CN102895938B - Preparation method of graphene covered silica gel - Google Patents
Preparation method of graphene covered silica gel Download PDFInfo
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- CN102895938B CN102895938B CN201210451454.1A CN201210451454A CN102895938B CN 102895938 B CN102895938 B CN 102895938B CN 201210451454 A CN201210451454 A CN 201210451454A CN 102895938 B CN102895938 B CN 102895938B
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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 the preparation method of a kind of Graphene parcel silica gel material, belong to Sample Pretreatment Technique Used.
Background technology
Graphene is by the two-dimentional material of the former molecular six side's honey comb structures of monolayer carbon, is prepared, just receive the common concern of whole world scientist from 2004 by experiment first.Graphene has very large theoretical specific surface area (2630 m
2/ g), thus can provide abundant adsorption site; Graphene is a kind of material being rich in π-electron system, can produce π-π interact with the material containing phenyl ring; Graphene has excellent heat and mechanical stability; The low production cost of Graphene.These advantages make Graphene become the enrichment material of sample pretreatment middle ideal above.
SPE (SPE) has the advantages such as enrichment times is high, the rate of recovery is high, organic solvent consumption is few, expense is low, is a kind of conventional Sample Pretreatment Technique Used.It is a kind of excellent SPE adsorbent that the good characteristic of Graphene determines it.But when pure Graphene being directly used as SPE filler, also can running into following problem: irreversible reunion can occur Graphene, cause effective adsorption site to reduce, and then cause adsorption capacity to reduce and desorb difficulty; Small Graphene particle can run off in actual applications, and then causes SPE pillar to block and extraction efficiency decline.
In order to overcome the above problems, ensure the good adsorbent performance of Graphene, Graphene-material silica gel composite is a kind of effective solution simultaneously.The method preparing Graphene-material silica gel composite of current bibliographical information mainly contains two kinds: first method is under Graphene exists, and carries out the sol-gel process of silylating reagent hydrolysis, can generate one deck silica matrix material in graphene planes structure; Second method is based on the electrostatic adsorption between graphene oxide and modified silica-gel (such as alkylamino silica gel) or dehydration condensation, graphene oxide is fixed on Silica Surface, finally restores graphene oxide.But in the material for preparing of first method, a large amount of adsorption site of Graphene can be occupied by silica gel, causes adsorbance to reduce; In composite prepared by second method, Graphene is wrapped in Silica Surface, can effectively address this problem, but, not only manufacturing cycle is long for the method for bibliographical information, and in the reduction process of graphene oxide, used the poisonous material such as hydrazine, be unfavorable for that people's is healthy, also do not meet the demand for development of Green Chemistry simultaneously.The more important thing is, because dehydration conditions in course of reaction is harsh, make the bonded amount of Graphene in finally prepd material lower.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of gentle, green, the preparation method of the Graphene parcel silica gel that Graphene content is high simultaneously.
The present invention is yes for solving the problems of the technologies described above adopted technical scheme: a kind of preparation method of Graphene parcel silica gel material, preparation graphene oxide dispersion and alkylamino silica gel dispersion liquid; By two dispersion liquid mixing, in mixed liquor, the concentration of alkylamino silica gel is 3.5 ~ 35 mg/mL, and the concentration of graphene oxide is 0.5 ~ 2.5 mg/mL, is uniformly mixed liquid, mixing time >=1 h; Mixed liquor is put into reactor and carries out hydrothermal reduction process, hydrothermal temperature >=200 DEG C, hydro-thermal time >=2 h; With organic solvent, flotation is carried out to product, remove the Graphene be not wrapped on silica gel, obtain pure Graphene parcel silica gel.
Hydrothermal temperature in hydrothermal reduction process is 200 ~ 230 DEG C, 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 preparing Graphene parcel silica gel material, graphene oxide is adsorbed on alkylamino silica gel surface by electrostatic interaction, then hydrothermal reduction process is carried out, obtain the silica gel material of Graphene parcel, after being free on the graphene oxide reduction outside silica gel before, Graphene parcel Silica Surface can be adsorbed on by pi-pi accumulation effect, ensure that the content of Graphene in material prepared by the method is higher.Then utilize Graphene to wrap up silica gel different with the density of Graphene, with organic solvent, flotation is carried out to product, remove the Graphene be not wrapped on silica gel, obtain pure Graphene parcel silica gel material.
Preparation method provided by the invention is simple and quick, gentle, green, favorable reproducibility, and 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 female hormone compounds, the enrichment of pentachlorophenol and the desalting steps of MALDI-TOF MS analysis, achieves good effect.
Accompanying drawing explanation
The photo of the Graphene parcel silica gel that Fig. 1 is alkylamino silica gel in embodiment 1, prepared by graphene oxide parcel silica gel and two kinds of distinct methods, in figure, A is alkylamino silica gel, 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 prior art obtains, and D is Graphene parcel silica gel prepared by the present invention.
The scanning electron microscope (SEM) photograph of the Graphene parcel silica gel that Fig. 2 is alkylamino silica gel in embodiment 1, prepared by graphene oxide parcel silica gel and two kinds of distinct methods, in figure, A is alkylamino silica gel, 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 prior art obtains, and D is Graphene parcel silica gel prepared by the present invention.
Fig. 3 is that Graphene parcel silica gel is with the effectiveness comparison of other commercializations SPE filler when enrichment pentachlorophenol, in figure, A is alkylamino silica gel, C is the Graphene parcel silica gel that the method for a redox graphene parcel silica gel material in prior art obtains, CNTs is CNT, GCB is Graphon, and C18 is C18 bonded silica gel, and D is Graphene parcel silica gel prepared by the present invention.
Fig. 4 is that the adsorbance of pentachlorophenol on Graphene parcel silica gel C and Graphene parcel silica gel D measures.
Fig. 5 is that Graphene parcel silica gel is with the effectiveness comparison of other commercializations SPE filler when enrichment female hormone compounds.In figure, A is alkylamino silica gel, and D is Graphene parcel silica gel prepared by the present invention, and C18 is C18 bonded silica gel, and CNTs is CNT, and GCB is Graphon.
Fig. 6 is that the adsorbance of estriol on alkylamino silica gel and Graphene parcel silica gel measures.
Fig. 7 is that the MALDI-TOF MS of polypeptide in Graphene parcel silica gel enrichment bovine serum albumin(BSA) BSA enzymolysis product schemes, and is followed successively by the design sketch after 10 nM BSA enzymolysis product Direct Analysis and enrichment from top to bottom.
Fig. 8 is that Graphene wraps up silica gel for MALDI-TOF MS desalting steps design sketch, is followed successively by the design sketch after 200 nM BSA enzymolysis product Direct Analysis, efflux and desalination from top to bottom.
Detailed description of the invention
By the following examples the present invention is described further.
Embodiment 1
(1) preparation of Graphene parcel silica gel
First compound concentration is the alkylamino silica gel dispersion liquid of 7.0 g/mL and the graphene oxide dispersion of 2.0 g/mL, then the two is mixed, after mixing, the concentration of alkylamino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL, be uniformly mixed liquid 2 h, mixed liquor is put into reactor, at 230 DEG C, react 3 h, with N, dinethylformamide carries out flotation to product, removes the Graphene be not wrapped on silica gel, obtains Graphene parcel silica gel D(as shown in Figure 2).
(2) contrast of material prepared of the material prepared of the present invention and prior art
In order to wrap up the Measures compare of silica gel material with a redox graphene in prior art, by the removing of free graphene oxide before thermal reduction, only graphene oxide is wrapped up silica gel carries out thermal reduction, prepare Graphene parcel silica gel material C(as shown in Figure 2), concrete steps are: be the alkylamino silica gel dispersion liquid of 7.0 g/mL and the graphene oxide dispersion mixing of 2.0 g/mL by the concentration of above-mentioned preparation.After mixing, the concentration of alkylamino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL, be uniformly mixed liquid 2 h, with N, dinethylformamide carries out the free graphene oxide of flotation removing to it, finally pure zirconia Graphene parcel silica gel is put into reactor, at 230 DEG C, react 3 h.Obtain Graphene parcel silica gel material C.Above-mentioned Graphene parcel silica gel C and Graphene parcel silica gel D ethanol are washed, dry at 60 DEG C.As shown in Figure 1, because graphene oxide is brown, compared to alkylamino silica gel A, the color of graphene oxide parcel silica gel B is brown, describes the existence of graphene oxide; The color of Graphene parcel silica gel C and Graphene parcel silica gel D is grey and black respectively simultaneously, and the existence of Graphene is described.As shown in Figure 2, alkylamino silica gel smooth surface, after electrostatic interaction adsorption and oxidation Graphene, alkylamino silica gel surface becomes coarse, shows that graphene oxide is successfully wrapped in alkylamino silica gel surface; After thermal reduction, Graphene is successfully wrapped in outside silica gel.Tentatively can judge that the content of Graphene Graphene parcel silica gel D is higher than Graphene parcel silica gel C from scanning electron microscope (SEM) photograph.Through elementary analysis, the content that can calculate graphene oxide in graphene oxide parcel silicon B is 2.6%, and in Graphene parcel silica gel C and Graphene parcel silica gel D, the content of Graphene is respectively 3.3% and 8.3%.The result of photo, ESEM and elementary analysis is proved mutually, describes this method and can prepare the high Graphene parcel silica gel material of Graphene content.
Embodiment 2
The preparation of Graphene parcel silica gel
First compound concentration is the alkylamino silica gel dispersion liquid of 7.0 g/mL and the graphene oxide dispersion of 1.0 g/mL, then the two is mixed, in mixed liquor, the concentration of alkylamino silica gel and graphene oxide is respectively 3.5 g/mL and 0.5 g/mL, be uniformly mixed liquid 2 h, mixed liquor is put into reactor, at 230 DEG C, react 3 h, with N, dinethylformamide carries out flotation to product, removes the Graphene be not wrapped on silica gel, obtains Graphene parcel silica gel.
Embodiment 3
The preparation of Graphene parcel silica gel
First compound concentration is the alkylamino silica gel dispersion liquid of 7.0 g/mL and the graphene oxide dispersion of 5.0 g/mL, then the two is mixed.After mixing, the concentration of alkylamino silica gel and graphene oxide is respectively 3.5 g/mL and 2.5 g/mL, is uniformly mixed liquid 1 h.Mixed liquor is put into reactor, at 230 DEG C, reacts 3 h.With DMF, flotation is carried out to product afterwards, remove the Graphene be not wrapped on silica gel, obtain Graphene parcel silica gel.
Embodiment 4
The preparation of Graphene parcel silica gel
First compound concentration is the alkylamino silica gel dispersion liquid of 70 g/mL and the graphene oxide dispersion of 2.0 g/mL, then the two is mixed.After mixing, the concentration of alkylamino silica gel and graphene oxide is respectively 35 g/mL and 1.0 g/mL, is uniformly mixed liquid 1 h.Mixed liquor is put into reactor, at 230 DEG C, reacts 3 h.With DMF, flotation is carried out to product afterwards, remove the Graphene be not wrapped on silica gel, obtain Graphene parcel silica gel.
Embodiment 5
The preparation of Graphene parcel silica gel
First compound concentration is the alkylamino silica gel dispersion liquid of 7.0 g/mL and the graphene oxide dispersion of 2.0 g/mL, then the two is mixed.After mixing, the concentration of alkylamino silica gel and graphene oxide is respectively 3.5 g/mL and 1.0 g/mL, is uniformly mixed liquid 2 h.Mixed liquor is put into reactor, at 200 DEG C, reacts 2 h.With METHYLPYRROLIDONE, flotation is carried out to product afterwards, remove the Graphene be not wrapped on silica gel, obtain Graphene parcel silica gel.
Embodiment 6
Graphene parcel silica gel is as the contrast when enrichment pentachlorophenol of SPE filler and other commercializations SPE filler
The Graphene prepared parcel silica gel ethanol is washed, dry at 60 DEG C, get 20 mg Graphene parcel silica fillers and insert in SPE void column pipe, then this filler is activated and balance with 3 mL acetonitriles and 3 mL water successively.By the pentachlorophenol standard aqueous solution of 5 mL 50 ng/mL by 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 are joined in 50 mL methyl alcohol and obtain the methyl alcohol that alkalizes.All SPE steps all make solution flow by gravity.Before high performance liquid chromatography-ultraviolet (HPLC-UV) is analyzed, with the alkali in 30 microlitre 1 M HCl and in stripping liquid.HPLC-UV condition: mobile phase to be acetonitrile/pH be 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 μm), column temperature is 40 DEG C, and UV detect wavelength is 300 nm.As shown in Figure 3, can find out that the effect of extracting of prepared material to pentachlorophenol is better than other commercial materials.
Embodiment 7
Graphene parcel silica gel is as the mensuration of SPE filler to pentachlorophenol adsorbance
0.2 μ g/mL pentachlorophenol solution of different volumes, successively by being equipped with the SPE pillar of 20 mg Graphene parcel silica fillers, is calculated by the amount of the object of materials adsorption by the content meter measuring pentachlorophenol in efflux.Data are used Langmuir models fitting, obtain the adsorption capacity of two kinds of Graphene parcel silica gel to pentachlorophenol and be respectively 781.5 μ g/g and 286.3 μ g/g.Due to the raising of Graphene bonded amount, the adsorbance of Graphene parcel silica gel D to pentachlorophenol is 2.7 times of the Graphene parcel silica gel C that the method for a redox graphene parcel silica gel material in prior art obtains.As shown in Figure 4.
Embodiment 8
Graphene parcel silica gel is as the contrast at enrichment female hormone compounds of SPE filler and other commercializations SPE filler
The Graphene prepared parcel silica gel ethanol is washed, dry at 60 DEG C, getting 20 mg Graphene parcel silica fillers inserts in SPE void column pipe, again this filler is activated and balance with 3 mL acetonitriles and 3 mL water successively, by the female hormone compounds standard aqueous solution of 5 mL 50 ng/mL by SPE filler, with 1 mL acetonitrile desorb, by stripping liquid N with mitigation at 35 DEG C
2dry up rear use 0.1 mL mobile phase to dissolve, then carry out HPLC-UV analysis.All SPE steps all make solution flow by gravity.HPLC-UV condition: mobile phase is acetonitrile/water (v/v, 48/52), flow velocity 1.0 mL/min, chromatographic column is HiSep C18 (250 mm × 4.6 mm i.d., 5 μm), and column temperature is 40 DEG C, and UV detect wavelength is 280 nm.Can find out that the effect of extracting of prepared material to female hormone compounds is better than other commercial materials.As shown in Figure 5.
Embodiment 9
Graphene parcel silica gel and alkylamino silica gel are respectively as the mensuration of SPE filler to estriol adsorbance
0.2 μ g/mL estriol solution of different volumes, successively by being equipped with the SPE pillar of 20 mg adsorbents, is calculated by the amount of the object of materials adsorption by the content meter measuring estriol in efflux.Data are used Langmuir models fitting, obtain alkylamino silica gel and the Graphene parcel adsorption capacity of silica gel to estriol is respectively 25.1 μ g/g and 104.1 μ g/g.As shown in Figure 6.
Embodiment 10
Graphene parcel silica gel is as the polypeptide in SPE filler enrichment bovine serum albumin(BSA) BSA enzymolysis product
The Graphene prepared parcel silica gel ethanol is washed, dry at 60 DEG C, getting 20 mg Graphene parcel silica fillers inserts in SPE void column pipe, again this filler is carried out activating and balancing with 1 mL stripping liquid and 2 mL water successively, stripping liquid is 0.1% trifluoroacetic acid aqueous solution/acetonitrile mixture (v/v, 20/80), by the bovine serum albumin(BSA) BSA enzymolysis liquid of 4 mL 10 nmol/L by SPE filler, with 1 mL water cleaning, finally use 0.5 mL stripping liquid desorb.All SPE steps all make solution flow by gravity.20 μ L stripping liquid vacuum be spin-dried for, and dissolve with 2 μ L matrix solutions, matrix solution is dissolved in 0.1% trifluoroacetic acid aqueous solution/acetonitrile (v/v, 50/50) mixed liquor by alpha-cyano-4-hydroxycinnamic acid (CHCA), makes the concentration of CHCA be 2 mg/mL.Dropped on MALDI target plate afterwards, room temperature carries out maldi analysis after drying.MALDI data are submitted to short range MASCOT server (Matrix Science, London, UK) and carry out database search, 24 polypeptide signals can be retrieved.As shown in Figure 7.
Embodiment 11
Graphene parcel silica gel is used for MALDI-TOF MS desalting steps as SPE filler
The Graphene prepared parcel silica gel ethanol is washed, dry at 60 DEG C, getting 20 mg Graphene parcel silica fillers inserts in SPE void column pipe, again this filler is carried out activating and balancing with 1 mL stripping liquid and 2 mL water successively, stripping liquid is 0.1% trifluoroacetic acid aqueous solution/acetonitrile mixture (v/v, 20/80).Be that the bovine serum albumin(BSA) BSA enzymolysis liquid of 200 nmol/L is by SPE filler by 0.5 mL concentration.With 2 mL water cleanings, finally use 0.5 mL stripping liquid desorb.All SPE steps all make solution flow by gravity.20 μ L stripping liquid vacuum be spin-dried for, and dissolve with 2 μ L matrix solutions, matrix solution is dissolved in 0.1% trifluoroacetic acid aqueous solution/acetonitrile (v/v, 50/50) mixed liquor by alpha-cyano-4-hydroxycinnamic acid (CHCA), makes the concentration of CHCA be 2 mg/mL.Dropped on MALDI target plate afterwards, room temperature carries out maldi analysis after drying.Owing to there is a large amount of salt in sample solution, the ionization signature of object can be suppressed when carrying out maldi analysis, polypeptide signal is not observed in efflux, the polypeptide signal observed in stripping liquid is not only many than number in sample solution, and signal strength signal intensity also increases, illustrate that material prepared by the present invention has good application at MALDI-TOF MS analysis desalting steps.As shown in Figure 8.
Claims (5)
1. a preparation method for Graphene parcel silica gel material, is characterized in that: preparation graphene oxide dispersion and alkylamino silica gel dispersion liquid; By two dispersion liquid mixing, in mixed liquor, the concentration of alkylamino silica gel is 3.5 ~ 35 mg/mL, and the concentration of graphene oxide is 0.5 ~ 2.5 mg/mL, is uniformly mixed liquid, mixing time >=1 h; Mixed liquor is put into reactor and carries out hydrothermal reduction process, hydrothermal temperature >=200 DEG C, hydro-thermal time >=2 h; With organic solvent, flotation is carried out to product, remove the Graphene be not wrapped on 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 in described hydrothermal reduction process is 200 ~ 230 DEG C, 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, 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, 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, is characterized in that: described organic solvent is METHYLPYRROLIDONE or DMF.
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| CN104624177A (en) * | 2013-11-07 | 2015-05-20 | 中国石油天然气股份有限公司 | Preparation method of oxidized-graphene-modified silica gel chromatography filling material |
| CN104130309A (en) * | 2013-12-25 | 2014-11-05 | 常州碳宇纳米科技有限公司 | Pretreatment method used for improving purity of purified protein |
| CN104258598B (en) * | 2014-09-25 | 2017-01-25 | 深圳粤网节能技术服务有限公司 | Solid phase extraction column and preparation method thereof as well as chemical sample pretreatment method based on solid phase extraction column |
| CN104489922B (en) * | 2014-12-11 | 2017-09-26 | 上海烟草集团有限责任公司 | A kind of preparation and application of graphene oxide bonded silica gel composite |
| CN104525174B (en) * | 2015-01-05 | 2016-08-24 | 重庆文理学院 | A kind of method preparing graphene-based composite based on graphene oxide self assembly |
| CN106092717A (en) * | 2016-05-26 | 2016-11-09 | 苏州佰锐生物科技有限公司 | A kind of method that novel solid extracting agent synchronizes enrichment desalination to bovine serum albumin |
| CN105954349B (en) * | 2016-06-02 | 2018-11-27 | 南开大学 | A kind of method of qualitative analysis graphene oxide |
| CN107262078B (en) * | 2017-08-16 | 2020-03-31 | 淄博海关综合技术服务中心 | Graphene/silica gel solid phase extraction material and application thereof |
| 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 |
| CN109336990B (en) * | 2018-10-25 | 2021-04-30 | 西北农林科技大学 | Method for removing plant polysaccharide pigment from protonated amino graphene and application |
| CN111450573B (en) * | 2019-01-22 | 2022-01-21 | 福州奥尼多生物科技有限公司 | Graphene mixed filler, preparation method thereof, graphene mixed filler chromatographic column and application thereof |
| CN110907572B (en) * | 2019-11-14 | 2023-03-10 | 云南中烟工业有限责任公司 | Device and method for measuring 8-isomeric prostaglandin F2 alpha in urine |
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| 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 |
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| 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 |
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