CN111659899A - Flower-like palladium oxide-gold nano composite material and preparation method and application thereof - Google Patents
Flower-like palladium oxide-gold nano composite material and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 84
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 67
- 239000010931 gold Substances 0.000 title claims abstract description 50
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 27
- 238000000034 method Methods 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 14
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 9
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 6
- 239000012498 ultrapure water Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 14
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910003445 palladium oxide Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001239 high-resolution electron microscopy Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000002651 drug therapy Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 gold ions Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention discloses a synthesis method of a flower-shaped palladium oxide-gold nano composite material, which comprises the following steps: (1) selecting N, N-dimethylformamide, Pd (acac)2Uniformly mixing citric acid, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone to obtain orange red liquid; (2) adding tungsten hexacarbonyl into the orange-red liquid, and adjusting the temperature in an argon atmosphere to perform stirring reaction to obtain blue hexagonal palladium nanosheets; (3) by mixing acetone and ethanolPurifying the blue hexagonal palladium nanosheets by using a solvent to obtain purified palladium; (4) dissolving the purified palladium in ultrapure water to obtain a palladium nano solution, and stirring and reacting the palladium nano solution and chloroauric acid to obtain the flower-like palladium oxide-gold nano composite material. Also discloses a flower-shaped palladium oxide-gold nano composite material synthesized by the method, application of the composite material as an active substrate in surface-enhanced Raman scattering and application in the aspect of photothermal effect.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a flower-shaped palladium oxide-gold nano composite material as well as a preparation method and application thereof.
Background
Metal Nanoparticles (NPs) can be widely used in various fields of application, and thus have been a hot point of research. For example, due to their efficient interaction with light, including Localized Surface Plasmon Resonances (LSPRs), metal nanoparticles are used in optical and photothermal applications, such as sensing (adv. mater.2012,24, 4811-. The surface plasmon resonance of noble metal nanoparticles depends on their size, shape, composition and structure. Of these, Au/Pd has proven to be an interesting system because it is largely synthetically controlled, allowing its size, morphology and composition to be adjusted (Langmuir 2012,28, 9055-. Due to their application in the fields of Surface Enhanced Raman Spectroscopy (SERS), drug delivery and therapy, nonlinear optics, catalysis, biosensors, etc., they have become undeniable part of nanotechnology (Nano lett.2015,15, 5427-. For bimetallic nanoparticles, in addition to shape, size and material, the surface plasmon resonance of the nanoparticle depends on the relative size and shape of its core-shell, which is an important parameter for controlling the properties of the nanoparticle. Bimetallic nanoparticles have unusual electronic, catalytic, magnetic and optical properties compared to single metal nanoparticles (J Colloid Inte6 surface Sci 2013,392, 90-95; Crystal growth Des.2006,6, 1801-. Palladium (Pd) nanoparticles lack the SPR band in the visible region of the spectrum, and their SPR properties remain to be further studied compared to gold and silver nanoparticles (spectrochim. acta Part a 1997,53, 1595-. Pd nanoparticles are widely applied to the industrial field due to the catalytic performance thereof, such as hydrogen storage (J.alloys Compd.2005,389, 234-242), main catalysts for reducing polluted gases (J.Am.chem.Soc.2013,126, 5940-5941), electrode materials in electrocatalysis and the like (ACS Catal.2016,6, 8115-. The Pd nanoparticles have low SERS activity.
The existing patents on the nano-materials mainly aim at the preparation methods of octahedral, flocculent and three-pointed star palladium nano-materials, such as CN110170643A, CN109847742A, CN108031834A and the like. The related technologies are all improvements on the synthesis method, and further do not relate to flower-shaped Au-PdOXThe synthesis and application of bimetallic nanometer material are disclosed.
Disclosure of Invention
The invention aims to provide a synthesis method of a flower-shaped palladium oxide-gold nano composite material, which has simple process and can obtain a flower-shaped gold-palladium oxide core-shell (Au @ PdO) without an additional reducing agentX) A nanocomposite.
The invention also aims to provide a flower-like palladium oxide-gold nano composite material synthesized by the method, and the composite material can enhance Au-PdO by adding Au cores into Pd nano particlesXSERS activity of core-shell nanoparticles.
The last purpose of the invention is to provide the application of the flower-shaped palladium oxide-gold nano composite material as an active substrate in Surface Enhanced Raman Scattering (SERS) and the application of the flower-shaped palladium oxide-gold nano composite material in the aspect of photothermal effect.
The first object of the present invention can be achieved by the following technical solutions: a synthetic method of a flower-shaped palladium oxide-gold nano composite material comprises the following steps:
(1) selecting N, N-dimethylformamide, Pd (acac)2Uniformly mixing citric acid, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone to obtain orange red liquid;
(2) adding tungsten hexacarbonyl into the orange-red liquid, and adjusting the temperature in an argon atmosphere to perform stirring reaction to obtain blue hexagonal palladium nanosheets;
(3) purifying the blue hexagonal palladium nanosheets by using a mixed solvent of acetone and ethanol to obtain purified palladium;
(4) dissolving the purified palladium in ultrapure water to obtain a palladium nano solution, and stirring and reacting the palladium nano solution and chloroauric acid to obtain the flower-like palladium oxide-gold nano composite material.
In the synthesis method of the flower-like palladium oxide-gold nano composite material, the following steps are carried out:
preferably, N-Dimethylformamide (DMF), Pd (acac) as described in step (1)2The dosage relationship of the citric acid, the Cetyl Trimethyl Ammonium Bromide (CTAB) and the polyvinylpyrrolidone (PVP) is as follows: 5-15 mL: 16-26 mg: 1-10 mg: 50-100 mg: 20-40 mg.
More preferably, N-Dimethylformamide (DMF), Pd (acac) as described in step (1)2The dosage relationship of the citric acid, the Cetyl Trimethyl Ammonium Bromide (CTAB) and the polyvinylpyrrolidone (PVP) is as follows: 10mL of: 16 mg: 1 mg: 60 mg: 20 mg.
Wherein Pd (acac)2The chemical name of (1) is palladium diacetone.
Preferably, the tungsten hexacarbonyl (W (CO) in step (2)6) And the Pd (acac)2The dosage relationship is 100-120 mg: 16-26 mg.
More preferably, the tungsten hexacarbonyl (W (CO) in step (2)6) And the Pd (acac)2The dosage relationship is 100 mg: 16 mg.
Preferably, in the step (2), the temperature is adjusted to be 75-120 ℃ in an argon atmosphere, and the stirring reaction is carried out for 0.5-2 hours.
More preferably, in the step (2), the reaction is carried out for 1h under the argon atmosphere by stirring at the temperature of 80 ℃.
Preferably, the volume ratio of the acetone to the ethanol in the step (3) is 1: 0.1-0.3, wherein the volume percentage of the ethanol is 95%.
More preferably, the volume ratio of the acetone to the ethanol in the step (3) is 1:0.25, wherein the volume percentage of the ethanol is 95%.
Preferably, the concentration of the palladium nano solution in the step (4) is 0.8-1.2 mg/mL; the concentration of the chloroauric acid is 1-10 mM, and the volume ratio of the palladium nano solution to the chloroauric acid is 1: 0.2-0.5, stirring and reacting the palladium nano solution with chloroauric acid for 5-20 min.
More preferably, the concentration of the palladium nano solution in the step (4) is 1.0 mg/mL; the concentration of the chloroauric acid is 5mM, and the volume ratio of the palladium nano solution to the chloroauric acid is 1: 0.5, stirring and reacting the palladium nano solution with chloroauric acid for 5 min.
Preferably, the particle size of the flower-like palladium oxide-gold nanocomposite material in the step (4) is 100-200 nm.
The second object of the present invention can be achieved by the following technical solutions: the flower-like palladium oxide-gold nano composite material is prepared by the method.
The third object of the present invention can be achieved by the following technical solutions: the application of the flower-shaped palladium oxide-gold nano composite material as an active substrate in Surface Enhanced Raman Scattering (SERS) and the application of the flower-shaped palladium oxide-gold nano composite material in the aspect of photo-thermal effect.
Compared with the prior art, the invention has the following advantages:
(1) on the basis of synthesizing palladium (Pd) with good chemical reducibility, the method creatively utilizes the reducibility of Pd to reduce gold ions adsorbed on the surface of Pd into elemental gold, and successfully synthesizes a flower-like gold-palladium oxide core-shell (Au @ PdO) for the first timeX) A nanocomposite;
(2) the synthesis method adds Au nucleus into Pd nano-particles, and finds the generated flower-like gold-palladium oxide core-shell (Au @ PdO)X) The nano-composite can enhance Au @ PdOXSERS activity of core-shell nanoparticles with a photothermal effect;
(3) firstly, synthesizing regular hexagon Pd, and then carrying out oxidation-reduction reaction on the Pd and chloroauric acid to generate flower-shaped Au @ PdOXNano particles and characterizing the nano particles;
(4) the method of the invention can realize the core-shell (Au @ PdO) of the flower-like gold-palladium oxide by utilizing the reducibility of the palladium (Pd) nanosheet without an additional reducing agentX) NanocompositeThe preparation method has simple process and easy operation.
Drawings
FIG. 1 is a graph of the product made in example 1 of the invention, where a is a palladium hexagonal plate, b and c are Au @ PdOXTransmission electron microscope image of the nanocomposite, d image is Au @ PdOXHigh resolution Electron microscopy (HRTEM) of the nanocomposites, e-plot is Au @ PdOXHigh angular annular dark field pattern (HADDF) of the nanocomposite;
FIG. 2 is Au @ PdOXSEM image of the nanocomposite, panel a is Au @ PdOXScanning electron micrographs of the nanocomposite; b is a distribution diagram of O elements; c is a Pd element distribution diagram; d is a distribution diagram of Au elements; the existence and distribution conditions of O, Pd and Au elements are described;
FIG. 3 Au @ PdO in example 1 of the present inventionXXRD, IR and XPS characterization patterns of the nano-composite, wherein a pattern is Au @ PdOXX-ray diffraction pattern (XRD) of the nano-composite, wherein JCPDS No.87-0637 in a pattern is an XRD standard comparison card of Pd, JCPDSNo.65-8601 is an XRD standard comparison card of Au, and b pattern is Au @ PdOXThe infrared spectrum (IR) of the nanocomposite, and the c chart is Au @ PdOXX-ray photoelectron spectroscopy (XPS) of Pd element in the compound, and d is Au @ PdOXAn Au element X-ray photoelectron spectroscopy characterization (XPS) of the nanocomposite;
FIG. 4 is Au @ PdO in example 4 of the present inventionXSERS effect of the nano-composite, wherein a is a graph of Raman enhancement spectrum of Au @ PdOX nano-composite as a substrate to Methylene Blue (MB) dye with gradient concentration, and b is a graph of Au @ PdOXThe relationship between the Raman enhancement factor and the concentration of the nano-composite to the MB dye is shown in the graph c, at Au @ PdOXRandomly taking 20 points on a sample with the nano composite as a substrate MB as a probe molecule, and drawing d is Au @ PdOXThe nano-composite is a Raman three-dimensional image of 20 points randomly taken from a sample with a substrate MB as a probe molecule;
FIG. 5 is Au @ PdO in example 5 of the present inventionXPhotothermal effect of aqueous nanocomposite solution.
Detailed Description
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Example 1
To 10mL of N, N-Dimethylformamide (DMF), 16mg of Pd (acac)21mg of citric acid, 60mg of cetyltrimethylammonium bromide (CTAB) and 20mg of polyvinylpyrrolidone (PVP) were mixed and stirred for 1 hour to obtain an orange-red liquid.
Then transferred to a 25mL flask and added 100mg of tungsten hexacarbonyl (W (CO))6) Heating and stirring at 80 ℃ for 1 hour in an argon atmosphere to obtain blue hexagonal palladium nanosheets, as shown in a diagram in figure 1.
The volume ratio of acetone to ethanol is 8: 2 is used to purify the palladium.
Dissolving the purified palladium in 2mL of ultrapure water to obtain 1mg/mL palladium nano solution, and mixing 500. mu.L of palladium nano solution with 250. mu.L of 5mM HAuCl chloroauric acid4Stirring for 5 minutes to obtain flower-shaped palladium nano-gold.
The characterization of the nano-material prepared in this example can be seen in fig. 1-3.
The product patterns are shown in FIG. 1, where a is a palladium hexagonal plate, b and c are Au @ PdOXTransmission electron microscope images of different magnifications of the nanocomposite, d is Au @ PdOXHigh resolution Electron microscopy (HRTEM) of the nanocomposites, e-plot is Au @ PdOXHigh angle annular dark field pattern (HADDF) of the nanocomposite.
For Au @ PdO in FIG. 1XThe morphology (b picture) and the microscopic lattice fringes (c picture) and (d picture) of the nano-composite are observed, and the composite is found to be a flower-shaped crystal structure.
As can be seen from FIGS. b to e of FIG. 1, the flower-like palladium oxide-gold nanocomposite material has an approximate particle size of 100 to 200 nm.
FIG. 2 shows SEM images of Au @ PdOX nanocomposites, wherein a is Au @ PdOXScanning electron micrographs of the nanocomposite; b is a distribution diagram of O elements; c is a Pd element distribution diagram; d is a distribution diagram of Au elements; the existence and distribution of O, Pd and Au elements are described.
FIG. 3 shows the preparationAu@PdOXXRD, IR and XPS characterization patterns of the nano-composite.
FIG. 3, panel a is Au @ PdOXThe X-ray diffraction pattern (XRD) of the nano composite shows the crystal structure of the composite and contains Au and Pd elements, in the a picture, JCPDS No.87-0637 is an XRD standard comparison card of Pd, JCPDS No.65-8601 is an XRD standard comparison card of Au, and in the b picture, Au @ PdOXThe infrared spectrum (IR) of the nanocomposite, and the c chart is Au @ PdOXX-ray photoelectron spectroscopy (XPS) of Pd element in the compound, and d is Au @ PdOXThe X-ray photoelectron spectroscopy (XPS) of the Au element of the nanocomposite indicates the presence of Au.
Example 2
To 15mL of N, N-Dimethylformamide (DMF) were added in order 26mg of Pd (acac)25mg of citric acid, 90mg of cetyltrimethylammonium bromide (CTAB) and 40mg of polyvinylpyrrolidone (PVP) were mixed and stirred for 1 hour to obtain an orange-red liquid.
Then transferred to a 25mL flask and an additional 120mg of tungsten hexacarbonyl (W (CO))6) Heating and stirring for 0.5 hour at 100 ℃ in an argon atmosphere to obtain the blue hexagonal palladium nanosheet.
The volume ratio of acetone to ethanol is 1: 0.3, wherein the ethanol is 95 percent ethanol by volume.
Dissolving the purified palladium in 2mL of ultrapure water to obtain a palladium nano solution with a concentration of about 1mg/mL, and mixing 500. mu.L of the palladium nano solution with 150. mu.L of 5mM HAuCl chloroauric acid4Stirring for 8 minutes to obtain flower-shaped palladium nano gold.
Example 3
To 5mL of N, N-Dimethylformamide (DMF), 20mg of Pd (acac) was added210mg of citric acid, 50mg of cetyltrimethylammonium bromide (CTAB) and 30mg of polyvinylpyrrolidone (PVP) were mixed and stirred for 1 hour to obtain an orange-red liquid.
Then transferred to a 25mL flask and added 100mg of tungsten hexacarbonyl (W (CO))6) Heating and stirring for 1 hour at 80 ℃ in an argon atmosphere to obtain the blue hexagonal palladium nanosheet.
The volume ratio of acetone to ethanol is 1:0.1 is used for purifying palladium, wherein ethanol is ethanol with the volume percentage of 95 percent.
Dissolving the purified palladium in 2mL of ultrapure water to obtain a palladium nano solution with a concentration of about 1mg/mL, and mixing 500. mu.L of the palladium nano solution with 100. mu.L of 5mM HAuCl chloroauric acid4Stirring for 15 minutes to obtain flower-shaped palladium nano-gold.
Example 4
The Au @ PdO prepared in example 1XThe nano-composite is used for SERS detection of dye molecules MB. The method comprises the following specific steps: 5mMAu @ PdOXAnd (3) mixing the nano composite with dye molecules in a ratio of 1:1, sucking a small amount of mixture sample, placing the mixture sample on a silicon wafer, drying, and detecting under a Raman spectrometer.
The instrument selects a Renysha invia type micro Raman spectrum system, and parameters are set as follows: 785nm laser excitation, power 0.1mW, central wavelength 1200cm-1Exposure time 6 s.
Au@PdOXThe SERS effect of the nanocomplexes is shown in fig. 4.
FIG. 4, panel a, is a Raman enhancement profile of Au @ PdOX nanocomplexes as substrate versus gradient concentrations of Methylene Blue (MB) dye, indicating that Au @ PdOX as Raman substrate has enhancement effect on MB.
FIG. 4, panel b, is a graph of the relationship between the concentration and the Raman enhancement factor of the Au @ PdOX nanocomposite on the MB dye, which shows that the Au @ PdOX as a Raman substrate has a good enhancement effect on the MB, and the enhancement factor can be as high as 4.72 × 107。
The c plot in fig. 4 is a random 20 spots on the sample with Au @ PdOX nanocomplex as substrate MB as probe molecule to demonstrate a good reproducible RSD value of 8.89%.
The d-plot in fig. 4 is a raman three-dimensional plot of 20 random spots on the sample with Au @ PdOX nanocomposite as substrate MB as probe molecule to prove its good homogeneity.
Example 5
The Au @ PdO prepared in example 1XAnd (4) detecting the photo-thermal effect of the nano-composite.
The method comprises the following specific steps: the Au @ PdO prepared in example 1XThe nanocomposite was prepared into a suspended aqueous solution at a concentration of 0.2mg/mL, followed byTransferred to a 1.5mL EP tube; then, the suspension was irradiated with a laser beam (power: 2W) having a wavelength of 808nm, and the temperature of the suspension was measured by a thermal infrared imager every 30 seconds, and the temperature change of the liquid was recorded.
FIG. 5 shows Au @ PdOXPhoto-thermal effect of the nanocomposite, as can be seen from fig. 5, Au @ PdO was obtained under 10min laser irradiationXThe temperature of the suspension is continuously increased and is increased to 83 ℃ after 10 min; the blank control group ultra-pure aqueous solution has small temperature change, which proves that the Au @ PdOX nano compound has good photo-thermal effect.
Thus, Au @ PdO may be usedXThe nano composite is used for detecting photothermal effect.
FIG. 5 is Au @ PdO in example 5 of the present inventionXPhotothermal effect of aqueous nanocomposite solution.
The present invention is illustrated by the following examples, which are not intended to limit the scope of the invention. Other insubstantial modifications and adaptations of the present invention can be made without departing from the scope of the present invention.
Claims (10)
1. A synthetic method of a flower-shaped palladium oxide-gold nano composite material is characterized by comprising the following steps:
(1) selecting N, N-dimethylformamide, Pd (acac)2Uniformly mixing citric acid, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone to obtain orange red liquid;
(2) adding tungsten hexacarbonyl into the orange-red liquid, and adjusting the temperature in an argon atmosphere to perform stirring reaction to obtain blue hexagonal palladium nanosheets;
(3) purifying the blue hexagonal palladium nanosheets by using a mixed solvent of acetone and ethanol to obtain purified palladium;
(4) dissolving the purified palladium in ultrapure water to obtain a palladium nano solution, and stirring and reacting the palladium nano solution and chloroauric acid to obtain the flower-like palladium oxide-gold nano composite material.
2. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: n, N-dimethylformamide, Pd (acac) as described in step (1)2The dosage relationship of the citric acid, the cetyl trimethyl ammonium bromide and the polyvinylpyrrolidone is as follows: 5-15 mL: 16-26 mg: 1-10 mg: 50-100 mg: 20-40 mg.
3. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: the tungsten hexacarbonyl in the step (2) reacts with the Pd (acac)2The dosage relationship is 100-120 mg: 16-26 mg.
4. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: in the step (2), the temperature is adjusted to be 75-120 ℃ in the argon atmosphere, and stirring reaction is carried out for 0.5-2 h.
5. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: the volume ratio of the acetone to the ethanol in the step (3) is 1: 0.1-0.3, wherein the volume percentage of the ethanol is 95%.
6. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: the concentration of the palladium nano solution in the step (4) is 0.8-1.2 mg/mL; the concentration of the chloroauric acid is 1-10 mM, and the volume ratio of the palladium nano solution to the chloroauric acid is 1: 0.2-0.5, stirring and reacting the palladium nano solution with chloroauric acid for 5-20 min.
7. The method for synthesizing flower-shaped palladium oxide-gold nanocomposite material according to claim 1, wherein the method comprises the following steps: the particle size of the flower-shaped palladium oxide-gold nano composite material in the step (4) is 100-200 nm.
8. The flower-like palladium oxide-gold nanocomposite prepared by the method of any one of claims 1 to 6.
9. Use of the flower-like palladium oxide-gold nanocomposite material of claim 8 as an active substrate in Surface Enhanced Raman Scattering (SERS).
10. Use of the flower-like palladium oxide-gold nanocomposite material of claim 8 for photothermal effects.
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