CN114223670A - Antibacterial agent and preparation method thereof - Google Patents
Antibacterial agent and preparation method thereof Download PDFInfo
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- CN114223670A CN114223670A CN202111393058.3A CN202111393058A CN114223670A CN 114223670 A CN114223670 A CN 114223670A CN 202111393058 A CN202111393058 A CN 202111393058A CN 114223670 A CN114223670 A CN 114223670A
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- antibacterial agent
- deionized water
- reaction kettle
- alooh
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- -1 Polytetrafluoroethylene Polymers 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000003517 fume Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000187479 Mycobacterium tuberculosis Species 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 229960000190 bacillus calmette–guérin vaccine Drugs 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
An antibacterial agent is prepared from Al (NO)3)3Adding the mixture into deionized water, then sequentially adding PVP, ethanol and acetone, and uniformly stirring to obtain a mixed solution; adding Ni (NO) to the mixed solution3)2Transferring the solution to a hydrothermal reaction kettle containing a Polytetrafluoroethylene (PTFE) lining for hydrothermal reaction, pouring out reaction liquid, centrifugally washing, drying and grinding to obtain a carrier, wherein the carrier is named as Ni-AlOOH; dispersing Ni-AlOOH in deionized water, adding AgNO3And (3) stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product. The invention enables the material to have strong assembly capability through nickel doping,the synthetic material has good biocompatibility and also has good antibacterial performance.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to a nano Ag-loaded nickel modified nano flower-shaped AlOOH antibacterial agent and a preparation method thereof.
Background
Pathogenic contamination in the environment has raised serious public concern. Due to the complexity of the hospital environment, various infectious microorganisms have strong resistance to disinfectants and drugs. The united states centers for disease control and prevention (CDC) estimates that, despite hospital disinfection being valued, approximately 170 million patients in the united states infect hospital-related infections each year, with an additional medical cost of $ 45-65 billion per year. Therefore, broad-spectrum and highly effective bactericides have been the focus of research.
Chlorination is the most common method of reducing the risk of nosocomial infections due to the pungent odor and the limitation of harmful by-products of the sterilization product. At present, many methods related to the resistance of microorganisms and antibacterial agents, particularly the application of inorganic nanoparticles such as Cu, ZnO, Ti, Ag, have been studied. The silver nanoparticles have broad-spectrum antibacterial activity and can be used for targeted treatment of some stubborn microorganisms. It is noted, however, that controlling the state of the silver nano-species, including size and shape, is critical to enhance antimicrobial activity, since silver ions are reasonably released from the final nanomaterial. In addition, the interaction between the constructed nano-species and the support also affects the release of Ag ions to attack these bacteria. For example, Cheng et al (New Chemical Materials,2020,48(7):265-270) attempted to load Ag nanoparticles onto mesoporous silica using a designed strategy, but these results tended to encapsulate the Ag nanoparticles into their limited mesopores, which may prevent efficient release of silver ions due to the long diffusion distance of silver ions through the mesoporous channels to the bacteria. In addition, silica lacks abundant surface groups and fails to build strong interactions between silver nano-species and bacteria to trigger controlled attack pathways. Patent CN109221249A discloses a method for preparing a ZnO nanorod-supported nano-Ag composite antibacterial agent, but the synthesized antibacterial agent must have antibacterial activity under the condition of ultraviolet irradiation. Therefore, designing powerful two-dimensional materials that assemble and modify functional silver species to trigger better antimicrobial performance can be a challenge.
Disclosure of Invention
The technical problem to be solved is as follows: the present invention provides an antimicrobial agent and a method for preparing the same, which produces a powerful two-dimensional material for assembling and modifying functional silver species to trigger better antimicrobial properties.
The technical scheme is as follows: a method for preparing an antibacterial agent comprises the following steps: step 1, adding Al (NO)3)3Adding into deionized water, sequentially adding PVP, ethanol and acetone, and stirring to obtain mixed solution, wherein Al (NO) is3)3The mass ratio of the PVP to the PVP, water, ethanol to acetone is 1 (0.2-2.5) to (40-60) to (9.6-111) to (10-60); step 2, adding 0.5-1 wt.% of Ni (NO) into the mixed solution obtained in the step 13)2Solution, Ni (NO)3)2The concentration of the carrier is 0.5-1 mol/L, then the carrier is transferred to a hydrothermal reaction kettle containing Polytetrafluoroethylene (PTFE) lining, hydrothermal reaction is carried out for 12-32 h at the temperature of 150-200 ℃, then reaction liquid is poured out, and the carrier is obtained by centrifugal washing, drying and grinding, and is named as Ni-AlOOH; step 3, dispersing Ni-AlOOH in deionized water, and adding AgNO3Stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product, wherein the calcining heating rate is 1-5 ℃/min, the calcining temperature is 200-500 ℃, and the time is 1-5 h.
Preferably, Al (NO) in step 13)3The mass ratio of the PVP to the water to the ethanol to the acetone is 1:1.2:60:60:10
Preferably, Ni (NO) in step 23)2The concentration of (2) is 0.6 mol/L.
The set rotating speed and the set time of the centrifuge in the step 2 and the step 3 are 5000-10000 r/min and 2-6 min respectively.
Preferably, the volume of the deionized water in the step 3 is 50mL, and the volume is Ni-AlOOH or AgNO3The amount of the raw materials is 0.1g and 0.7084 g respectively, and the stirring time is 3-12 h.
Preferably, in the step 3, the temperature rise rate in the tubular furnace is 2 ℃/min, the calcination temperature is 450 ℃, and the time is 1-5 h.
The antibacterial agent prepared by the above preparation method
Has the advantages that: the nickel doping enables the material to have strong assembly capability (as can be embodied in fig. 2). The synthetic material has good biocompatibility. The material has good antibacterial performance (table 1, as shown in figure 2).
Drawings
FIG. 1 is a schematic diagram of the synthesis procedure;
the left picture of fig. 2 is an electron microscope photo of the composite material of the nickel modified nanometer flower-shaped AlOOH loaded with the nanometer Ag, and the right picture is an electron microscope photo of the composite material of the nanometer flower-shaped AlOOH loaded with the nanometer Ag.
FIG. 3 shows the inhibition zones of the nanocomposite (a) AlNiO, (B) AlO, (C) Ag-AlNiO and (D) Ag-AlO on (A) gram-negative E.coli, (B) Pseudomonas aeruginosa, (C) Staphylococcus aureus, and (D) Candida albicans.
Detailed Description
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Example 1
Mixing Al (NO)3)3·9H2O in 30mL deionized water, followed by 0.6g PVP in 30mL ethanol and 5mL acetone with a pipette in a fume hood, and finally 400. mu.L of 0.6mol/L Ni (NO) with a pipette gun3)2And transferring the solution into a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature, then obtaining a white precipitate, transferring the reaction kettle into a centrifuge tube in a fume hood, washing the reaction kettle once at a rotating speed of 6000r/min for 6 minutes, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at 70 ℃, grinding the reaction kettle with an agate mortar, and collecting the product, namely AlNiO.
Example 2
Mixing Al (NO)3)3·9H2Dissolving O in 30mL of deionized water, adding 0.6g of PVP dissolved in 30mL of ethanol, adding 5mL of Acetone (AR) in a fume hood by using a pipette, transferring the mixture to a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature to obtain a white precipitate, transferring the reaction kettle to a centrifuge tube in the fume hood at the rotating speed of 6000r/min for 6min, washing the reaction kettle once with waterWashing with ethanol twice, drying in an oven at 70 deg.C, grinding with agate mortar, and collecting and named AlO.
Example 3
Mixing Al (NO)3)3·9H2O in 30mL deionized water, followed by 0.6g PVP in 30mL ethanol and 5mL acetone with a pipette in a fume hood, and finally 400. mu.L of 0.6mol/L Ni (NO) with a pipette gun3)2Transferring the solution into a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the reaction kettle, transferring the reaction kettle into a centrifuge tube in a fume hood, washing the reaction kettle once at a rotating speed of 6000r/min for 6 minutes, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at 70 ℃, grinding the reaction kettle with agate, collecting the solution, dissolving 0.10g of Ni-AlOOH in 50mL of deionized water, and weighing 1wt.% of AgNO3Dissolving the solution in the solution, stirring the solution for 8 hours on a magnetic stirrer, washing the solution by water and ethanol once respectively, drying the solution at 70 ℃, grinding the solution, and then carrying out heat treatment on the ground solution in a tubular furnace for 2 hours to obtain a product named as Ag-AlNiO, wherein the heating rate in the tubular furnace is 2 ℃/min, and the calcining temperature is 450 ℃.
Example 4
Mixing Al (NO)3)3·9H2Dissolving O in 30mL of deionized water, adding 0.6g of PVP dissolved in 30mL of ethanol, adding 5mL of Acetone (AR) in a fume hood by using a pipette, transferring the mixture to a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature to obtain a white precipitate, transferring the reaction kettle to a centrifuge tube in the fume hood at the rotating speed of 6000r/min for 6 minutes, washing the reaction kettle once, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at the temperature of 70 ℃, grinding the reaction kettle with agate, collecting the product, dissolving 0.10g of nano flower-shaped AlOOH in 50mL of deionized water, weighing 1wt.% of AgNO, dissolving the product in 50mL of deionized water, and grinding the product with an agate mortar to obtain a fine powder3Dissolving the solution in the solvent, adding a rotor, stirring the solution for 8 hours on a magnetic stirrer, washing the solution by water and ethanol once respectively, drying the solution at the temperature of 70 ℃, grinding the solution, and then carrying out heat treatment on the solution for 2 hours in a tubular furnace to obtain a product named as Ag-AlO, wherein the heating rate in the tubular furnace is 2 ℃/min, and the calcining temperature is 450 ℃.
The above examples 1-4 were evaluated for the antifungal properties of Ag-AlNiO, Ag-AlO and AlO using the Microplate Alamar Blue method. The Minimum Inhibitory Concentration (MIC) values are shown in Table 1. Wherein BCG and MDR are BCG vaccine and multidrug resistant respectively. (MIC (minimum inhibition concentration): minimum inhibitory concentration) of the lowest drug concentration that completely inhibits the growth of bacteria in a test tube or a small hole in the dilution method for microorganism identification)
TABLE 1 MIC values (μ g/mL) of the synthesized nanocomposites for Mycobacterium tuberculosis
Claims (7)
1. The preparation method of the antibacterial agent is characterized by comprising the following steps: step 1, adding Al (NO)3)3Adding into deionized water, sequentially adding PVP, ethanol and acetone, and stirring to obtain mixed solution, wherein Al (NO) is3)3The mass ratio of the PVP to the PVP, water, ethanol to acetone is 1 (0.2-2.5) to (40-60) to (9.6-111) to (10-60); step 2, adding 0.5-1 wt.% of Ni (NO) into the mixed solution obtained in the step 13)2Solution, Ni (NO)3)2The concentration of the carrier is 0.5-1 mol/L, then the carrier is transferred to a hydrothermal reaction kettle containing Polytetrafluoroethylene (PTFE) lining, hydrothermal reaction is carried out for 12-32 h at the temperature of 150-200 ℃, then reaction liquid is poured out, and the carrier is obtained by centrifugal washing, drying and grinding, and is named as Ni-AlOOH; step 3, dispersing Ni-AlOOH in deionized water, and adding AgNO3Stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product, wherein the calcining heating rate is 1-5 ℃/min, the calcining temperature is 200-500 ℃, and the time is 1-5 h.
2. The method for producing the antibacterial agent according to claim 1, wherein Al (NO) in step 13)3The mass ratio of the PVP to the water to the ethanol to the acetone is 1:1.2:60:60: 10.
3. The method for producing the antibacterial agent according to claim 1, wherein Ni (NO) in step 23)2The concentration of (2) is 0.6 mol/L.
4. The method for producing an antibacterial agent according to claim 1, characterized in that: in the step 2 and the step 3, the set rotating speed and the set time of the centrifuge are 5000-10000 r/min and 2-6 min respectively.
5. The method for producing an antibacterial agent according to claim 1, characterized in that: step 3, the volume of the deionized water is 50mL, and the deionized water is Ni-AlOOH and AgNO3The amount of the raw materials is 0.1g and 0.7084 g respectively, and the stirring time is 3-12 h.
6. The method for producing an antibacterial agent according to claim 1, characterized in that: and 3, heating in the tubular furnace at a rate of 2 ℃/min, calcining at a temperature of 450 ℃ for 1-5 h.
7. An antibacterial agent obtained by the process according to any one of claims 1 to 6.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105948087A (en) * | 2016-03-25 | 2016-09-21 | 南开大学 | Preparation method of gamma-AlOOH and gamma-Al2O3 nanotube and nanostructure |
CN107897203A (en) * | 2017-10-11 | 2018-04-13 | 河南师范大学 | A kind of nickel cobalt layered double-hydroxide composite material of silver ion and its preparation method and application |
CN108991016A (en) * | 2018-08-02 | 2018-12-14 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of alumina load copper zinc antibacterial agent |
CN110015676A (en) * | 2018-01-09 | 2019-07-16 | 中国石油天然气股份有限公司 | Alumina material and preparation method thereof |
-
2021
- 2021-11-23 CN CN202111393058.3A patent/CN114223670A/en active Pending
Patent Citations (4)
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CN105948087A (en) * | 2016-03-25 | 2016-09-21 | 南开大学 | Preparation method of gamma-AlOOH and gamma-Al2O3 nanotube and nanostructure |
CN107897203A (en) * | 2017-10-11 | 2018-04-13 | 河南师范大学 | A kind of nickel cobalt layered double-hydroxide composite material of silver ion and its preparation method and application |
CN110015676A (en) * | 2018-01-09 | 2019-07-16 | 中国石油天然气股份有限公司 | Alumina material and preparation method thereof |
CN108991016A (en) * | 2018-08-02 | 2018-12-14 | 张家港市汇鼎新材料科技有限公司 | A kind of preparation method of alumina load copper zinc antibacterial agent |
Non-Patent Citations (3)
Title |
---|
YAO ZHOU ET AL.: "Adsorption and On-Site Transformation of Transition Metal Cations on Ni-Doped AlOOH Nanoflowers for OER Electrocatalysis", 《ACS SUSTAINABLE CHEM. ENG.》 * |
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许孟飞 等: "Al2O3/ZnO纳米复合材料的制备及其应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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