CN111496268A - Size-controllable Pt/MnO2Nano material and preparation method thereof - Google Patents
Size-controllable Pt/MnO2Nano material and preparation method thereof Download PDFInfo
- Publication number
- CN111496268A CN111496268A CN202010403199.8A CN202010403199A CN111496268A CN 111496268 A CN111496268 A CN 111496268A CN 202010403199 A CN202010403199 A CN 202010403199A CN 111496268 A CN111496268 A CN 111496268A
- Authority
- CN
- China
- Prior art keywords
- mno
- nano
- solution
- shell
- size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a Pt/MnO with controllable size2A nano material and a preparation method thereof. The method comprises the following steps: (1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a porous Pt nano particle colloidal solution; (2) adding alkali solution to regulate pH, adding manganese acetate solution, and utilizing the space between manganese ion in metal salt and oxygen atom in molecular chain of nonionic surfactantThe manganese ions are hydrolyzed on the surface of the platinum nano-particles through electrostatic interaction, and MnO is further formed through condensation reaction2Shell layer to obtain Pt/MnO2Of (4) a nanomaterial of (2). The nano material prepared by the invention takes porous Pt nano as an inner core and MnO with a nano scale2For the shell, the sizes of the inner core and the shell are accurately adjusted by controlling the molar ratio of the platinum precursor to the nonionic surfactant and the dosage of the manganese acetate.
Description
Technical Field
The invention belongs to the technical field of precious metal/semiconductor composite nano-material preparation, and particularly relates to a size-controllable porous core-shell structure material and a preparation method thereof.
Background
The noble metal material mainly refers to a material composed of 8 metal elements such as gold, silver and platinum group metals (ruthenium, rhodium, palladium, osmium, iridium, platinum), the noble metal nanoparticles are attracted to researchers in the biomedical field due to the unique property (physics, 2014,43,290 SPR) of localized Surface plasmon resonances (L optically localized Surface Plasmons Resonance, L SPR) of the noble metal nanoparticles, which is defined as that when incident light irradiates the nanoscale noble metal material, the noble metal nanomaterials can strongly absorb photons if the incident photon frequency is consistent with the Surface electronic vibration frequency of the noble metal material, so the noble metal nanomaterials are widely used in the fields of drug research, cell labeling, molecular dynamics research (chemical society, 2012,41, 2943-.
Because it is difficult for the single-component nanoparticles to simultaneously satisfy a plurality of requirements in clinical treatment, such as biocompatibility, targeting property, high efficiency, etc., researchers often compound several nanoparticles to obtain a multifunctional nanocomposite through modification. Among them, the most common method is to form a carrier with a core-shell type nano-structure, thereby achieving the purpose of treating tumors with multiple functions. When noble metals are combined with metal oxide semiconductor Materials to form core-shell nanoparticles, a plasma enhanced chemical reaction effect (Advanced Materials,2014,26, 5274-. The phenomenon enables the noble metal-semiconductor composite material to have huge application potential in the fields of chemistry and biomedicine.
Platinum (Pt) is a common noble metal material, and Pt nanoparticles have been applied to both photocatalytic and photothermal therapies in recent years due to broadband absorption over the entire visible light region, and porous Pt nanoparticles have additional advantages in light absorption and photothermal conversion compared to non-porous nanoparticles, and can be applied to drug loading (advanced health Materials 2016, 5, 3165-. Manganese dioxide (MnO)2) The material not only has pH responsiveness, but also contains oxygen in degradation products, so MnO is2Can be used as pH response material and can also be used as material for enhancing the effect of photodynamic therapy (Advanced Functional Materials,2016,26, 5490-5498). Takes porous Pt nano particles as an inner core and MnO2The core-shell structure material of the shell can utilize the noble metal-metal semiconductor interface reaction to act on the photodynamic therapy of the tumor. At present, no porous Pt/MnO with adjustable inner core and outer shell is found2The synthesis method of the core-shell structure is reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides Pt/MnO with controllable size2The problems in the background art are solved by the nanometer material and the preparation method thereof.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a Pt/MnO with controllable size2The preparation method of the nano material comprises the following steps:
1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a porous Pt nano particle colloidal solution; the non-ionic surfactant is polyoxyethylene lauryl ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene stearate, polyethylene glycol cetyl ether or lauryl alcohol polyoxyethylene ether, the platinum precursor is chloroplatinic acid, potassium chloroplatinite or potassium chloroplatinate, and the reducing agent is sodium borohydride, ascorbic acid, glucose or sodium citrate;
2) MnO is added into the colloidal solution of the platinum nano-particles2Obtaining a second mixed solution from the aqueous solution of the metal salt precursor (manganese acetate), and standing for reaction; then adding alkali liquor to adjust the pH value of the second mixed solution to 8-14, carrying out ultrasonic reaction, and centrifugally separating the reaction solution to obtain MnO with porous Pt nano particles as an inner core2Is a core-shell structure material of the shell.
In a preferred embodiment of the present invention, the concentration of the Pt precursor in the first mixed solution is 0.1 to 10 mmol/L, and the concentration of the nonionic surfactant is 1 to 100 g/L.
In a preferred embodiment of the present invention, the concentration of manganese acetate in the second mixed solution is 0.1 to 0.3 mmol/L.
In a preferred embodiment of the present invention, in the step 2), an alkali solution is added to adjust the pH of the second mixed solution, wherein the alkali solution is one of ammonia water, sodium hydroxide, sodium carbonate, sodium bicarbonate, disodium hydrogen phosphate and urea.
The second technical scheme adopted by the invention for solving the technical problems is as follows: provides Pt/MnO prepared by the method2Core-shell nanomaterial comprising an inner core of porous Pt nanoparticles and MnO2A shell of nanoparticles, wherein the particle diameter of the Pt nanoparticles is 20-100 nm, the pore size is 1-10 nm, MnO2The thickness of the shell layer is 20-50 nm, and the coating rate is 100%.
Compared with the background technology, the technical scheme has the following advantages:
the proposal provides Pt/MnO with controllable size and novel structure2Composite materials and methods for making the same. Passing MnO2The coating on the surface of the porous Pt nano-particles endows the Pt nano-particles with pH responsiveness and is based on noble metal/metal oxygenThe compound enhances the properties of the photodynamic reaction. By controlling the molar ratio of Pt precursor solution to nonionic surfactant, MnO2The dosage of the metal salt precursor can creatively realize the aim of Pt/MnO2And (3) precisely regulating and controlling the size of the core-shell nano material. Pt/MnO of different sizes2The nuclear shell nano material has different light absorption performance in an ultraviolet-visible-near infrared region, and further can convert light energy into heat energy or active oxygen with a killing effect on cancer cells through photodynamic reaction. Therefore, by utilizing the illumination with specific wavelength and the loading of the medicine on the porous platinum core, the Pt/MnO provided by the scheme can be predicted2The nano material has great application prospect in photo-thermal, photodynamic and drug treatment of tumors.
Drawings
FIG. 1 shows Pt/MnO obtained in example 12Transmission electron microscopy of nanomaterials.
FIG. 2 is a diagram of Pt/MnO obtained in example 22Transmission electron microscopy of nanomaterials.
FIG. 3 is a diagram of Pt/MnO obtained in example 22Elemental profile of the nanomaterial.
FIG. 4 shows Pt/MnO obtained in example 32Transmission electron microscopy of nanomaterials.
Fig. 5 is a transmission electron micrograph of the Pt nanoparticles obtained in example 4.
FIG. 6 shows Pt/MnO obtained in example 42Transmission electron microscopy of nanomaterials.
Fig. 7 is a transmission electron micrograph of the Pt nanoparticles obtained in example 5.
FIG. 8 shows Pt/MnO obtained in example 52Transmission electron microscopy of nanomaterials.
Detailed Description
Example 1
Pt/MnO of this example2The preparation method of the nano material comprises the following steps:
the potassium chloroplatinite solution was mixed with the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer solution in a centrifuge tube, followed by addition of the ascorbic acid solution. ControlPreparing potassium chloroplatinite with the concentration of 5 mmol/L, simultaneously, the molar ratio of the potassium chloroplatinite to ascorbic acid is 1: 3, the concentration of polyoxyethylene ether is 100 g/L, reacting in a 200W ultrasonic cleaning machine for 1h, carrying out reduction reaction under the condition, centrifuging the product at the rotating speed of 10000r/min for 12min, removing supernatant, adding water for dispersing to obtain nano platinum particles, then taking 1mg of colloidal solution of the platinum nano particles, adding aqueous solution of manganese acetate to ensure that the concentration is 0.125 mmol/L, standing for 30min, adding sodium carbonate to the mixed solution under ultrasonic to ensure that the concentration is 1.2 mmol/L, ultrasonically treating the product for 30min, centrifuging at the rotating speed of 7000r/min for 10min, removing supernatant, adding water for dispersing to obtain Pt/MnO, and carrying out water dispersion to obtain Pt/MnO2Colloidal solution of core-shell nano material. The average size of the core-shell structure obtained in the example is 74nm, the average size of the inner core is 34nm, the average size of the outer shell is 20nm, and fig. 1 is a transmission electron microscope image of the product of the example.
Example 2
Example 2 comprises the following steps:
mixing a potassium chloroplatinite solution and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer solution in a centrifuge tube, adding an ascorbic acid solution, controlling the concentration of the potassium chloroplatinite to be 5 mmol/L, simultaneously controlling the molar ratio of the potassium chloroplatinite to the ascorbic acid to be 1: 3, controlling the concentration of polyoxyethylene ether to be 50 g/L, reacting for 1h in a 200W ultrasonic cleaning machine, carrying out reduction reaction under the condition, centrifuging the product at the rotating speed of 9000r/min for 10min, removing supernatant, adding water to disperse the product to obtain nano platinum particles, taking 1mg of colloidal solution of the platinum nano particles, adding an aqueous solution of manganese acetate to make the concentration of the manganese acetate to be 0.25 mmol/L, standing for 30min, adding sodium carbonate to the mixed solution under ultrasonic sound waves to make the concentration of the sodium carbonate to be 1.2 mmol/L, centrifuging the product at the rotating speed of 6500r/min for 10min, removing supernatant, adding water to disperse the product to obtain Pt/polypropylene oxide-polyethylene oxide triblock copolymer solution, and adding water to disperse the Pt/MnO to obtain Pt/polyethylene oxide2Colloidal solution of core-shell nano material. The average size of the core-shell structure obtained in the example is 124nm, the average size of the core is 45nm, the average size of the shell is 39nm, and fig. 2 is a transmission electron microscope image of the product of the example; FIG. 3 is an elemental distribution diagram of the product of this example, which shows that the product of this example uses Pt nanoparticles as the platinumInner core and coating MnO2And (4) a nano shell.
Example 3
Example 3 comprises the following steps:
mixing a potassium chloroplatinite solution and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer solution in a centrifuge tube, then adding an ascorbic acid solution, controlling the concentration of the potassium chloroplatinite to be 5 mmol/L, simultaneously controlling the molar ratio of the potassium chloroplatinite to the ascorbic acid to be 1: 3, controlling the concentration of polyoxyethylene ether to be 2 g/L, reacting for 1h in a 200W ultrasonic cleaning machine, carrying out reduction reaction under the condition, centrifuging the product for 10min at the rotation speed of 8000r/min, removing supernatant, adding water to disperse the product to obtain nano platinum particles, then taking 1mg of colloidal solution of the platinum nano particles, adding an aqueous solution of manganese acetate to ensure the concentration to be 0.25 mmol/L, standing for 30min, adding sodium carbonate to the mixed solution under ultrasound to ensure the concentration to be 1.2 mmol/L, centrifuging the product for 30min at the rotation speed of 5500r/min, removing the supernatant, adding water to disperse the product to obtain Pt/MnO2Colloidal solution of core-shell nano material. The average size of the core-shell structure obtained in the example is 123nm, the average size of the core is 53nm, the average size of the shell is 35nm, and fig. 4 is a transmission electron microscope image of the product of the example.
Example 4
Example 4 comprises the following steps:
mixing a potassium chloroplatinite solution and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer solution in a centrifuge tube, then adding an ascorbic acid solution, controlling the concentration of the potassium chloroplatinite to be 0.6 mmol/L, simultaneously controlling the molar ratio of the potassium chloroplatinite to the ascorbic acid to be 1: 6, controlling the concentration of polyoxyethylene ether to be 100 g/L, reacting in a 200W ultrasonic cleaning machine for 1h, carrying out reduction reaction under the condition, centrifuging the product at the rotating speed of 10000r/min for 10min, removing supernatant, adding water to disperse to obtain nano platinum particles, then taking a colloidal solution of 1mg of the platinum nano particles, adding an aqueous solution of manganese acetate to make the concentration of 0.125 mmol/L, standing for 30min, adding sodium carbonate into the mixed solution under ultrasonic sound waves to make the concentration of 1.2 mmol/L, centrifuging the product at the rotating speed of 7000r/min for 10min, removing the productRemoving supernatant, adding water and dispersing to obtain Pt/MnO2Colloidal solution of core-shell nano material. The average size of the core-shell structure obtained in the example is 61nm, the average size of the inner core is 21nm, the average size of the outer shell is 20nm, fig. 5 is a transmission electron microscope image of the Pt nanoparticles in the example, and fig. 6 is a transmission electron microscope image of the product in the example.
Example 5
Example 5 includes the following steps:
mixing a potassium chloroplatinite solution and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer solution in a centrifuge tube, adding an ascorbic acid solution, controlling the concentration of the potassium chloroplatinite to be 0.8 mmol/L, simultaneously controlling the molar ratio of the potassium chloroplatinite to the ascorbic acid to be 1: 6, controlling the concentration of polyoxyethylene ether to be 100 g/L, reacting in a 200W ultrasonic cleaning machine for 1h, carrying out reduction reaction under the condition, centrifuging the product at the rotating speed of 9000r/min for 10min, removing supernatant, adding water to disperse the product to obtain nano platinum particles, taking a colloidal solution of 1mg of platinum nanoparticles, adding an aqueous solution of manganese acetate to make the concentration of 0.25 mmol/L, standing for 30min, adding sodium carbonate to the mixed solution under ultrasonic to make the concentration of 1.2 mmol/L, centrifuging the product at the rotating speed of 6500r/min to remove supernatant, adding MnO to disperse the product to obtain Pt/polypropylene oxide2Colloidal solution of core-shell nano material. The average size of the core-shell structure obtained in this example is 100nm, the average size of the core is 30nm, the average size of the shell is 35nm, fig. 7 is a transmission electron microscope image of the Pt nanoparticles in this example, and fig. 8 is a transmission electron microscope image of the product of this example.
Example 6
Example 6 includes the following steps:
the procedure is as in example 4, the concentration of potassium chloroplatinite is changed to 0.4 mmol/L, the average size of the core-shell structure obtained in this example is 58nm, the average size of the core is 18nm, and the average size of the shell is 20 nm.
Example 7
Example 7 includes the following steps:
the procedure is as in example 5, the concentration of potassium chloroplatinite is changed to 0.4 mmol/L, the average size of the core-shell structure obtained in this example is 88nm, the average size of the core is 18nm, and the average size of the shell is 35 nm.
Example 8
Example 8 includes the following steps:
the procedure is as in example 4, the concentration of potassium chloroplatinite is changed to 0.7 mmol/L, the average size of the core-shell structure obtained in this example is 65nm, the average size of the core is 25nm, and the average size of the shell is 20 nm.
Example 9
Example 9 includes the following steps:
the procedure is as in example 5, the concentration of potassium chloroplatinite is changed to 0.7 mmol/L, the average size of the core-shell structure obtained in this example is 95nm, the average size of the core is 25nm, and the average size of the shell is 35 nm.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (6)
1. Size-controllable Pt/MnO2The preparation method of the nano material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing a non-ionic surfactant with a platinum precursor solution, adding a reducing agent, and reacting under the conditions of ultrasound and room temperature to obtain a colloidal solution of porous platinum nanoparticles;
the nonionic surfactant is polyoxyethylene lauryl ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene stearate, polyethylene glycol cetyl ether or polyoxyethylene lauryl ether;
the platinum precursor is chloroplatinic acid, potassium chloroplatinite or potassium chloroplatinate;
the reducing agent is sodium borohydride, ascorbic acid, glucose or sodium citrate;
wherein the molar ratio of the platinum precursor to the reducing agent is 1: 1-10;
2) adding into the colloidal solution of the platinum nanoparticlesInto MnO2Obtaining a second mixed solution from the aqueous solution of the metal salt precursor of the manganese dioxide, and standing for reaction; then adding alkali liquor to adjust the pH value of the second mixed solution to 8-14, carrying out ultrasonic reaction, and centrifugally separating the reaction solution to obtain MnO with porous Pt nano particles as an inner core2Is a core-shell structure material of the shell.
2. A size-controllable Pt/MnO according to claim 12The preparation method of the nano material is characterized in that the concentration of a platinum precursor in the first mixed solution is 0.1-10 mmol/L, and the concentration of the nonionic surfactant is 1-100 g/L.
3. A size-controllable Pt/MnO according to claim 12The preparation method of the nano material is characterized in that the concentration of manganese acetate in the second mixed solution is 0.1-0.3 mmol/L.
4. A size-controllable Pt/MnO according to claim 12The preparation method of the nano material is characterized by comprising the following steps: and in the step 2), adding an alkali liquor to adjust the pH value of the second mixed solution, wherein the alkali liquor is one of ammonia water, sodium hydroxide, sodium carbonate, sodium bicarbonate, disodium hydrogen phosphate and urea.
5. A size-controllable Pt/MnO according to claim 12The preparation method of the nano material is characterized by comprising the following steps: the MnO2The metal salt precursor of (a) includes manganese acetate.
6. A size-controlled Pt/MnO prepared by the method of any one of claims 1 to 52Nanomaterial characterized by: the core-shell structure material has an inner core of porous Pt nano particles and MnO2Wherein the Pt nano core has a diameter of 20-100 nm, a pore size of 1-10 nm, and MnO2The thickness of the shell layer is 20-50 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010403199.8A CN111496268A (en) | 2020-05-13 | 2020-05-13 | Size-controllable Pt/MnO2Nano material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010403199.8A CN111496268A (en) | 2020-05-13 | 2020-05-13 | Size-controllable Pt/MnO2Nano material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111496268A true CN111496268A (en) | 2020-08-07 |
Family
ID=71878450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010403199.8A Pending CN111496268A (en) | 2020-05-13 | 2020-05-13 | Size-controllable Pt/MnO2Nano material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111496268A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523418A (en) * | 1978-07-27 | 1980-02-19 | Yokogawa Hokushin Electric Corp | Measuring instrument for total amount of carbon in liquid sample |
| CN105092843A (en) * | 2015-07-03 | 2015-11-25 | 济南大学 | Preparation method and application of Pt-manganese dioxide/ferroferric oxide pancreatic cancer marker biosensor |
| US20180229299A1 (en) * | 2017-02-15 | 2018-08-16 | The Board Of Trustees Of The University Of Arkansas | Copper-silica core-shell nanoparticles and methods |
| CN108816225A (en) * | 2018-07-02 | 2018-11-16 | 大连理工大学 | Fabricated in situ Pt/MnO for VOCs catalysis burning2@Mn3O4Catalyst, preparation method and applications |
| CN109079130A (en) * | 2018-07-19 | 2018-12-25 | 华侨大学 | A kind of preparation method of the adjustable yolk-eggshell structural porous composite material of partial size of platinum nano inner core cerium dioxide nano shell |
| WO2019136822A1 (en) * | 2018-01-11 | 2019-07-18 | 苏州大学 | Core-shell type gold-ruthenium oxide nano-composite material and preparation method therefor |
-
2020
- 2020-05-13 CN CN202010403199.8A patent/CN111496268A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523418A (en) * | 1978-07-27 | 1980-02-19 | Yokogawa Hokushin Electric Corp | Measuring instrument for total amount of carbon in liquid sample |
| CN105092843A (en) * | 2015-07-03 | 2015-11-25 | 济南大学 | Preparation method and application of Pt-manganese dioxide/ferroferric oxide pancreatic cancer marker biosensor |
| US20180229299A1 (en) * | 2017-02-15 | 2018-08-16 | The Board Of Trustees Of The University Of Arkansas | Copper-silica core-shell nanoparticles and methods |
| WO2019136822A1 (en) * | 2018-01-11 | 2019-07-18 | 苏州大学 | Core-shell type gold-ruthenium oxide nano-composite material and preparation method therefor |
| CN108816225A (en) * | 2018-07-02 | 2018-11-16 | 大连理工大学 | Fabricated in situ Pt/MnO for VOCs catalysis burning2@Mn3O4Catalyst, preparation method and applications |
| CN109079130A (en) * | 2018-07-19 | 2018-12-25 | 华侨大学 | A kind of preparation method of the adjustable yolk-eggshell structural porous composite material of partial size of platinum nano inner core cerium dioxide nano shell |
Non-Patent Citations (2)
| Title |
|---|
| GUANGBAO YANG等: "Hollow MnO2 as a tumor-microenvironment-responsive biodegradable nano-platform for combination therapy favoring antitumor immune responses", 《NATURE COMMUNICATIONS》 * |
| NINA JIANG等: "(Metal yolk)/(porous ceria shell) nanostructures for high-performance plasmonic photocatalysis under visible light", 《NANO RESEARCH》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Synthesis, structures and applications of single component core-shell structured TiO2: a review | |
| CN106493381B (en) | A kind of preparation method and applications of silver/cuprous oxide micro-nano structure composite | |
| Chen et al. | Doping nano-Co3O4 surface with bigger nanosized Ag and its photocatalytic properties for visible light photodegradation of organic dyes | |
| CN106345459A (en) | Preparation method of composite microsphere | |
| US9415442B2 (en) | Stable oxide encapsulated metal clusters and nanoparticles | |
| CN104525937B (en) | A kind of porous silver micro nano structure and pattern thereof and the controlled preparation method of size | |
| Smrithi et al. | Carbon dots decorated cadmium sulphide heterojunction-nanospheres for the enhanced visible light driven photocatalytic dye degradation and hydrogen generation | |
| CN104550998A (en) | Preparation method of golden hollow ball/cuprous copper nanometer core-shell structure | |
| CN105806911B (en) | A kind of ZnO Au@CdS photoelectricity composite materials and its preparation method and application | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN104607185A (en) | Monodispersed spherical titanium dioxide core-shell structure composite material and preparation method thereof | |
| CN106000474B (en) | A kind of porphyrin/titanium dioxide uniformly organizes the preparation method and applications of nanosphere altogether | |
| AU2021102201A4 (en) | Polydopamine-platinum granular nanomaterial doped with moo2 and preparation method thereof | |
| KR20130020897A (en) | Tungsten oxide photocatalyst and method for producing the same | |
| Ye et al. | SiO2/TiO2/Ag multilayered microspheres: Preparation, characterization, and enhanced infrared radiation property | |
| CN105834448B (en) | One-step method prepares Ag@TiO2Nanocomposite | |
| CN107694561A (en) | A kind of support type disperses noble metal quantum site catalyst and preparation method thereof | |
| CN110240125B (en) | Hollow zinc selenide nanocrystal and preparation method and application thereof | |
| CN107497455B (en) | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification | |
| Liu et al. | Ag/black phosphorus composite based on multilayer black phosphorus: Its preparation and photocatalytic methyl orange degradation performance | |
| CN106075470B (en) | The application of gold-nano-piece synthetic method and gold-nano-piece in terms of breast cancer diagnosis and treatment | |
| CN105749908B (en) | A kind of Au@TiO2Hollow core-shell structure photochemical catalyst and preparation method thereof | |
| CN104458705B (en) | Preparing method of surface enhancing Raman chip | |
| CN113118432B (en) | Noble metal nano particle and preparation method and application thereof | |
| CN109079130B (en) | Preparation method of particle size-adjustable yolk-eggshell structure porous composite material with platinum nano-core cerium dioxide nano-shell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200807 |
|
| WD01 | Invention patent application deemed withdrawn after publication |