CN102895938A - Preparation method of graphene covered silica gel - Google Patents
Preparation method of graphene covered silica gel Download PDFInfo
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- CN102895938A CN102895938A CN2012104514541A CN201210451454A CN102895938A CN 102895938 A CN102895938 A CN 102895938A CN 2012104514541 A CN2012104514541 A CN 2012104514541A CN 201210451454 A CN201210451454 A CN 201210451454A CN 102895938 A CN102895938 A CN 102895938A
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Abstract
The invention discloses a preparation method of graphene covered silica gel. The method comprises the following steps of: firstly adsorbing graphene oxide on the surface of amino silica gel through an electrostatic adsorption effect; and then carrying out hydrothermal reduction treatment to obtain a material of the graphene covered silica gel. The material has a simple preparation method, is safe and environment-friendly, and has good reproducibility. The material obtained by the preparation method has high graphene content; the prepared graphene covered silica gel material is used as a filler of solid phase extraction (SPE) so as to have the higher adsorption amount when being compared with a document value; and the material is used for a desalting step of enriching peptide in a bovine serum albumin (BSA) enzymolysis solution and analyzing a matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS), so as to obtain the better effect.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene parcel silica gel material, belong to Sample Pretreatment Technique Used.
Background technology
Graphene is the two-dimentional material by the former molecular six side's honey comb structures of monolayer carbon, is prepared by first experiment from 2004, just has been subject to whole world scientist's common concern.Graphene has very large theoretical specific area (2630 m
2/ g), thereby abundant adsorption site can be provided; Graphene is the material of a kind of π of being rich in-electron system, can produce π-π with the material that contains phenyl ring and interact; Graphene has good heat and mechanical stability; The low production cost of Graphene.Above these advantages make Graphene become enrichment material desirable in the sample pretreatment.
SPE (SPE) has the advantages such as enrichment times is high, the rate of recovery is high, the organic solvent consumption is few, expense is low, is a kind of Sample Pretreatment Technique Used commonly used.The good characteristic of Graphene has determined that it is a kind of good SPE adsorbent.But when pure Graphene directly was used as the SPE filler, also can run into following problem: irreversible reunion can occur in Graphene, caused effective adsorption site to reduce, and then caused that adsorption capacity reduces and the desorb difficulty; Small Graphene particle can run off in actual applications, and then causes the SPE pillar to stop up and extraction efficiency decline.
In order to overcome the above problems, guarantee simultaneously the good absorption property of Graphene, Graphene-material silica gel composite is a kind of effective solution.The method for preparing Graphene-material silica gel composite of bibliographical information mainly contains two kinds at present: first method is in the presence of Graphene, carries out the sol-gel process of silylating reagent hydrolysis, can generate one deck silica matrix material in the Graphene planar structure; Second method is based on electrostatic adsorption or the dehydration condensation between graphene oxide and the modified silica-gel (for example amino silica gel), and graphene oxide is fixed on Silica Surface, restores at last graphene oxide and gets final product.Yet in the material that first method prepares, a large amount of adsorption site of Graphene can be occupied by silica gel, causes adsorbance to reduce; In the composite of second method preparation, Graphene is to be wrapped in Silica Surface, can effectively address this problem, but, the method of bibliographical information not only manufacturing cycle is long, and in the reduction process of graphene oxide, used the poisonous materials such as hydrazine, and be unfavorable for the healthy of people, do not satisfy the demand for development of Green Chemistry simultaneously yet.The more important thing is, because dehydration conditions is harsh in the course of reaction, so that the bonded amount of Graphene is lower in the finally prepd material.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of gentleness, green are provided, the preparation method of the Graphene parcel silica gel that Graphene content is high simultaneously.
The present invention is that to solve the problems of the technologies described above the technical scheme that adopts be yes: a kind of preparation method of Graphene parcel silica gel material, preparation graphene oxide dispersion liquid and amino colloidal silica dispersion; Two dispersion liquids are mixed, and the concentration of amino silica gel is 3.5 ~ 35 mg/mL in the mixed liquor, and the concentration of graphene oxide is 0.5 ~ 2.5 mg/mL, mixes liquid, mixing time 〉=1 h; Mixed liquor is put into reactor carry out hydrothermal reduction and process, hydrothermal temperature 〉=200 ℃, hydro-thermal time 〉=2 h; With organic solvent product is carried out flotation, remove the Graphene that is not wrapped on the silica gel, obtain pure Graphene parcel silica gel.
Hydrothermal temperature during hydrothermal reduction is processed is 200 ~ 230 ℃, and the hydro-thermal time is 2 ~ 3 h.
The mixing time of mixed liquor is 1 ~ 2 h.
Organic solvent is METHYLPYRROLIDONE or DMF.
In the process of preparation Graphene parcel silica gel material, graphene oxide is adsorbed on amino Silica Surface by electrostatic interaction, then it being carried out hydrothermal reduction processes, obtain the silica gel material of Graphene parcel, because after being free on the graphene oxide reduction outside the silica gel before, can be adsorbed on Graphene parcel Silica Surface by the pi-pi accumulation effect, guarantee that the content of Graphene in the material of the method preparation is higher.Then utilize the density of Graphene parcel silica gel and Graphene different, with organic solvent product is carried out flotation, remove the Graphene that is not wrapped on the silica gel, obtain pure Graphene parcel silica gel material.
Preparation method's Simple fast provided by the invention, gentleness, green, favorable reproducibility, not only Graphene content is high for prepared Graphene parcel silica gel material, and has good absorption property.This Graphene parcel silica gel material is used for the enrichment of female hormone compounds, pentachlorophenol and the desalination step that MALDI-TOF MS analyzes, has obtained preferably effect.
Description of drawings
Fig. 1 is the photo of the Graphene parcel silica gel of amino silica gel, graphene oxide parcel silica gel and two kinds of distinct methods preparations among the embodiment 1, A is amino silica gel among the figure, B is graphene oxide parcel silica gel, C is the Graphene parcel silica gel that the method for a redox graphene parcel silica gel material in the prior art obtains, and D is the Graphene parcel silica gel that the present invention prepares.
Fig. 2 is the scanning electron microscope (SEM) photograph of the Graphene parcel silica gel of amino silica gel, graphene oxide parcel silica gel and two kinds of distinct methods preparations among the embodiment 1, A is amino silica gel among the figure, B is graphene oxide parcel silica gel, C is the Graphene parcel silica gel that the method for a redox graphene parcel silica gel in the prior art obtains, and D is the Graphene parcel silica gel that the present invention prepares.
Fig. 3 is Graphene parcel silica gel with the effect of other commercializations SPE filler when the enrichment pentachlorophenol relatively, among the figure, A is amino silica gel, C is the Graphene parcel silica gel that the method for a redox graphene parcel silica gel material in the prior art obtains, CNTs is CNT, GCB is Graphon, and C18 is the C18 bonded silica gel, and D is the Graphene parcel silica gel that the present invention prepares.
Fig. 4 is that the adsorbance of pentachlorophenol on Graphene parcel silica gel C and Graphene parcel silica gel D measured.
Fig. 5 is Graphene parcel silica gel with the effect of other commercializations SPE filler when the enrichment female hormone compounds relatively.Among the figure, A is amino silica gel, and D is the Graphene parcel silica gel that the present invention prepares, and C18 is the C18 bonded silica gel, and CNTs is CNT, and GCB is Graphon.
Fig. 6 is that the adsorbance of estriol on amino silica gel and Graphene parcel silica gel measured.
Fig. 7 is the MALDI-TOF MS figure of polypeptide in the Graphene parcel silica gel enrichment bovine serum albumin(BSA) BSA enzymolysis product, is followed successively by from top to bottom the design sketch after 10 nM BSA enzymolysis product Direct Analysis and the enrichment.
Fig. 8 is that Graphene parcel silica gel is used for MALDI-TOF MS desalination step design sketch, is followed successively by from top to bottom the design sketch after 200 nM BSA enzymolysis product Direct Analysis, efflux and the desalination.
The specific embodiment
By the following examples the present invention is done further introduction.
Embodiment 1
(1) preparation of Graphene parcel silica gel
At first compound concentration is the amino colloidal silica dispersion of 7.0 g/mL and the graphene oxide dispersion liquid of 2.0 g/mL, then with the two mixing, the concentration of amino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL after mixing, mix liquid 2 h, mixed liquor is put into reactor, 230 ℃ of lower reaction 3 h, use N, dinethylformamide carries out flotation to product, removes the Graphene that is not wrapped on the silica gel, obtains Graphene parcel silica gel D(as shown in Figure 2).
(2) contrast of the material of the material of the present invention's preparation and prior art preparation
For with prior art in redox graphene parcel silica gel material method relatively, before thermal reduction, free graphene oxide is removed, only graphene oxide is wrapped up silica gel carries out thermal reduction, prepared Graphene parcel silica gel material C(as shown in Figure 2), concrete steps are: be that the amino colloidal silica dispersion of 7.0 g/mL and the graphene oxide dispersion liquid of 2.0 g/mL mix with the concentration of above-mentioned preparation.The concentration of amino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL after mixing, mix liquid 2 h, use N, dinethylformamide carries out flotation to it and removes free graphene oxide, at last pure zirconia Graphene parcel silica gel is being put into reactor, 230 ℃ of lower reaction 3 h.Obtain Graphene parcel silica gel material C.Above-mentioned Graphene parcel silica gel C and Graphene parcel silica gel D are washed with ethanol, and 60 ℃ lower dry.As shown in Figure 1, because graphene oxide is brown, than amino silica gel A, the color of graphene oxide parcel silica gel B is brown, and the existence of graphene oxide has been described; The color of Graphene parcel silica gel C and Graphene parcel silica gel D is respectively grey and black simultaneously, and the existence of Graphene is described.As shown in Figure 2, amino Silica Surface is smooth, and behind electrostatic interaction adsorption and oxidation Graphene, amino Silica Surface becomes coarse, shows that graphene oxide successfully is wrapped in amino Silica Surface; Through after the thermal reduction, Graphene successfully is wrapped in the silica gel outside.Can judge tentatively that from scanning electron microscope (SEM) photograph the content of Graphene the Graphene parcel silica gel D is higher than Graphene parcel silica gel C.Through elementary analysis, the content that can calculate graphene oxide among the graphene oxide parcel silicon B is 2.6%, and the content of Graphene is respectively 3.3% and 8.3% among Graphene parcel silica gel C and the Graphene parcel silica gel D.The result of photo, ESEM and elementary analysis proves mutually, has illustrated that the high Graphene of Graphene content parcel silica gel material can be prepared by this method.
The preparation of Graphene parcel silica gel
At first compound concentration is the amino colloidal silica dispersion of 7.0 g/mL and the graphene oxide dispersion liquid of 1.0 g/mL, then with the two mixing, the concentration of amino silica gel and graphene oxide is respectively 3.5 g/mL and 0.5 g/mL in the mixed liquor, mix liquid 2 h, mixed liquor is put into reactor, 230 ℃ of lower reaction 3 h, use N, dinethylformamide carries out flotation to product, removes the Graphene that is not wrapped on the silica gel, obtains Graphene parcel silica gel.
Embodiment 3
The preparation of Graphene parcel silica gel
At first compound concentration is the amino colloidal silica dispersion of 7.0 g/mL and the graphene oxide dispersion liquid of 5.0 g/mL, then with the two mixing.The concentration of amino silica gel and graphene oxide is respectively 3.5 g/mL and 2.5 g/mL after mixing, and mixes liquid 1 h.Mixed liquor is being put into reactor, 230 ℃ of lower reaction 3 h.With DMF product is carried out flotation afterwards, remove the Graphene that is not wrapped on the silica gel, obtain Graphene parcel silica gel.
Embodiment 4
The preparation of Graphene parcel silica gel
At first compound concentration is the amino colloidal silica dispersion of 70 g/mL and the graphene oxide dispersion liquid of 2.0 g/mL, then with the two mixing.The concentration of amino silica gel and graphene oxide is respectively 35 g/mL and 1.0 g/mL after mixing, and mixes liquid 1 h.Mixed liquor is being put into reactor, 230 ℃ of lower reaction 3 h.With DMF product is carried out flotation afterwards, remove the Graphene that is not wrapped on the silica gel, obtain Graphene parcel silica gel.
Embodiment 5
The preparation of Graphene parcel silica gel
At first compound concentration is the amino colloidal silica dispersion of 7.0 g/mL and the graphene oxide dispersion liquid of 2.0 g/mL, then with the two mixing.The concentration of amino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL after mixing, and mixes liquid 2 h.Mixed liquor is being put into reactor, 200 ℃ of lower reaction 2 h.With METHYLPYRROLIDONE product is carried out flotation afterwards, remove the Graphene that is not wrapped on the silica gel, obtain Graphene parcel silica gel.
Embodiment 6
Graphene parcel silica gel is as the contrast when the enrichment pentachlorophenol of SPE filler and other commercializations SPE filler
The Graphene parcel silica gel for preparing is washed with ethanol, and 60 ℃ lower dry, gets 20 mg Graphenes parcel silica filler and insert in the SPE void column pipe, this filler activated and balance with 3 mL acetonitriles and 3 mL water successively again.The pentachlorophenol standard water solution of 5 mL, 50 ng/mL is passed through the SPE filler, with 1 mL stripping liquid desorb.The stripping liquid of C18 bonded silica gel (C18) filler is for being 1 mL methyl alcohol, and all the other are 1 mL alkalization methyl alcohol, 1.5 mL1 M NaOH solution is joined in the 50 mL methyl alcohol obtain the methyl alcohol that alkalizes.All SPE steps all make flow of solution by gravity.Before high performance liquid chromatography-ultraviolet (HPLC-UV) is analyzed, with among 30 microlitres, the 1 M HCl with stripping liquid in alkali.The HPLC-UV condition: mobile phase is that acetonitrile/pH is 2.5 20 mM phosphate buffers (v/v, 80/20), flow velocity 1.0 mL/min, chromatographic column is HiSep C18 (250 mm * 4.6 mm i.d., 5 μ m), column temperature is 40 ℃, and it is 300 nm that ultraviolet detects wavelength.As shown in Figure 3, can find out that prepared material is better than other commercial materials to the effect of extracting of pentachlorophenol.
Embodiment 7
Graphene parcel silica gel is as the mensuration of SPE filler to the pentachlorophenol adsorbance
0.2 μ g/mL pentachlorophenol solution of different volumes by the SPE pillar of 20 mg Graphenes parcel silica filler is housed, is calculated the amount of the object that is adsorbed by material by the content meter of measuring pentachlorophenol in the efflux successively.With data Langmuir models fitting, obtain two kinds of Graphenes parcel silica gel the adsorption capacity of pentachlorophenol is respectively 781.5 μ g/g and 286.3 μ g/g.Because the raising of Graphene bonded amount, Graphene parcel silica gel D is 2.7 times of the Graphene parcel silica gel C that obtains of the method for a redox graphene parcel silica gel material in the prior art to the adsorbance of pentachlorophenol.As shown in Figure 4.
Graphene parcel silica gel is as the contrast at enrichment female hormone compounds of SPE filler and other commercializations SPE filler
The Graphene parcel silica gel for preparing is washed with ethanol, 60 ℃ lower dry, getting 20 mg Graphenes parcel silica filler inserts in the SPE void column pipe, again this filler is activated and balance with 3 mL acetonitriles and 3 mL water successively, the female hormone compounds standard water solution of 5 mL, 50 ng/mL is passed through the SPE filler, with 1 mL acetonitrile desorb, with stripping liquid N with mitigation under 35 ℃
2Dry up rear usefulness 0.1 mL mobile phase dissolving, then carry out HPLC-UV and analyze.All SPE steps all make flow of solution by gravity.The HPLC-UV condition: mobile phase is acetonitrile/water (v/v, 48/52), flow velocity 1.0 mL/min, and chromatographic column is HiSep C18 (250 mm * 4.6 mm i.d., 5 μ m), and column temperature is 40 ℃, and it is 280 nm that ultraviolet detects wavelength.Can find out that prepared material is better than other commercial materials to the effect of extracting of female hormone compounds.As shown in Figure 5.
Embodiment 9
Graphene parcel silica gel and amino silica gel are respectively as the mensuration of SPE filler to the estriol adsorbance
0.2 μ g/mL estriol solution of different volumes by the SPE pillar of 20 mg adsorbents is housed, is calculated the amount of the object that is adsorbed by material by the content meter of measuring estriol in the efflux successively.With data Langmuir models fitting, obtain amino silica gel and Graphene parcel silica gel the adsorption capacity of estriol is respectively 25.1 μ g/g and 104.1 μ g/g.As shown in Figure 6.
Graphene parcel silica gel is as the polypeptide in the SPE filler enrichment bovine serum albumin(BSA) BSA enzymolysis product
The Graphene parcel silica gel for preparing is washed with ethanol, 60 ℃ lower dry, getting 20 mg Graphenes parcel silica filler inserts in the SPE void column pipe, again this filler is activated and balance with 1 mL stripping liquid and 2 mL water successively, stripping liquid is 0.1% trifluoroacetic acid aqueous solution/acetonitrile mixed liquor (v/v, 20/80), with the bovine serum albumin(BSA) BSA enzymolysis liquid of 4 mL, 10 nmol/L by the SPE filler, clean with 1 mL water, use at last 0.5 mL stripping liquid desorb.All SPE steps all make flow of solution by gravity.20 μ L stripping liquid vacuum are spin-dried for, and dissolve with 2 μ L matrix solutions, matrix solution is that alpha-cyano-4-hydroxycinnamic acid (CHCA) is dissolved in 0.1% trifluoroacetic acid aqueous solution/acetonitrile (v/v, 50/50) mixed liquor, and the concentration that makes CHCA is 2 mg/mL.Afterwards it is dropped on the MALDI target plate, carry out maldi analysis after room temperature is dried.The MALDI data are submitted to short range MASCOT server (Matrix Science, London, UK) carry out database search, can retrieve 24 polypeptide signals.As shown in Figure 7.
Embodiment 11
Graphene parcel silica gel is used for MALDI-TOF MS desalination step as the SPE filler
The Graphene parcel silica gel for preparing is washed with ethanol, 60 ℃ lower dry, getting 20 mg Graphenes parcel silica filler inserts in the SPE void column pipe, again this filler is activated and balance with 1 mL stripping liquid and 2 mL water successively, stripping liquid is 0.1% trifluoroacetic acid aqueous solution/acetonitrile mixed liquor (v/v, 20/80).Be that the bovine serum albumin(BSA) BSA enzymolysis liquid of 200 nmol/L is by the SPE filler with 0.5 mL concentration.Clean with 2 mL water, use at last 0.5 mL stripping liquid desorb.All SPE steps all make flow of solution by gravity.20 μ L stripping liquid vacuum are spin-dried for, and dissolve with 2 μ L matrix solutions, matrix solution is that alpha-cyano-4-hydroxycinnamic acid (CHCA) is dissolved in 0.1% trifluoroacetic acid aqueous solution/acetonitrile (v/v, 50/50) mixed liquor, and the concentration that makes CHCA is 2 mg/mL.Afterwards it is dropped on the MALDI target plate, carry out maldi analysis after room temperature is dried.In the sample solution owing to there being a large amount of salt, the ionization signal that when carrying out maldi analysis, can suppress object, do not observe polypeptide signal in the efflux, the polypeptide signal of observing in the stripping liquid is not only many than number in the sample solution, and signal strength signal intensity also increases, and the material that the present invention's preparation is described is analyzed the desalination step at MALDI-TOF MS and had good application.As shown in Figure 8.
Claims (5)
1. the preparation method of a Graphene parcel silica gel material is characterized in that: preparation graphene oxide dispersion liquid and amino colloidal silica dispersion; Two dispersion liquids are mixed, and the concentration of amino silica gel is 3.5 ~ 35 mg/mL in the mixed liquor, and the concentration of graphene oxide is 0.5 ~ 2.5 mg/mL, mixes liquid, mixing time 〉=1 h; Mixed liquor is put into reactor carry out hydrothermal reduction and process, hydrothermal temperature 〉=200 ℃, hydro-thermal time 〉=2 h; With organic solvent product is carried out flotation, remove the Graphene that is not wrapped on the silica gel, obtain pure Graphene parcel silica gel.
2. the preparation method of a kind of Graphene parcel silica gel material according to claim 1, it is characterized in that: the hydrothermal temperature during described hydrothermal reduction is processed is 200 ~ 230 ℃, and the hydro-thermal time is 2 ~ 3 h.
3. the preparation method of a kind of Graphene parcel silica gel material according to claim 1 and 2, it is characterized in that: the mixing time of described mixed liquor is 1 ~ 2 h.
4. the preparation method of a kind of Graphene parcel silica gel material according to claim 1 and 2, it is characterized in that: described organic solvent is METHYLPYRROLIDONE or DMF.
5. the preparation method of a kind of Graphene parcel silica gel material according to claim 3, it is characterized in that: described organic solvent is METHYLPYRROLIDONE or DMF.
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|---|---|---|---|---|
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| CN108906005A (en) * | 2018-07-12 | 2018-11-30 | 山东佳星环保科技有限公司 | A kind of graphene silica gel solid phase extraction material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935036A (en) * | 2009-05-26 | 2011-01-05 | 巴莱诺斯清洁能源控股公司 | Individual layer and the stabilising dispersions of multi-layer graphene layer in solution |
| CN102343239A (en) * | 2011-05-20 | 2012-02-08 | 四川大学 | Oxidized graphene or graphene/inorganic particle core/shell material and preparation method thereof |
-
2012
- 2012-11-13 CN CN201210451454.1A patent/CN102895938B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935036A (en) * | 2009-05-26 | 2011-01-05 | 巴莱诺斯清洁能源控股公司 | Individual layer and the stabilising dispersions of multi-layer graphene layer in solution |
| CN102343239A (en) * | 2011-05-20 | 2012-02-08 | 四川大学 | Oxidized graphene or graphene/inorganic particle core/shell material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| QIAN LIU, JIANBO SHI, JIANTENG SUN,ET AL: "Graphene and Graphene Oxide Sheets Supported on Silica as Versatile and High-Performance Adsorbents for Solid-Phase Extraction", 《ANGEWANDTE CHEMIE》 * |
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