mixed solution with 30mL of 0.1mol/L acetic acid-sodium acetate buffer solution (pH = 4.5) until the pH value is 5-6, placing the mixture in a constant-temperature water bath kettle at 40 ℃ for reaction for 1h, centrifugally separating the product at 12000rpm, and washing the product with deionized water for three times to obtain modified nanoparticles (wherein the thickness of the polyphthalamide layer is 10-40 nm).
The morphology of the resulting modified nanoparticles was characterized using transmission electron microscopy and the results are shown in figure 1. FIG. 1 is a TEM image of a modified nanoparticle of example 1 of the present invention. The core-shell structure in fig. 1 shows that the polymer is uniformly coated on the surface of the prussian blue nanocube, which indicates the successful preparation of the modified prussian blue.
In this example, the result of nuclear magnetic resonance analysis of the obtained modified nanoparticles is shown in fig. 2. FIG. 2 is a NMR spectrum of modified nanoparticles of example 1 of the present invention. Hydrogen nuclear magnetic resonance spectroscopy: 1 h NMR (300 MHz, solute: DMSO-d 6), with 1H resonance peak in the range of 6 to 8ppm coinciding with the position of the resonance peak of the polyphenylenediamine, indicating the formation of the poly-o-phenylenediamine.
In this example, FT-IR characterization was performed on the obtained modified nanoparticles, and the results are shown in fig. 3. FIG. 3 shows modified nanoparticles of example 1 of the present inventionFTIR plot of the photons. Wherein POPD curve represents FTIR spectrum of modified nanoparticle of inventive example 1, and OPD curve represents FTIR spectrum of o-phenylenediamine monomer. As can be seen from FIG. 3, at 1530cm -1 And 1622cm -1 The peaks observed therein are due to stretching vibrations of the benzene and quinone rings representing the polymer structure, indicating the formation of poly-o-phenylenediamine.
Example 2
1. Synthesizing ferroferric oxide nano particles:
dissolving 0.811g of ferric chloride in 40mL of ethylene glycol, shaking for 30min to form a clear solution, then adding 3.6g of sodium acetate and 2.0g of polyethylene glycol (PEG), magnetically stirring the mixture for 30min, then placing the mixture into a 50mL high-pressure reaction kettle, and transferring the high-pressure reaction kettle into a blowing oven at 190 ℃ for reaction for 9h. And then cooling the reactant, centrifuging at 12000rpm for 10min, alternately washing the product with ethanol and water for six times, and drying in a vacuum oven at 60 ℃ for 6h to obtain the ferroferric oxide nanoparticles. And finally, dispersing the obtained ferroferric oxide nano particles in 10mL of deionized water for storage.
2. Taking 0.2mL of ferroferric oxide nanoparticle dispersion liquid (the concentration is 15mmol/L, the particle size of the ferroferric oxide nanoparticles is 300-500 nm), adding 3mL of sodium dodecyl sulfate aqueous solution (the concentration is 10 mmol/L), wherein the molar ratio of the ferroferric oxide nanoparticles to the sodium dodecyl sulfate is 1:10, placing the mixture in a constant-temperature water bath kettle at the temperature of 30 ℃ for 10min, and then mixing the mixture with 0.3mL of o-phenylenediamine aqueous solution (0.2 mol/L) and 0.6mL of hydrogen peroxide solution (the mass concentration is 30%), wherein the molar ratio of the o-phenylenediamine to the hydrogen peroxide to the sodium dodecyl sulfate is 2:1:1, performing ultrasonic treatment for 10min at the frequency of 30kHz by adopting a KQ-300DE type numerical control ultrasonic cleaner, and oscillating for 15min at room temperature by adopting a DT96-4 type oscillator to obtain a mixed solution;
3. and (2) mixing the mixed solution with 30mL of 0.1mol/L acetic acid-sodium acetate buffer solution (pH = 4.5) until the pH value is 5-6, placing the mixture in a constant-temperature water bath kettle at 40 ℃ for reaction for 40min, centrifugally separating a product at 12000rpm, and washing the product with deionized water for three times to obtain modified nanoparticles (wherein the thickness of the polyphthalamide layer is 20-40 nm).
Example 3
1. Synthesis of platinum (Pt) nanoparticles:
dissolving 1.2g PVP and 0.16g glycine in 10mL deionized water, shaking and ultrasonic treating to form a uniform solution, and adding 4.2mL 10mmol/L H 2 PtCl 6 Transferring the solution into a hydrothermal kettle, and reacting for 6 hours in a forced air drying oven at 180 ℃ to obtain a brownish black product. After that, the product was centrifuged (8000rpm, 3min), and washed 3 times with ethanol, to obtain Pt nanoparticles. The obtained Pt nanoparticles were finally re-dispersed in 10mL of water.
2. Taking 0.3mL of Pt nanoparticle dispersion (the concentration is 10mmol/L, the particle size of the Pt nanoparticles is 20-30 nm), adding 3mL of sodium dodecyl sulfate aqueous solution (the concentration is 10 mmol/L), wherein the molar ratio of the Pt nanoparticles to the sodium dodecyl sulfate is 1:10, placing the mixture in a constant-temperature water bath kettle at the temperature of 30 ℃ for 25min, and then mixing the mixture with 0.3mL of o-phenylenediamine aqueous solution (0.2 mol/L) and 0.4mL of hydrogen peroxide solution (30% by mass), wherein the molar ratio of the o-phenylenediamine to the hydrogen peroxide to the sodium dodecyl sulfate is 2:1:1, performing ultrasonic treatment for 10min at the frequency of 30kHz by adopting a KQ-300DE type numerical control ultrasonic cleaner, and oscillating for 15min at room temperature by adopting a DT96-4 type oscillator to obtain a mixed solution;
3. and (2) mixing the mixed solution with 35mL0.1mol/L acetic acid-sodium acetate buffer solution (pH = 4.5) until the pH is 5-6, placing the mixture in a constant-temperature water bath kettle at 40 ℃ for reaction for 45min, centrifugally separating the product at 15000rpm, and washing the product with deionized water for three times to obtain modified nanoparticles (wherein the thickness of the polyphthalamide layer is 10-30 nm).
Example 4
1. Cerium oxide (CeO) 2 ) And (3) synthesis of nanoparticles:
0.038g of Ce (NO) 3 ) 3 Dissolved in a mixture of 13mL of deionized water and 10mL of ethanol. Stirring at 1000rpm for 10min, pouring the mixture into a 25mL high-pressure hydrothermal reaction kettle, heating to 150 deg.C at 10 deg.C/min, maintaining for 1.5h, cooling to room temperature at 10 deg.C/min to obtain milky white product, centrifuging (15000rpm, 3min), and washing with water for three times to obtain CeO 2 Nanoparticles. Finally, ceO is added 2 The nanoparticles were redispersed in 30mLIonized water.
3. 1mL of CeO was taken 2 Nanoparticle dispersion (concentration 15mmol/L, ceO) 2 The grain diameter of the nano particles is 40-60 nm), 5mL of lauryl sodium sulfate aqueous solution (the concentration is 10 mmol/L) and CeO are added 2 The molar ratio of the nanoparticles to the sodium dodecyl sulfate is 1: and 10, placing the mixture in a constant-temperature water bath kettle at the temperature of 30 ℃ for 30min, and then mixing the mixture with 0.9mL of o-phenylenediamine aqueous solution (0.2 mol/L) and 0.8mL of hydrogen peroxide solution (30% by mass), wherein the molar ratio of o-phenylenediamine to hydrogen peroxide to sodium dodecyl sulfate is 2:1:1, performing ultrasonic treatment for 15min at the frequency of 30kHz by adopting a KQ-300DE type numerical control ultrasonic cleaner, and oscillating for 15min at room temperature by adopting a DT96-4 type oscillator to obtain a mixed solution;
3. and mixing the mixed solution with 80mL of 0.1mol/L acetic acid-sodium acetate buffer solution (pH = 4.5) until the pH is 5-6, placing the mixture in a constant-temperature water bath kettle at 40 ℃ for reaction for 80min, centrifugally separating the product at 15000rpm, and washing the product with deionized water for three times to obtain modified nanoparticles (wherein the thickness of the polyphthalamide layer is 10-30 nm).
The morphology of the resulting modified nanoparticles was characterized using a transmission electron microscope and the results are shown in fig. 4. FIG. 4 is a TEM image of a modified nanoparticle of example 4 of the present invention. Fig. 4 is a core-shell structure of a diamond-shaped ceria-polymer, the polymer uniformly coating the nanoparticles. The successful synthesis of modified ceria nanoparticles is demonstrated.
Example 5
Modified nanoparticles (Fe) prepared in example 2 3 O 4 @ POPD) as a nano-enzyme to catalyze a reaction system containing oxygen, water and TMB, and simultaneously, ferroferric oxide (Fe) without coating poly-o-phenylenediamine 3 O 4 ) The test was carried out as a nanoenzyme catalyzing a reaction system containing oxygen, water, TMB: to an aqueous solution containing 2mmol of TMB, 10. Mu.L each of the modified nanoparticles (Fe) prepared in example 2 was added 3 O 4 @ POPD) (Experimental group) and ferroferric oxide (Fe) 3 O 4 ) (contrast group), ultrasonic treating for 30s, placing in 30 ℃ water bath for constant temperature reaction, and testing the ultraviolet-visible light absorption peak (wavelength 300-800 nm) every 3 min.
The test results are shown in fig. 5, 6 and 7.
FIG. 5 is a graph showing the color change of the experimental group and the control group after 30min of reaction in example 5 of the present invention. Wherein, the left graph is an experimental group, the right graph is a control group, and the left graph experimental group is a solution containing modified nanoparticles, oxygen, water and TMB; the TMB was gradually oxidized and the solution turned blue. The right control group is a solution containing unmodified nanoparticles, oxygen, water, TMB; TMB was not oxidized and the solution color did not change.
FIG. 6 is a graph showing the change of UV-visible absorption peak with time during the reaction in the experimental group of example 5 of the present invention. As can be seen from fig. 6, the product produced an ultraviolet-visible absorption peak at 672nm that gradually increased with time with the addition of the experimental group of modified nanoparticles, indicating that TMB was oxidized and continued to occur.
FIG. 7 is a graph showing the change of the UV-visible absorption peak with time in the reaction process of the control group in example 5 of the present invention. As can be seen from fig. 7, the control group to which the unmodified nanoparticles were added did not produce a uv-vis absorption peak, indicating that TMB was not oxidized.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The modified nano particles are used as redox type nano enzyme;
the modified nano particles catalyze oxygen and water to react at the pH value of 7.0 to generate hydrogen peroxide;
the modified nanoparticles comprise:
inorganic nanoparticles;
and a polyphthalamide layer coated on the surface of the inorganic nanoparticles;
the inorganic nanoparticles comprise gold, silver, platinum, palladium and Fe 3 O 4 、CeO 2 Prussian blue, V 2 O 5 、ZnCo 2 O 4 、CoFe 2 O 4 And CuCo 2 O 4 At least one of;
the thickness of the polyphthalamide layer is 10 to 40nm.
2. The use according to claim 1, wherein the inorganic nanoparticles have a particle size of 20 to 500nm.
3. The use according to claim 1, wherein the method for preparing the modified nanoparticles comprises the following steps:
a) Uniformly mixing the inorganic nanoparticle dispersion liquid, the aqueous solution of the surfactant, the aqueous solution of o-phenylenediamine and the hydrogen peroxide solution to obtain a mixed solution;
b) And adjusting the pH value of the mixed solution to 4-6, and reacting at 35-45 ℃ to obtain the modified nanoparticles.
4. The use according to claim 3, wherein in step A), the molar ratio of the inorganic nanoparticles to the surfactant is 1 to 10:10 to 500;
the molar ratio of the o-phenylenediamine to the hydrogen peroxide to the surfactant is 2 to 50:1 to 25:1 to 25;
the surfactant comprises at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and polystyrene sulfonate.
5. The use according to claim 3, wherein in step A), the mixing is achieved by ultrasound and oscillation;
the equipment adopted by the ultrasound is a KQ-300DE type numerical control ultrasonic cleaner, the frequency of the ultrasound is 30 to 45kHz, and the time is 10 to 20min;
the adopted equipment for oscillation is a DT96-4 type oscillator, the temperature of the oscillation is room temperature, and the time is 15-35 min.
6. The use according to claim 3, wherein in step B), the reagent for adjusting the pH value of the mixed solution is an acetic acid-sodium acetate buffer;
the concentration of the acetic acid-sodium acetate buffer solution is 0.1 to 0.2mol/L, and the pH value is 3.8 to 6.4.
7. The use according to claim 3, wherein in step B), the temperature of the reaction is 40 ℃ and the reaction time is 40min to 2h.
8. The use according to claim 3, wherein step B) further comprises, after the reaction:
centrifugal separation and water washing;
the rotation speed of the centrifugal separation is 12500-13500 rpm.
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