AU2021105937A4 - Preparation Method of PB capped Au-Fe3O4 Nanomaterial and its Application of water sterilization - Google Patents
Preparation Method of PB capped Au-Fe3O4 Nanomaterial and its Application of water sterilization Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004659 sterilization and disinfection Methods 0.000 title description 29
- 230000001954 sterilising effect Effects 0.000 title description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 64
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 239000010931 gold Substances 0.000 claims abstract description 38
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052737 gold Inorganic materials 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 150000002505 iron Chemical class 0.000 claims abstract description 8
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 8
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910003803 Gold(III) chloride Inorganic materials 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 229940076131 gold trichloride Drugs 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 18
- 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 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 229960003351 prussian blue Drugs 0.000 abstract description 12
- 239000013225 prussian blue Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000012266 salt solution Substances 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000002147 killing effect Effects 0.000 description 8
- 241000588724 Escherichia coli Species 0.000 description 7
- 229940023064 escherichia coli Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000004083 survival effect Effects 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 206010059866 Drug resistance Diseases 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- 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 3
- 239000002699 waste material Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003894 drinking water pollution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron salt Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000015145 nougat Nutrition 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
-
- 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
- B22F1/16—Metallic particles coated with a non-metal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/487—Treatment of water, waste water, or sewage with magnetic or electric fields using high frequency electromagnetic fields, e.g. pulsed electromagnetic fields
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- 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
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/25—Oxide
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/056—Particle size above 100 nm up to 300 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
The invention discloses a preparation method of a PB capped Au-Fe304 nanomaterial, its
products and application thereof. The method comprises the following steps. Firstly, prepare
water-soluble gold nanoparticles dispersion and water-soluble ferroferric oxide nanoparticles
dispersion, and add them into potassium ferrocyanide solution containing citric acid to get the
mixed solution. Then add the iron salt solution containing citric acid dropwise to the mixed
solution, and mechanically stir the mixed solution at 60°C for reaction. After the reaction, cool
the mixed solution to room temperature and magnetically separate it, then wash the precipitate
with ethanol for three times to get the PB capped Au-Fe304 nanomaterial with a diameter of
40-200 nm. The preparation process is simple, and the conditions are mild. The prepared
nanomaterial has uniform particle size and good dispersibility in water. According to the
method, gold/ferroferric oxide and Prussian blue are compounded, and the introduction of gold
and ferroferric oxide nanoparticles shows good photothermal heating property and excellent
magnetic recovery property.
1/4
Figure 1
Figure 2
Description
1/4
Figure 1
Figure 2
Preparation Method of PB capped Au-Fe304 Nanomaterial and its Application of
Water Sterilization
The invention belongs to the field of water treatment, and particularly relates to a
preparation method of a PB capped Au-Fe304 nanomaterial, its products and application
thereof.
Drinking water is closely related to people's life, health and safety. Bacteria and viruses, as
pollutants, have seriously threatened people's health and safety of life and property for a
long time. There are still 2 billion people who cannot drink healthy drinking water.
Therefore, the problem of drinking water pollution has always been a focus of attention.
How to obtain safe and sufficient drinking water is a major challenge. Rapid and effective
killing of bacteria in water has become a key issue. Among various sterilization
technologies, the mature traditional sterilization technologies include physical sterilization
methods such as ultraviolet lamp sterilization and membrane filtration technology, and the
well-known chemical sterilization methods include chlorination sterilization, ozone
oxidation sterilization and antibiotic sterilization. Although the above-mentioned methods
can effectively kill most harmful microorganisms, there are some limitations and
shortcomings, such as follows. 1) The waste of energy will be caused. During the use of
membrane filtration technology, there will be clogging of biological sludge, thereby
making maintenance more complicated and increasing costs. 2) Although the cost of
ultraviolet lamp sterilization is low, the sterilization is incomplete and there is a dead zone, and the bacteria are easy to revive. 3) Chlorine disinfection produces a large amount of disinfection by-products. A large number of studies have shown that drinking water from disinfection by-products increases the risk of cancer. 4) Long-term use of antibiotics will lead to strong drug resistance of bacteria and cause secondary pollution.
Photothermal materials (PTAs) convert the absorbed light in the near infrared region into
heat energy, and heat local areas to produce thermal effects. By converting light into heat
with the help of photothermal nanomaterials, this characteristic is applied to killing bacteria
in water. This provides a new research direction for killing bacteria in water. The method
can use sunlight as a light source, is a green energy-saving method. It also prevents bacteria
from developing drug resistance. The ideal photothermal water sterilization material should
have the characteristics of safety and non-toxicity, high photothermal conversion efficiency
and good water dispersibility. Meanwhile, the good recovery property of the material can
avoid the waste of the material and the material can be reused. However, the materials used
for water sterilization at present have some disadvantages, such as harsh preparation
conditions, complex preparation methods, low photothermal conversion ability, and
difficult reuse. Therefore, it is of great significance to develop new photothermal
nanomaterials for killing bacteria in sunlight and water.
At present, there are no reports on the preparation of photothermal material and the
application of water sterilization based on gold-ferroferric oxide embedded in Prussian blue
(PB) blocks.
In view of this, the present invention provides a preparation method of PB capped Au
Fe304 nanomaterial, its products and applications thereof. It aims to solve the problems
such as high maintenance cost, incomplete sterilization, carcinogenic risk of disinfection
by-products, energy waste, bacterial drug resistance in the existing sterilization technology.
It further aims to solve the problems such as complex synthesis process, poor photothermal
conversion ability and poor reusability of the existing photothermal sterilization
nanomaterial.
In order to achieve the above technical purpose, the present invention provides the
following technical scheme.
Technical scheme 1: a preparation method of PB capped Au-Fe304 nanomaterial. The
method comprises the following steps.
Mix citric acid and potassium ferrocyanide aqueous solution, then add water-soluble gold
nanoparticle dispersion and water-soluble ferroferric oxide nanoparticle dispersion. Stir the
above-mentioned solution and dispersions while heating at 60°C to obtain solution A.
Mix citric acid and ferric salt aqueous solution to obtain solution B.
Add the solution B into the solution A under stirring condition, react at 60°C for 10min.
Cool and separate the mixed solution, and wash the precipitate with ethanol for three times,
then freeze-dry the precipitate to obtain PB capped Au-Fe304 nanomaterial. The grain size
of the obtained nanomaterial is 40-200 nm, and the morphology is similar to nougat
structure.
Preferably, when preparing solution A, the molar ratio of citric acid to potassium
ferrocyanide is (7.5-25): 1. The concentration of potassium ferrocyanide aqueous s
olution is 1-2 mM.
When preparing solution B, the molar ratio of citric acid to ferric salt is (7.5-25):
1.
Preferably, the gold source of the water-soluble gold nanoparticles is one or more of
chloroauric acid, gold potassium cyanide or gold trichloride. The concentration of iron salt
aqueous solution is 1-2 mM.
Preferably, the particle size of the water-soluble gold nanoparticles is 10-50 nm.
Preferably, the water-soluble ferroferric oxide nanoparticles comprise one or more of
ferroferric oxide nanoparticles with amino groups, carboxyl groups, hydroxyl groups and
ethylene.
Preferably, the particle size of the water-soluble ferroferric oxide nanoparticles is 10-50
nm.
Preferably, the iron salt is one or more of ferric chloride, ferric nitrate or ferric dichloride.
The preparation method of the water-soluble gold nanoparticle dispersion is as follows.
After heating the gold source aqueous solution to boiling for 10 minutes, add sodium citrate
with a mass fraction of 1% to continue the reaction for 30 min. The gold nanoparticles are
dispersed in water to obtain a water-soluble gold nanoparticle dispersion.
The preparation method of the water-soluble ferroferric oxide nanoparticle dispersion is as
follows.
Add FeCl3 and FeCl2-4H20 into 50 mL deionized water, stir them until they are completely
dissolved. Functionalize groups, recover the ferroferric oxide nanoparticles with magnets,
wash the nanoparticles with ethanol, and disperse them in water to obtain water-soluble
ferroferric oxide nanoparticle dispersion.
Technical scheme 2: A kind of PB capped Au-Fe304 nanomaterial.
Technical scheme 3: application of the PB capped Au-Fe304 nanomaterial in the field of
water quality bactericides.
The key to the preparation of the PB capped Au-Fe304 nanomaterial in the invention is to
coat gold and ferroferric oxide nanoparticles uniformly in Prussian blue. It is mainly
realized through two aspects: one is that the two kinds of nanoparticles have suitable size
and excellent water dispersibility; the second is that gold and ferroferric oxide are used as
nucleation sites to control the growth rate of Prussian blue.
Compared with the prior art, the invention has the beneficial effects as follows.
(1) The preparation process of the nanomaterial is simple and the conditions are mild. (2)
The size of the nanomaterial can be adjusted by changing the amount of citric acid,
therefore the size is easy to optimize and freely controllable. (3) The obtained nanomaterial
is a nougat-like structure. Gold nanoparticles and ferroferric oxide nanoparticles are
uniformly embedded in Prussian blue with uniform particle size. They have good
dispersibility when dispersed in aqueous solution and can exist stably in aqueous solution
for a long time. (4) The obtained nougat-like nanomaterial has excellent magnetic recovery
property, photothermal heating ability and photothermal sterilization characteristics.
In order to explain the embodiments of the present invention or the technical scheme in the
prior art more clearly, the figures needed in the embodiments will be briefly introduced
below. Obviously, the figures in the following description are only some embodiments of
the present invention, and for ordinary technicians in the field, other figures can be obtained
according to these figures without paying creative labor.
Figure 1 A TEM graph of the PB capped Au-Fe304 nanomaterial prepared in Embodiments
1-3 of the present invention
a The TEM graph of the PB capped Au-Fe304 nanomaterial prepared in Embodiment 1
b The TEM graph of the PB capped Au-Fe304 nanomaterial prepared in Embodiment 2
c The TEM graph of the PB capped Au-Fe304 nanomaterial prepared in Embodiment 3
Figure 2 An optical photo of the properties of the PB capped Au-Fe304 nanomaterial
Left figure The figure of the dispersion property of the PB capped Au-Fe304 nanomaterial
in water
Right figure The figure of the magnetic recovery property of the PB capped Au-Fe304
nanomaterial
Figure 3 A photothermal heating curve of the PB capped Au-Fe304 nanomaterial aqueous
dispersions with different concentrations
Figure 4 A temperature difference diagram of photothermal heating of the PB capped Au
Fe304 nanomaterial aqueous dispersions with different concentrations
Figure 5 An optical photo of the killing of Escherichia coli by the PB capped Au-Fe304
nanomaterial under different illumination times
Figure 6 The survival rate of the PB capped Au-Fe304 nanomaterial co-incubated with
Escherichiacoli under different illumination times
Figure 7 The killing effect of the PB capped Au-Fe304 nanomaterial on Escherichiacoli in
three cycles
Various exemplary embodiments of the present invention will now be described in detail.
This detailed description should not be taken as a limitation of the present invention, but
rather as a more detailed description of certain aspects, characteristics and embodiments of
the present invention.
It should be understood that the terms described in the present invention are only for
describing specific embodiments, and are not intended to limit the present invention. In
addition, as for the numerical range in the present invention, it should be understood that
every intermediate value between the upper limit and the lower limit of the range is also
specifically disclosed. Intermediate values within any stated value or stated range and every
smaller range between any other stated value or intermediate values within the stated range
are also included in the present invention. The upper and lower limits of these smaller
ranges can be independently included or excluded from the range.
Unless otherwise stated, all technical and scientific terms used herein have the same
meanings as commonly understood by those skilled in the art to which the present invention
relates. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe methods and/or materials related to the documents. In case of conflict with any incorporated documents, the contents of this specification shall prevail.
Without departing from the scope or spirit of the invention, it is obvious to those skilled in
the art that many modifications and changes can be made to the specific embodiments of
the specification of the invention. Other embodiments derived from the description of the
present invention will be apparent to the skilled person. The specification and embodiments
of this application are only exemplary.
As used herein, "comprising", "including", "having", "containing", etc., are all open terms,
which means including but not limited to.
The water-soluble gold nanoparticles used in the embodiments of the invention have a
particle size of 10-50 nm and the water-soluble ferroferric oxide nanoparticles have a
particle size of 10-50 nm.
The room temperature referred to in the present invention is the indoor temperature, which
is well known to those skilled in the art and will not be described in detail here. In
particular, the room temperature referred to in the present invention is 25°C.
Embodiment 1
Preparation of PB capped Au-Fe304nanomaterial.
(1) Water-soluble ferroferric oxide nanoparticle dispersion
Add 162mgFeCl3 and 99 mgFeCl2-4H20 into 50mL deionized water, stir them fully until
the salt is completely dissolved. Then add 6 mmol dimethylacetamide (or NH3H20) into
the above mixed solution, react at 80°C for 30 min. After the reaction, recover the
ferroferric oxide nanoparticles with magnets, wash them with ethanol for three times, and
then disperse them in 12 mL water to obtain water-soluble ferroferric oxide nanoparticle
dispersion for later use.
(2) Water-soluble gold nanoparticle dispersion
Add 500 mL of chloroauric acid aqueous solution with the concentration of 100 mmol/L
into a 200 mL round-bottom flask, heat the solution to boil for 10mmin. Then add 1.5 mL of
1% sodium citrate to continue the reaction for 30 min. After centrifugation, the gold
nanoparticles are dispersed into 8 mL of water to obtain water-soluble gold nanoparticle
dispersion for later use.
(3) Add 60 mg citric acid into 20 mL potassium ferrocyanide aqueous solution with a
concentration of 1.0 mM, stir them uniformly. Add 4 mL water-soluble ferroferric oxide
nanoparticle dispersion and 4 mL water-soluble gold nanoparticle dispersion prepared in
steps (1) and (2) dropwise to the above solution respectively, and then stir them while
heating at 60°C to obtain solution A.
(4) Add 60 mg citric acid into 20 mL aqueous solution of FeCl3-6H20 with a concentration
of 1.0 mM as iron salt to obtain solution B.
(5) Add the solution B into the solution A dropwise, and continue mechanical stirring at
°C and react for 5min. After the reaction, recover the the nanomaterial with magnets.
Cool the mixed solution to room temperature and then separate it. Wash the precipitate with ethanol for three times, and then freeze-dry it to obtain the PB capped Au-Fe304 nanomaterial.
Figure la is a transmission electron microscope (TEM) graph of the PB capped Au-Fe304
nanomaterial prepared in this embodiment. It can be seen that the shape of the prepared
nanomaterial is a uniform nougat-like block structure with a particle size of 70-100 nm,
and the gold nanoparticles and ferroferric oxide nanoparticles are uniformly embedded in
Prussian blue with good dispersibility.
Figure 2 is an optical photo of the properties of the PB capped Au-Fe304 nanomaterial. The
left figure is the figure of the dispersion property of the PB capped Au-Fe304 nanomaterial
in water. It can be seen that the aqueous dispersion of PB capped Au-Fe304 is very uniform,
proving that PB capped Au-Fe304 has good dispersibility in water. The right figure is the
figure of the magnetic recovery property of the PB capped Au-Fe304 nanomaterial under
an external magnetic field. It can be seen that the particles quickly gather to the side of the
magnets, proving that the PB capped Au-Fe304 nanomaterial has excellent recoverability
and reusability.
Embodiment 2
Preparation of PB capped Au-Fe304 nanomaterial.
(1) The preparation method of the water-soluble ferroferric oxide nanoparticle dispersion
is the same as that of Embodiment 1.
(2) The preparation method of water-soluble gold nanoparticle dispersion is the same as
that of Embodiment 1.
(3) Add 80 mg citric acid into 20 mL potassium ferrocyanide aqueous solution with a
concentration of 2.0 mM, stir them uniformly. Add 4 mL water-soluble ferroferric oxide
nanoparticle dispersion and 4 mL water-soluble gold nanoparticle dispersion prepared in
steps (1) and (2) dropwise to the above solution respectively, and then stir them while
heating at 60°C to obtain solution A.
(4) Add 60 mg citric acid into 20 mL aqueous solution of FeCl3-6H20 with a concentration
of 2.0 mM as iron salt to obtain solution B.
(5) Add the solution B into the solution A dropwise, and continue mechanical stirring at
°C and react for 5min. After the reaction, recover the nanomaterial with magnets. Cool
the mixed solution to room temperature and then separate it. Wash the precipitate with
ethanol for three times, and then freeze-dry it to obtain the PB capped Au-Fe304
nanomaterial.
Figure lb is a transmission electron microscope (TEM) graph of the PB capped Au-Fe304
nanomaterial prepared in this embodiment. It can be seen that the shape of the prepared
nanomaterial is a uniform nougat-like block structure, and its particle size is increased
compared with that of Embodiment 1, ranging from 100-130 nm. Gold nanoparticles and
ferroferric oxide nanoparticles are embedded in Prussian blue, but the embedding amount
decreases with the increase of Prussian blue production.
Embodiment 3
Preparation of PB capped Au-Fe304 nanomaterial.
(1) The preparation method of the water-soluble ferroferric oxide nanoparticle dispersion
is the same as that of Embodiment 1.
(2) The preparation method of water-soluble gold nanoparticle dispersion is the same as
that of Embodiment 1.
(3) Add 100 mg citric acid into 20 mL potassium ferrocyanide aqueous solution with a
concentration of 1.0 mM, stir them uniformly. Add 4 mL water-soluble ferroferric oxide
nanoparticle dispersion and 4 mL water-soluble gold nanoparticle dispersion prepared in
steps (1) and (2) and dropwise to the above solution respectively, and then stir them while
heating at 60°C to obtain solution A.
(4) Add 100 mg citric acid into 20 mL aqueous solution of FeCl3-6H20 with a concentration
of 1.0 mM as iron salt to obtain solution B.
(5) Add the solution B into the solution A dropwise, and continue mechanical stirring at
°C and react for 5min. After the reaction, recover the nanomaterial with magnets. Cool
the mixed solution to room temperature and then separate it. Wash the precipitate with
ethanol for three times, and then freeze-dry it to obtain the PB capped Au-Fe304
nanomaterial.
Figure l cis a transmission electron microscope (TEM) graph of the PB capped Au-Fe304
nanomaterial prepared in this embodiment. It can be seen that the shape of the prepared
nanomaterial is a uniform nougat-like block structure, and its particle size is reduced
compared with that of Embodiment 1, ranging from 50-70 nm. Gold nanoparticles and
ferroferric oxide nanoparticles are uniformly embedded in Prussian blue, but the amount
of embedding in Prussian blue decreases due to the reduction of the particle size of the
Prussian blue.
Embodiment 4
Preparation of PB capped Au-Fe304 nanomaterial.
(1) Water-soluble ferroferric oxide nanoparticle dispersion
Add 162 mg FeCl3 and 99 mg FeCl2-4H20 into 50 mL deionized water, stir them fully until
the salt is completely dissolved. Then add 6 mmol ethylene glycol into the above mixed
solution, react at 80°C for 30 min. After the reaction, recover the ferroferric oxide
nanoparticles with magnets, wash them with ethanol for three times, and then disperse them
in 12 mL water to obtain water-soluble ferroferric oxide nanoparticle dispersion for later
use.
(2) Water-soluble gold nanoparticle dispersion
Add 500 mL of gold potassium cyanide aqueous solution with the concentration of 100
mmol/L into a 200 mL round-bottom flask, heat the solution to boil for 10min. Then add
1.5 mL of 1% sodium citrate to continue the reaction for 30 min. After centrifugation, the
gold nanoparticles are dispersed into 8 mL of water to obtain water-soluble gold
nanoparticle dispersion for later use.
Steps (3), (4) and (5) are the same as Embodiment 1. The PB capped Au-Fe304
nanomaterial with uniform nougat-like block structure is obtained, and the dispersibility is
good.
Embodiment 5
Same as Embodiment 1, except that ferric nitrate is used as iron salt in step (4).
The PB capped Au-Fe304 nanomaterial with a uniform nougat-like block structure is
obtained, and the dispersibility is good.
Embodiment 6
Same as Embodiment 1, except that ferric chloride is used as iron salt in step (4).
The PB capped Au-Fe304 nanomaterial with a uniform nougat-like block structure is
obtained, and the dispersibility is good.
Embodiment 7
Same as Embodiment 1, except that the heating temperature in step (3) and step (5) is 40°C.
The PB capped Au-Fe304 nanomaterial with a uniform nougat-like block structure is
obtained, and the dispersibility is good.
Embodiment 8
Same as Embodiment 1, except that the heating temperature in step (3) and step (5) is 80°C.
The PB capped Au-Fe304 nanomaterial with a uniform nougat-like block structure is
obtained, and the dispersibility is good.
Embodiment 9
Photothermal heating test of PB capped Au-Fe304nanomaterial.
Take 3 mL of aqueous solutions of PB capped Au-Fe304 nanoparticles (products pre
pared in Embodiment 1) with concentrations of 0 g/mL for 1, 20 g/mL for 2, 40
pg/mL for 3, 60 g/mL for 4, 80 g/mL for 5 and 100 g/mL for 6, respectively, pl
ace them in cuvettes, and irradiate them with 808 nm laser with power of 2 W/cm 2 f
or 10min. Detect the heating of this series of dispersions with different concentration
s by thermocouple during this period. The results are shown in Figure 3 and Figure
4. The results show that the temperature of aqueous dispersions of the PB capped A
u-Fe304 nanomaterial can rise rapidly under the irradiation of 808 nm light, and the
heating has obvious concentration dependence, indicateing that the PB capped Au-Fe3
04 nanomaterial has excellent photothermal heating function.
Embodiment 10
Photothermal killing ability test of PB capped Au-Fe304 nanomaterial.
Incubate 3 mL of aqueous dispersion of PB capped Au-Fe304 nanomaterial (product
prepared in Embodiment 1) with a concentration of 100 g/mL with Escherichia coli.
Irradiate the aqueous dispersion with near infrared light with a power of 2 W/cm 2 at 808nm
for different times (0, 1, 2, 3, 4, 5 min), while the control group is Escherichiacoli without
illumination. Figure 5 is an optical picture of the survival of bacteria after sampling,
dilution, coating and incubation, and Figure 6 shows the survival rate of Escherichiacoli
after counting the bacteria. It can be seen that the survival rate of bacteria in the
experimental group is almost zero after 5 min of illumination, indicating that PB capped
Au-Fe304 nano-blocks have excellent photothermal sterilization effect.
Embodiment 11
Cyclic sterilization ability test of PB capped Au-Fe304 nanomaterial.
The operation steps of the sterilization experiment are the same as those in Embodiment
11, wherein the near infrared light is illuminated for 5 min. After completing one
sterilization experiment, recover the materials under the action of an external magnetic
field, wash them with ethanol for three times, and then the next cycle experiment is carried
out. Figure 7 is the data of the survival rate of bacteria after three times of cyclic sterilization experiments. It can be seen that the killing efficiency of the PB capped Au
Fe304 nanomaterial to Escherichia coli is still above 98% after three times of cyclic
sterilization experiments, indicating that the material has excellent reusability.
Comparative example 1
Same as Embodiment 1, except that no water-soluble gold nanoparticles are added.
The results show that the obtained photothermal property of the Fe304-PB nanomaterial is
weaker than that of the PB capped Au-Fe304nanomaterial.
Comparative example 2
Same as Embodiment 1, except that water-soluble ferroferric oxide nanoparticles are not
added.
The results show that the obtained Au-PB nanomaterial ie not magnetic and recoverable.
Comparative example 3
Same as Embodiment 1, except that ferroferric oxide without functionalization is directly
added.
The results show that the obtained PB capped Au-Fe304nanomaterial is agglomerated and
has poor dispersibility.
Comparative example 4
Same as Embodiment 1, except that water-soluble gold nanoparticles and water-soluble
ferroferric oxide nanoparticles are not added.
The results show that the obtained pure Prussian blue nanomaterial is nonmagnetic and its
photothermal property is weaker than that of the PB capped Au-Fe304 nanomaterial.
Comparative example 5
Same as Embodiment 1, except that the heating temperature in step (3) and step (5) is 90°C.
The results show that because the temperature is too high and the reaction is too fast,
nanoparticles can not be formed and agglomeration occurred.
The above are only preferred embodiments of the present invention, and are not intended
to limit the present invention. Any modifications, equivalent substitutions and
improvements made within the spirit and principles of the present invention shall be
included in the scope of protection of the present invention.
Claims (10)
1. A preparation method of a PB capped Au-Fe304 nanomaterial, characterized by
comprising the following steps:
mix citric acid and potassium ferrocyanide aqueous solution, then add water-soluble gold
nanoparticle dispersion and water-soluble ferroferric oxide nanoparticle dispersion; stir the
above-mentioned solution and dispersions while heating to obtain solution A;
mix citric acid and ferric salt aqueous solution to obtain solution B;
add the solution B into the solution A under stirring condition, heat them for reaction; cool
and separate the mixed solution, wash the precipitate and then freeze-dry it to obtain the
PB capped Au-Fe304 nanomaterial.
2. The preparation method according to Claim 1, characterized in that when preparin
g solution A, the molar ratio of citric acid to potassium ferrocyanide is (7.5-25):
1; when preparing solution B, the molar ratio of citric acid to ferric salt is (7.5-2
): 1.
3. The preparation method according to Claim 1, characterized in that the gold source of
the water-soluble gold nanoparticles is one or more of chloroauric acid, gold potassium
cyanide or gold trichloride.
4. The preparation method according to Claim 3, characterized in that the particle size of
the water-soluble gold nanoparticles is 10-50 nm.
5. The preparation method according to Claim 1, characterized in that the water-soluble
ferroferric oxide nanoparticles comprise one or more of ferroferric oxide nanoparticles with
amino groups, carboxyl groups, hydroxyl groups and ethylene.
6. The preparation method according to Claim 5, characterized in that the particle size of
the water-soluble ferroferric oxide nanoparticles is 10-50 nm.
7. The preparation method according to Claim 1, characterized in that the heating
temperature is 40-80°C.
8. The preparation method according to Claim 1, characterized in that the iron salt is one
or more of ferric chloride, ferric nitrate or ferric dichloride.
9. A PB capped Au-Fe304 nanomaterial obtained by the preparation method according to
any one of Claims 1-8.
10. Application of the PB capped Au-Fe304 nanomaterial in the field of water bactericides
according to Claim 9.
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