CN110455771A - A kind of composite nano materials and its preparation method and application - Google Patents
A kind of composite nano materials and its preparation method and application Download PDFInfo
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- CN110455771A CN110455771A CN201910743129.4A CN201910743129A CN110455771A CN 110455771 A CN110455771 A CN 110455771A CN 201910743129 A CN201910743129 A CN 201910743129A CN 110455771 A CN110455771 A CN 110455771A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention discloses one kind, and SERS substrate can be made with composite nano materials of more preferable sensitivity and its preparation method and application, surface enhanced Raman scattering substrate, detection device and detection method.The composite nano materials include two-dimentional MXene nanometer sheet and the one-dimensional metal nano material that is adsorbed in two-dimentional MXene nanometer sheet.The nano material passes through suction-operated, by 1-dimention nano metal material uniform load in two-dimensional nano on piece, its high reference area and physico-chemical property can generate more hot spot after load, achieve the purpose that enhance SERS signal, with sensitive Raman detection performance, the content of pesticide residue can be quickly detected, and 10 can be reached to the detectable limit of pesticide‑10mol/L.The detection of composite nano materials prepared by the present invention has good detection reproducibility as Raman substrate, can be widely applied to the detection of other organic pollutants such as food additives etc..
Description
Technical field
The present invention relates to technical field of composite materials, more particularly, to a kind of composite nano materials and preparation method thereof and answer
With.
Background technique
Pesticide plays an important role in agricultural development as important capital goods in the agricultural sector.However pesticide does not conform to
Reason uses and Use out of range, causes Residual Pesticides in Farm Produce exceeded, seriously threatens human health.In recent years, cereal crops agriculture
Medicine is exceeded to be refused that outlet, the exceeded poisoning of food pesticide, pesticide too high levels lead to not causing for phenomena such as drinking in water
Social extensive concern.The food of edible excessive pesticide residues, can cause the slow poisoning of humans and animals, lead to the hair of disease
It is raw, cancer is induced, or even influence the next generation.Therefore agricultural product quality and safety is ensured, to terminal Residual Pesticides in Farm Produce
It detects most important.
Current conventional Pesticides Testing method mainly has physics, chemistry and biological detection three categories method.Physical detection
Method includes chromatography and spectrum analysis, and chemical detection is then reagent reaction detection method, and biological detecting method type is more, often
That sees has: enzyme inhibition analysis, Enzyme-linked Immunosorbent Assay technology, biosensor etc..However conventional pesticide residue detection method at
This height, detection time is long, and pesticide residue content is often trace, so detection gets up to be not easy to.Specifically, chromatography
Gas-chromatography and liquid chromatography technology in technology there are high cost, time-consuming, high operation requirements and is unable to on-site test etc. no
Foot then early has been unable to meet the requirement of pesticide trace analysis by the chemical method that more reagents react.Enzyme inhibition analysis method conduct
Common method in bioassay method, although the factor that with half-quantitative detection, can influence result accuracy is more, and due to
Reaction mechanism, which limits, can only detect organophosphate and carbamate pesticide.So researching and developing one kind is applicable to detection food
Quick, sensitive, easy, the economic detection method of pesticide residue in product has very big value and realistic meaning.
Uniqueness of Surface enhanced Raman scattering (SERS) technology because of its hypersensitive discriminance analysis object molecular vibration having
Ability becomes one of representative technology of current spectral analysis technique.Since it can be with non-demolition feature, surface with high sensitivity
Enhancing Raman scattering techniques provide a kind of strong method for the trace level detection of analyte, and are widely used in environment
The fields such as monitoring, explosive detection, Homeland Security and biomedical science.In addition, it is to various pesticides and unimolecule pesticide
Detection has fabulous sensitivity, promotes its application as the substitution detection technique of quick Pesticides Testing.Surface enhanced is drawn
Graceful scattering can obtain highly sensitive signal on low concentration test substance, and the precondition for obtaining high quality Raman signal is
The quality of SERS active-substrate.Current major part SERS substrate is derived from pure noble metal nano particles (such as gold, silver nano particle), but
Its higher cost is especially low to the pesticide molecule detection sensitivity with complicated ingredient.Therefore, it is necessary to which providing one kind can make
SERS substrate has the composite nano materials of more preferable sensitivity.
Summary of the invention
The technical problem to be solved by the present invention is to how provide one kind SERS substrate can be made to have more preferable sensitivity
Composite nano materials and its preparation method and application, using the composite nano materials SERS substrate, use the composite Nano material
The detection device and detection method of material.
According to the first aspect of the invention, the present invention provides a kind of composite nano materials, according to an embodiment of the invention,
The composite nano materials include two-dimentional MXene nanometer sheet and the one-dimensional metal nano material that is adsorbed in two-dimentional MXene nanometer sheet.
Wherein, MXene material is a kind of two-dimentional transition metal carbide or carbonitride, has class graphene-structured,
Chemical formula is Mn+1XnTx, M can be the transition metal element for including but are not limited to Ti, V, Cr etc., and X is C and/or N, n
It is any one of 1,2,3, TxIt is then surface functional group, such as includes but are not limited to O, OH, F, Cl, NH2Equal functional groups.
The beneficial effects of the present invention are:
The present invention provides a kind of composite nano materials based on two-dimensional nano piece and one-dimensional metal nano material, this nanometer of material
Material is by suction-operated, by 1-dimention nano metal material uniform load in two-dimensional nano on piece, high reference area and object
More hot spot can be generated after load by changing property, achieve the purpose that enhance SERS signal, have sensitive Raman detection performance,
The content of pesticide residue can be quickly detected, and 10 can be reached to the detectable limit of pesticide-10mol/L.It is answered prepared by the present invention
Nano material detection, which is closed, as Raman substrate has good detection reproducibility, can be widely applied to other organic pollutants as eaten
The detection of product additive etc..
According to an embodiment of the invention, two dimension MXene nanometer sheet is Ti3C2TxNanometer sheet.
According to an embodiment of the invention, the length of two dimension MXene nanometer sheet is 300nm~500nm, it is MXene nanometers two-dimentional
Piece with a thickness of 3nm~6nm.
According to an embodiment of the invention, one-dimensional metal nano material in gold, silver, copper, nickel, platinum, palladium, aluminium at least one
Kind.
According to an embodiment of the invention, one-dimensional metal nano material includes but are not limited to be one-dimensional metal nanometer rods, one
Tie up metal nanometer line.
According to an embodiment of the invention, the length of one-dimensional metal nano material is 30nm~50nm, one-dimensional metal nanometer material
The diameter of material is 8nm~10nm.
According to the second aspect of the invention, the present invention provides a kind of preparation method of composite nano materials, according to this hair
Bright embodiment, the preparation methods of the composite nano materials the following steps are included:
Take the solution of two-dimentional MXene nanometer sheet to mix with the solution of one-dimensional metal nano material, ultrasound to obtain the final product.
According to an embodiment of the invention, the preparation of two dimension MXene nanometer sheet specifically uses following methods:
Under anaerobic, multilayer MXene powder is taken, multilayer MXene powder is dispersed in the first organic solvent, is obtained
Concentration is the dispersion liquid of 0.5mg/mL~1.0mg/mL, and dispersion liquid is first carried out Probe Ultrasonic Searching in the case where power is 700W~1400W
5h~10h then carries out water bath sonicator 6h~12h in the case where power is 200W~400W, after ultrasonic, 3000rpm~
4000rpm be centrifuged 5min~15min, collect supernatant, obtain two-dimentional MXene nanometer sheet, and then again 8000rpm~
After 12000rpm is centrifuged 10min, takes precipitating to be dispersed in 0.5mL~2mL water, obtain two-dimensional metallic nanometer sheet aqueous solution.
According to an embodiment of the invention, the partial size of multilayer MXene powder is 5 μm~10 μm.
According to an embodiment of the invention, the first organic solvent is selected from N-Methyl pyrrolidone, dimethylformamide, dimethyl
One of sulfoxide, acetone, tetrahydrofuran, dehydrated alcohol are a variety of.
According to an embodiment of the invention, the first organic solvent is N-Methyl pyrrolidone.
According to an embodiment of the invention, preparing one-dimensional metal nano material using one-step synthesis.
According to an embodiment of the invention, one-dimensional metal nano material is metal bar, the step of synthetic method, includes:
At room temperature, by concentration be 0.003mol/L~0.008mol/L chlorauric acid solution, concentration 0.1mol/
Enuatrol that the cetyltriethylammonium bromide of L~0.3mol/L, concentration are 0.05mol/L~0.2mol/L, concentration are
The aqueous solution of the silver nitrate of 0.002mol/L~0.006mol/L, the concentrated hydrochloric acid that concentration is 35%~37% and 30mL~60mL
The ascorbic acid of 0.05mol/L~0.2mol/L is then added, when mixed solution becomes in uniformly mixing into above-mentioned mixed solution
After colourless, the sodium borohydride aqueous solution of 0.005mol/L~0.02mol/L is added thereto, which stands at 35 DEG C
2h~6h is reacted, finally obtains gold nanorods, Centrifugal dispersion is in 5mL~20mL water.
According to an embodiment of the invention, the revolving speed being arranged when centrifugation is 10000~13000rpm/min, centrifugation time 10
~30min.
According to an embodiment of the invention, taking the one of the solution of the two-dimentional MXene nanometer sheet of 0.5mL~2mL and 2mL~8mL
In the solution of Vygen metal nanometer material, water bath sonicator obtains composite nano materials.
According to an embodiment of the invention, the ultrasonic time of water bath sonicator is 30min~60min.
According to an embodiment of the invention, composite nano materials are finally dispersed in the 250 μ L aqueous solutions of μ L~1000.
According to an embodiment of the invention, composite nano materials are finally dispersed in 500 μ L aqueous solutions.
The preparation method of composite nano materials provided by the present invention is simple, and reaction condition is mildly controllable.
According to the third aspect of the present invention, it is scattered in surface-enhanced Raman to provide a kind of above-mentioned composite nano materials by the present invention
The application hit.
According to the fourth aspect of the present invention, the present invention provides a kind of surface enhanced Raman scattering substrate, according to the present invention
Embodiment, the surface enhanced Raman scattering substrate, including above-mentioned composite nano materials.The surface enhanced Raman scattering substrate
Non-limiting example be ITO electro-conductive glass substrate be coated in substrate on above-mentioned composite nano materials.
According to the fifth aspect of the present invention, the present invention provides a kind of detection device, according to an embodiment of the invention, the inspection
Surveying device includes above-mentioned composite nano materials or surface enhanced Raman scattering substrate.Detection device includes but are not limited to miniflow
Control detection device, micro fluid control detection device are covered with above-mentioned composite nano materials and the SERS substrate that is formed on substrate.
According to the sixth aspect of the invention, the present invention provides a kind of detection method, according to an embodiment of the invention, the inspection
Survey method, comprising the following steps:
Sample to be tested liquid is contacted with above-mentioned composite nano materials or above-mentioned surface enhanced Raman scattering substrate, to
Sample to be tested liquid carries out Raman test after being evaporated.
According to an embodiment of the invention, sample to be tested liquid is remains of pesticide sample, the i.e. solution containing trace pesticide.Tool
Body, the type of trace pesticide can be at least one of thiram, diquat dibromide, isocarbophos.
According to an embodiment of the invention, the detection method is using composite nano materials as SERS substrate, testing molecule conduct
Raman microprobe molecule, comprising the following steps:
The aqueous solution of 2.5 μ L composite nano materials is added dropwise on clean silicon wafer, and control group is set, experimental group continues to drip
The concentration for adding equivalent is about 10-10Mol/L~10-6The sample to be tested liquid of mol/L, naturally dry；It is detected using Raman spectrometer
The characteristic signal of testing molecule and data collection and processing are carried out in composite nano materials on silicon wafer.According to the common sense of this field,
It can be using including but are not limited to method that pre-rendered corresponding standard curve is tested again come dense in sample survey
Degree.It include identical testing molecule in standard solution used in standard curve and sample to be tested liquid.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture of the two-dimentional MXene nanometer sheet of one embodiment of the present of invention.
Fig. 2 is the gold nanorods transmission electron microscope picture of one embodiment of the present of invention.
Fig. 3 is the composite nano materials scanning electron microscopic picture of one embodiment of the present of invention.
Fig. 4 is detection of the composite nano materials of one embodiment of the present of invention for various concentration thiram pesticide molecule
Raman signal figure.
Specific embodiment
It is carried out below with reference to technical effect of the embodiment to design of the invention, specific structure and generation clear, complete
Ground description, to be completely understood by the purpose of the present invention, feature and effect.Obviously, described embodiment is of the invention one
Section Example, rather than whole embodiments, based on the embodiment of the present invention, those skilled in the art are not paying creativeness
Other embodiments obtained, belong to the scope of protection of the invention under the premise of labour.
Embodiment 1
A kind of composite nano materials, it is compound by electrostatic adsorption with one-dimensional gold nanorods by two-dimentional MXene nanometer sheet
It forms.
The preparation method of the composite nano materials, comprising the following steps:
(1) preparation of two dimension MXene nanometer sheet:
Under anaerobic, multilayer MXene powder is taken, multilayer MXene powder is dispersed in N-Methyl pyrrolidone, is obtained
Dispersion liquid is first carried out Probe Ultrasonic Searching 10h in the case where power is 1000W, then in power by the dispersion liquid for being 1.0mg/mL to concentration
To carry out water bath sonicator 10h under 300W, after ultrasonic, 3500rpm/10min centrifugation collects supernatant, obtains two-dimentional MXene
And then precipitating is dispersed in 1mL water after 10000rpm/10min centrifugation by nanometer sheet again.
(2) preparation of one-dimensional gold nanorods:
Using one-step synthesis method gold nanorods.At room temperature, the chlorauric acid solution, dense for being 0.005mol/L by concentration
Spending the cetyltriethylammonium bromide for being 0.2mol/L, the enuatrol that concentration is 0.1mol/L, concentration is 0.004mol/L's
The aqueous solution of silver nitrate, the concentrated hydrochloric acid that concentration is 36% and 45mL uniformly mixes, and is then added into above-mentioned mixed solution
The sodium borohydride aqueous solution of 0.01mol/L is added after mixed solution becomes colorless in the ascorbic acid of 0.1mol/L thereto,
The mixed solution stands reaction 4h at 35 DEG C, finally obtains gold nanorods, Centrifugal dispersion is in 10mL water.
(3) preparation of composite nano materials:
Gained two dimension MXene nanometer sheet aqueous solution in 1mL step (1) is taken, is added to one-dimensional obtained in 4mL step (2)
In gold nanorods aqueous solution.Said mixture is placed in in water bath sonicator machine ultrasound after evenly mixing to get to composite Nano material
Material.
A kind of detection method of pesticide molecule thiram, includes the following steps:
(1) 6 silicon wafers cleaned up are taken, are laid on glass slide；
(2) solution of the 2.5 above-mentioned composite nano materials of μ L is added dropwise on above-mentioned 6 silicon wafers, leaves and takes wherein a piece of conduct pair
According to the concentration that remaining silicon wafer continues that equivalent is added dropwise respectively is 10-10Mol/L~10-6The thiram standard solution of mol/L, dries in the air naturally
It is dry；
(3) characteristic signal of thiram pesticide molecule in composite nano materials is detected using Raman spectrometer and carry out data
Collecting and dealing.
1 gained composite nano materials of the present embodiment are characterized, as a result as shown in FIG. 1 to 3, wherein Fig. 1 is this hair
The scanning electron microscopic picture of the two-dimentional MXene nanometer sheet of bright one embodiment.As shown in Figure 1, the two-dimentional MXene nanometer sheet of preparation
With relatively thin two-dimensional structure.Fig. 2 is the gold nanorods transmission electron microscope picture of one embodiment of the present of invention.As shown in Fig. 2, system
The one-dimensional gold nanorods obtained have relatively uniform size.Fig. 3 is that the composite nano materials of one embodiment of the present of invention scan
Electron microscopic picture.As shown in figure 3, one-dimensional gold nanorods are uniformly adsorbed on two-dimentional MXene nanometer sheet surface.Fig. 4 is of the invention
Detection Raman signal figure of the composite nano materials of one embodiment for various concentration thiram pesticide molecule.As shown in figure 4,
The concentration that 5 curves from top to bottom respectively represent thiram is 10-6mol/L、10-7mol/L、10-8mol/L、10-9mol/L、
10-10mol/L.It can be seen from figure 4 that even if in low concentration 10-10It is still blissful under the conditions of mol/L (i.e. bottom curve)
The characteristic signal of U.S. bimolecular, the result demonstrate composite nano materials provided by the present invention may be implemented to thiram down to
10-10The detection limit of mol/L.Other pesticides or molecule to be checked are also similarly.
Embodiment 2
A kind of preparation method of the composite nano materials for pesticide trace detection, comprising the following steps:
(1) preparation of two dimension MXene nanometer sheet:
Under anaerobic, multilayer MXene powder is taken, multilayer MXene powder is dispersed in the first organic solvent, is obtained
Concentration is the dispersion liquid of 0.5mg/mL, the dispersion liquid is first carried out Probe Ultrasonic Searching 8h in the case where power is 700W, then in power
To carry out water bath sonicator 8h under 400W, after ultrasonic, 3500rpm/10min centrifugation collects supernatant, obtains two-dimentional MXene
And then precipitating is dispersed in 0.5mL water after 10000rpm/10min centrifugation by nanometer sheet again.
(2) preparation of one-dimensional gold nanorods:
Using one-step synthesis method gold nanorods.At room temperature, the chlorauric acid solution, dense for being 0.004mol/L by concentration
Spending the cetyltriethylammonium bromide for being 0.1mol/L, the enuatrol that concentration is 0.2mol/L, concentration is 0.003mol/L's
The aqueous solution of silver nitrate, the concentrated hydrochloric acid that concentration is 35% and 35mL uniformly mixes, and is then added into above-mentioned mixed solution
The ascorbic acid of 0.05mol/L, after mixed solution becomes colorless, the sodium borohydride that 0.005mol/L is added thereto is water-soluble
Liquid, the mixed solution stand reaction 6h at 35 DEG C, finally obtain gold nanorods, Centrifugal dispersion is in 5mL water.
(3) preparation of composite nano materials:
Gained two dimension MXene nanometer sheet aqueous solution in 0.5mL step (1) is taken, is added to one obtained in 2mL step (2)
In Vygen nanometer rods aqueous solution.Said mixture is placed in water bath sonicator machine ultrasound after evenly mixing to get to composite Nano material
Material.
A kind of detection method of pesticide molecule diquat dibromide, includes the following steps:
(1) 5 silicon wafers cleaned up are taken, are laid on glass slide；
(2) 2.5 μ L composite nano materials are added dropwise on Xiang Shangshu silicon wafer, wherein leaving and taking a piece of as control, remaining dropwise addition
The concentration that the silicon wafer of composite nano materials continues that equivalent is respectively added dropwise is 10-10Mol/L~10-6The pesticide standard of mol/L is molten
Liquid, naturally dry；
(3) using Raman spectrometer detection composite nano materials in pesticide molecule characteristic signal and carry out data collection and
Processing.
Embodiment 3
A kind of preparation method of the composite nano materials for pesticide trace detection, comprising the following steps:
(1) preparation of two dimension MXene nanometer sheet:
Under anaerobic, multilayer MXene powder is taken, multilayer MXene powder is dispersed in the first organic solvent, is obtained
Concentration is the dispersion liquid of 0.75mg/mL, the dispersion liquid is first carried out Probe Ultrasonic Searching 5h in the case where power is 1400W, then in function
Rate is that water bath sonicator 6h is carried out under 200W, and after ultrasound, 3500rpm/10min centrifugation collects supernatant, obtains two dimension
And then precipitating is dispersed in 2mL water after 10000rpm/10min centrifugation by MXene nanometer sheet again.
(2) preparation of one-dimensional gold nanorods:
Using one-step synthesis method gold nanorods.At room temperature, the chlorauric acid solution, dense for being 0.004mol/L by concentration
Spend the cetyltriethylammonium bromide for being 0.25mol/L, the enuatrol that concentration is 0.15mol/L, concentration 0.005mol/L
Silver nitrate, the concentrated hydrochloric acid that concentration is 36% and the aqueous solution of 50mL uniformly mix, be then added into above-mentioned mixed solution
The ascorbic acid of 0.15mol/L, after mixed solution becomes colorless, the sodium borohydride that 0.015mol/L is added thereto is water-soluble
Liquid, the mixed solution stand reaction 3h at 35 DEG C, finally obtain one-dimensional gold nanorods, Centrifugal dispersion is in 20mL water.
(3) preparation of composite nano materials:
Gained two dimension MXene nanometer sheet aqueous solution in 2mL step (1) is taken, Jenner obtained in 8mL step (2) is added to
In rice stick aqueous solution.Said mixture is placed in water bath sonicator machine ultrasound after evenly mixing to get to composite nano materials.
Embodiment 4
A kind of composite nano materials, the difference from embodiment 1 is that, including two-dimentional MXene nanometer sheet and it is adsorbed on two dimension
One-dimensional silver nanowires in MXene nanometer sheet.
Embodiment 5
A kind of pesticide trace detection micro-fluidic device, including SERS substrate, SERS substrate use the raw material including embodiment 4
It is made.
Embodiment 6
A kind of composite nano materials, the difference from embodiment 1 is that, two-dimentional MXene nanometer sheet is Cr2CTxNanometer sheet,
In, TxFor surface functional group as hereinbefore, for example, it may be O, OH, F, Cl, NH2。
Embodiment 7
A kind of composite nano materials, the difference from embodiment 1 is that, two-dimentional MXene nanometer sheet is Ti2CTxNanometer sheet,
In, TxFor surface functional group as hereinbefore, for example, it may be O, OH, F, Cl, NH2。
It is to be illustrated to presently preferred embodiments of the present invention, but the present invention is not limited to the embodiment above,
Those skilled in the art can also make various equivalent deformation or replacement on the premise of without prejudice to spirit of the invention, this
Equivalent deformation or replacement are all included in the scope defined by the claims of the present application a bit.
Claims (10)
1. a kind of composite nano materials, which is characterized in that including two-dimentional MXene nanometer sheet and be adsorbed on the two dimension MXene and receive
The one-dimensional metal nano material of rice on piece.
2. composite nano materials according to claim 1, which is characterized in that the two dimension MXene nanometer sheet is Ti3C2Tx
Nanometer sheet.
3. composite nano materials according to claim 1, which is characterized in that the length of the two dimension MXene nanometer sheet is
300nm~500nm, the two dimension MXene nanometer sheet with a thickness of 3nm~6nm.
4. composite nano materials according to claim 1, which is characterized in that the one-dimensional metal nano material be selected from gold,
At least one of silver, copper, nickel, platinum, palladium, aluminium.
5. composite nano materials according to claim 1, which is characterized in that the length of the one-dimensional metal nano material is
30nm~50nm, the diameter of the one-dimensional metal nano material are 8nm~10nm.
6. the preparation method of the described in any item composite nano materials of Claims 1 to 5, which comprises the following steps:
Take the solution of two-dimentional MXene nanometer sheet to mix with the solution of one-dimensional metal nano material, ultrasound to obtain the final product.
7. application of the described in any item composite nano materials of Claims 1 to 5 in Surface enhanced Raman scattering.
8. a kind of surface enhanced Raman scattering substrate, which is characterized in that compound receive including Claims 1 to 5 is described in any item
Rice material.
9. a kind of detection device, which is characterized in that including composite nano materials described in Claims 1 to 5, claim 8 institute
Any one of surface enhanced Raman scattering substrate stated.
10. a kind of detection method, which comprises the following steps:
Composite nano materials described in sample to be tested liquid and Claims 1 to 5, surface enhanced according to any one of claims 8 are drawn
The contact of any one of graceful scattering substrate, carries out Raman test after the sample to be tested liquid is evaporated.
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| CN111007055A (en) * | 2019-12-04 | 2020-04-14 | 浙江亚通焊材有限公司 | Ti3C2TxPreparation process of/Ag nano composite material and application of Ag nano composite material as Raman substrate material |
| CN111545229A (en) * | 2020-04-20 | 2020-08-18 | 北京邮电大学 | Method for preparing MXene supported noble metal catalyst by ultrasonic-assisted method |
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