CN104999088A - Method for preparing gold nanoparticles based on quick reduction of graphene self-assembly multilayer films - Google Patents
Method for preparing gold nanoparticles based on quick reduction of graphene self-assembly multilayer films Download PDFInfo
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Abstract
The invention discloses a method for preparing gold nanoparticles based on quick reduction of graphene self-assembly multilayer films. The method comprises the following steps: (1) polyethyleneimine and polyacrylic acid serve as polyelectrolytes to prepare reduced-oxidized graphene multilayer film solution with good dispersibility through a layer by layer self-assembly technology by using hydrazine hydrate as a reducing agent; and (2) chloroauric acid is added to perform in-situ reduction by using the reducibility of the polyelectrolytes of the reduced-oxidized graphene multilayer films through an ultrasonic effect to obtain a gold nanoparticle-reduced-oxidized graphene multilayer film composite material. The method is simple in process, short in preparation period, controllable in size, strong in repeatability, excellent in stability and environment-friendly. The prepared composite material is excellent in stability in water solution, is not liable to be agglomerated, and has better photothermal conversion efficiency, better surface-enhanced Raman effect and good biological compatibility. The method has wide application prospect in such aspects as sensing, environmental protection, surface-enhanced Raman scattering and biological medicines.
Description
Technical field
The present invention relates to the preparation method of the Graphene preparation method of self-assembled film, golden nanometer particle and both composites layer by layer, belong to materials chemistry LBL self-assembly and preparing technical field.
Background technology
Laminated assembling technology is simple and easy, the multi-functional surface modification method of one that the nineties in last century, fast development was got up.By the method for successively alternating deposit, utilize weak interaction between layers, as electrostatic attraction, hydrogen bond, coordinate bond etc., make the spontaneous association that attracts each other of layer and layer become structural integrity and have supramolecular structure or the molecule aggregate of some specific function.
Graphene obtains the straightforward procedure first time of repeatedly peeling off graphite by extra large nurse (A.Geim) and the Nuo Woxiaoluofu (K.Novoselov) of Univ Manchester UK by use adhesive tape in 2004.They rely on the preeminent accomplishment in grapheme material field, jointly obtain 2010 annual Nobel Prizes in physics.
Graphite is the molecular crystal combined with Van der Waals force, has three-dimensional layer structure.Because the carbon-carbon bond on same plane layer combines very strong, extremely difficult fracture, therefore the fusing point of graphite is very high, chemical stabilization.Graphene is a kind of monolayer carbon atomic plane material separated from graphite material, and thickness only has 0.335 nm, and 200,000 Graphenes are superimposed and only have a hairline so thick.The structure of Graphene is plane hexagonal lattice, and wherein each carbon atom is sp
2hydridization, and contribute the electronics on residue p track to be formed greatly
key,
electronics can move freely, and makes Graphene have splendid electric conductivity.
Golden nanometer particle occurs the earliest, one of nano material of most study.There is unique skin effect, small-size effect and quantum size effect, the physicochemical properties different from macroscopic material with other, to construct and the various fields such as biochip test is with a wide range of applications at biomarker, sensor.But golden nanometer particle because of surface energy excessive, existence and stability is poor, the easy problem such as reunions, therefore prepares the effective way that golden nanometer particle composite becomes performance golden nanometer particle unique effect.
How by golden nanometer particle and redox graphene multilayer film compound, obtain that size is controlled, the Two-dimensional Composites of good stability, be a brand-new research topic.
Summary of the invention
The technical issues that need to address of the present invention are just that providing a kind of prepares golden nanometer particle method based on Graphene self-assembled multilayer film fast restore, it with polymine and polyacrylic acid for polyelectrolyte, be the redox graphene multilayer film that good dispersion prepared by reducing agent by layer-by-layer and with hydrazine hydrate, and at its surface in situ reduction gold chloride, obtain size controlled, the golden nanometer particle composite that the reduced oxygen functionalized graphene multilayer film of good stability is coated, the inventive method technique is simple, manufacturing cycle is short, environmental protection, repeatability is strong, combination product size is controlled, uniform and stable, preparation in enormous quantities can be realized.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The present invention's one prepares golden nanometer particle method based on Graphene self-assembled multilayer film fast restore, it is characterized in that, described method for polyelectrolyte, is redox graphene multilayer film solution that reducing agent prepare good dispersion by layer-by-layer, with hydrazine hydrate with polymine and polyacrylic acid; Gold chloride is added in redox graphene multilayer film solution, pass through ultrasonication at normal temperatures and pressures, utilize the reproducibility that in redox graphene multilayer film, polyelectrolyte has, in-situ reducing obtains golden nanometer particle-redox graphene multilayer film composite.
Particularly, described method step is:
The preparation of A redox graphene multilayer film:
1) graphene oxide water solution of 0.15-0.45mg/mL is prepared, ultrasonic disperse;
2) dispersion liquid of step 1) gained is dropwise joined in the polyethylenimine solution of same volume, stir 15-20 minute;
3) in step 2) add 15-20 μ L hydrazine hydrate, oil bath 1-3h at 80-90 DEG C in gained solution, obtain redox graphene monofilm solution;
4) by step 3) gained solution deionized water centrifuge washing 1-4 time repeatedly, unnecessary polymine is removed;
5) step 4) gained dropwise is joined in the polyacrylic acid solution of same volume, stir 15-30 minute;
6) by step 5) gained solution deionized water centrifuge washing 1-4 time repeatedly, unnecessary polyacrylic acid is removed;
7) repeat step 2), 4), 5), 6), obtain reduced graphene multilayer film solution;
The preparation of B golden nanometer particle and Graphene multilayer film three dimensional composite structure:
1) in reduced graphene multilayer film solution, the chlorauric acid solution that volume ratio is the 10-20mmol of 2:1 is added, ultrasonic 15-20mins at 25-30 DEG C;
2) by step 1) gained solution deionized water centrifuge washing 1-4 time repeatedly, remove unnecessary impurity, obtain golden nanometer particle and redox graphene multilayer film composite.
The present invention utilizes layer-by-layer to prepare finely dispersed Graphene multi-layer film material, and under ultrasound condition, normal temperature and pressure in-situ reducing growth golden nanometer particle, obtains size controlled, the golden nanometer particle composite that the reduced oxygen functionalized graphene multilayer film of good stability is coated.Present invention utilizes the cooperative effect of golden nanometer particle and redox graphene bi-material; make material have more excellent electric conductivity and biocompatibility, be with a wide range of applications in sensing, environmental protection, SERS and biological medicine etc.
The present invention has following advantage compared with other existing techniques:
1) the present invention adopts layer-by-layer to prepare redox graphene multi-layer film material, and at normal temperatures and pressures can growth in situ golden nanometer particle, and technique is simple, and manufacturing cycle is short, is applicable to producing in enormous quantities, has good industrialization prospect.
2) the present invention is in the process of reduction golden nanometer particle, make use of the reproducibility of polyelectrolyte (polymine) in redox graphene multilayer film, does not re-use other reducing agents, embody and economize on resources, the theory of environmental protection.
3) the present invention is in preparation process, and utilize the number of plies of ultrasonic means and adjustment multi-layer film material, the size achieving golden nanometer particle is simply controlled.
Accompanying drawing explanation
Fig. 1 is the AFM collection of illustrative plates that the present invention prepares redox graphene monofilm.
Fig. 2 is the transmission electron microscope collection of illustrative plates that the present invention prepares golden nanometer particle/redox graphene multilayer film composite.
Fig. 3 is that the present invention prepares golden nanometer particle/redox graphene multilayer film composite material surface enhancing Raman collection of illustrative plates, with 10
-6mmol rhodamine 6G is that probe molecule detects, Raman signal to fabulous enhancing, illustrate that this compound has excellent measuring ability.
Fig. 4 is that the present invention prepares golden nanometer particle/redox graphene multilayer film composite photothermal conversion effect figure.
Fig. 5 is that the present invention prepares golden nanometer particle/redox graphene multilayer film composite cytotoxicity result data and infrared radiation to the figure of the impact of cytotoxicity experiment.
Detailed description of the invention
embodiment 1
One, the preparation of redox graphene multilayer film:
1,5mg graphene oxide is got, the graphene oxide water solution 20mL of preparation 0.25mg/mL, ultrasonic disperse;
2, the dispersion liquid of step 1 gained is dropwise joined in 20mL polyethylenimine solution (5mg/mL), stir 20 minutes;
3, in step 2 gained solution, add 15 μ L hydrazine hydrates, oil bath 2h at 80 DEG C, obtain redox graphene monofilm solution;
4, by step 3 gained solution deionized water centrifuge washing 3 times repeatedly, unnecessary polymine is removed;
5, step 4 gained dropwise is joined in the polyacrylic acid solution (5mg/mL) of 20mL, stir 20 minutes;
6, by step 5 gained solution deionized water centrifuge washing 3 times repeatedly, unnecessary polyacrylic acid is removed;
7, repeat step 2,4,5,6, obtain reduced graphene multilayer film solution.
Two, the preparation of golden nanometer particle and Graphene multilayer film three dimensional composite structure:
8, in 1mL, 0.25mg/mL reduced graphene multilayer film solution, the chlorauric acid solution of 500 μ L, 10mmol is added, at room temperature ultrasonic 15mins;
9, by step 8 gained solution deionized water centrifuge washing 3 times repeatedly, remove unnecessary impurity, obtain golden nanometer particle and redox graphene multilayer film composite.
embodiment 2
Present embodiment prepares the graphene oxide water solution of 0.15mg/mL as different from Example 1 in step 1, and other are identical with embodiment 1.
embodiment 3
Present embodiment prepares the graphene oxide water solution of 0.35mg/mL as different from Example 1 in step 1, and other are identical with embodiment 1.
embodiment 4
Present embodiment prepares the graphene oxide water solution of 0.45mg/mL as different from Example 1 in step 1, and other are identical with embodiment 1.
embodiment 5
Present embodiment adds the chlorauric acid solution of 500 μ L, 20mmol as different from Example 1 in step 8, and other are identical with embodiment 1.
embodiment 6
The present embodiment adds the chlorauric acid solution of 500 μ L, 10mmol as different from Example 1 in step 8 in 1mL, 0.17mg/mL and 1mL 0.11mg/mL reduced graphene multilayer film solution, and other are identical with embodiment 1.
Fig. 1 is the AFM collection of illustrative plates that the present invention prepares redox graphene monofilm, and can see that membrane is flaky material, thickness is 12nm;
Fig. 2 is the transmission electron microscope collection of illustrative plates that the present invention prepares golden nanometer particle/redox graphene multilayer film composite, and can find out that golden nanometer particle is that reduced oxygen functionalized graphene multilayer film is coated, be tufted composite;
Fig. 3 is that the present invention prepares golden nanometer particle-redox graphene multilayer film composite material surface enhancing Raman collection of illustrative plates, with 10
-6mmol rhodamine 6G is that probe molecule detects, Raman signal to fabulous enhancing, illustrate that this compound has excellent measuring ability.
Fig. 4 is that the present invention prepares golden nanometer particle-redox graphene multilayer film composite photothermal deformation effect figure, illustrates that this material has good photothermal deformation effect;
Fig. 5 is that the present invention prepares golden nanometer particle-redox graphene multilayer film composite cytotoxicity result data and infrared radiation to the figure of the impact of cytotoxicity experiment, illustrates that this composite has extremely strong lethal effect to tumour cell after having good biocompatibility and medicine carrying.
The method technique is simple, and in-situ reducing generates golden nanometer particle only needs 3-5h, and manufacturing cycle is short, and the number of plies of adjustable redox graphene multilayer film controls the size of the golden nanometer particle generated, and size is controlled, and repeatability is strong, good stability, environmental protection.Prepared composite in aqueous good stability, not easily reunite, there is good photo-thermal conversion efficiency simultaneously, good surface-enhanced Raman effects, good biocompatibility.Be with a wide range of applications in sensing, environmental protection, SERS and biological medicine etc.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (2)
1. prepare golden nanometer particle method based on Graphene self-assembled multilayer film fast restore for one kind, it is characterized in that, described method for polyelectrolyte, is redox graphene multilayer film solution that reducing agent prepare good dispersion by layer-by-layer, with hydrazine hydrate with polymine and polyacrylic acid; Gold chloride is added in redox graphene multilayer film solution, pass through ultrasonication at normal temperatures and pressures, utilize the reproducibility that in redox graphene multilayer film, polyelectrolyte has, in-situ reducing obtains golden nanometer particle-redox graphene multilayer film composite.
2. prepare golden nanometer particle method based on Graphene self-assembled multilayer film fast restore as claimed in claim 1, it is characterized in that, described method step is:
The preparation of A redox graphene multilayer film:
1) graphene oxide water solution of 0.15-0.45mg/mL is prepared, ultrasonic disperse;
2) dispersion liquid of step 1) gained is dropwise joined in the polyethylenimine solution of same volume, stir 15-20 minute;
3) in step 2) add 15-20 μ L hydrazine hydrate, oil bath 1-3h at 80-90 DEG C in gained solution, obtain redox graphene monofilm solution;
4) by step 3) gained solution deionized water centrifuge washing 1-4 time repeatedly, unnecessary polymine is removed;
5) step 4) gained dropwise is joined in the polyacrylic acid solution of same volume, stir 15-30 minute;
6) by step 5) gained solution deionized water centrifuge washing 1-4 time repeatedly, unnecessary polyacrylic acid is removed;
7) repeat step 2), 4), 5), 6), obtain reduced graphene multilayer film solution;
The preparation of B golden nanometer particle and Graphene multilayer film three dimensional composite structure:
1) in reduced graphene multilayer film solution, the chlorauric acid solution that volume ratio is the 10-20mmol of 2:1 is added, ultrasonic 15-20mins at 25-30 DEG C;
2) by step 1) gained solution deionized water centrifuge washing 1-4 time repeatedly, remove unnecessary impurity, obtain golden nanometer particle and redox graphene multilayer film composite.
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| CN106237984A (en) * | 2016-07-29 | 2016-12-21 | 燕山大学 | A kind of method that graphene oxide and chemical modification thereof are prepared in diadust surface |
| CN106984363A (en) * | 2017-05-17 | 2017-07-28 | 中国地质大学（北京） | A kind of method that utilization LBL self-assembly prepares catalysis material |
| CN111230138A (en) * | 2020-01-16 | 2020-06-05 | 暨南大学 | Pi-Pi directional self-assembly-based three-dimensional gold super particle, preparation and application thereof in SERS substrate |
| CN111551536A (en) * | 2020-06-05 | 2020-08-18 | 广东石油化工学院 | Preparation method and application of SERS (surface enhanced Raman Scattering) probe based on electrostatic assembly and in-situ reduction |
| CN112897618A (en) * | 2021-01-25 | 2021-06-04 | 浙江大学 | Three-dimensional photothermal conversion material capable of efficiently treating saline water and wastewater, device and method |
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| CN106984363A (en) * | 2017-05-17 | 2017-07-28 | 中国地质大学（北京） | A kind of method that utilization LBL self-assembly prepares catalysis material |
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| CN111230138A (en) * | 2020-01-16 | 2020-06-05 | 暨南大学 | Pi-Pi directional self-assembly-based three-dimensional gold super particle, preparation and application thereof in SERS substrate |
| CN111230138B (en) * | 2020-01-16 | 2022-06-21 | 暨南大学 | Pi-Pi directional self-assembly-based three-dimensional gold super particle, preparation and application thereof in SERS substrate |
| CN111551536A (en) * | 2020-06-05 | 2020-08-18 | 广东石油化工学院 | Preparation method and application of SERS (surface enhanced Raman Scattering) probe based on electrostatic assembly and in-situ reduction |
| CN111551536B (en) * | 2020-06-05 | 2023-07-18 | 广东石油化工学院 | Preparation method and application of SERS probe based on electrostatic assembly and in-situ reduction |
| CN112897618A (en) * | 2021-01-25 | 2021-06-04 | 浙江大学 | Three-dimensional photothermal conversion material capable of efficiently treating saline water and wastewater, device and method |
| CN112897618B (en) * | 2021-01-25 | 2022-04-12 | 浙江大学 | Three-dimensional photothermal conversion material capable of efficiently treating saline water and wastewater, device and method |
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