CN105498287A - Method for preparing graphene oxide modification column - Google Patents
Method for preparing graphene oxide modification column Download PDFInfo
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- CN105498287A CN105498287A CN201510916387.XA CN201510916387A CN105498287A CN 105498287 A CN105498287 A CN 105498287A CN 201510916387 A CN201510916387 A CN 201510916387A CN 105498287 A CN105498287 A CN 105498287A
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- graphene oxide
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- capillary column
- post
- ultrasonic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/22—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the construction of the column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
Abstract
The invention relates to a method for preparing a graphene oxide modification column. The method specifically comprises the steps of preparation of a graphene oxide solution, pretreatment of a silica capillary column and modification of graphene oxide. The method disclosed by the invention has the advantages that the inner wall of the silica capillary column is modified by utilization of covalent interaction of the graphene oxide, so that not only can a capillary inner wall be modified as a stationary phase, but also an action site can be provided for separation of an analyte, and the separation capability of the capillary column can be improved.
Description
Technical field
The present invention relates to technical field of graphene, be specifically related to the preparation method that a kind of graphene oxide modifies post.
Background technology
Graphene oxide (GO) to be generally oxidized through strong acid by graphite and to obtain, preparation method primarily of Brodie method, Staudenmaier method and Hummers method.CN102225754A discloses one and prepares graphene oxide method, and adopt the mixing of graphite, concentrated acid and strong oxidizer, being obtained by reacting under the closed environment of 80 DEG C ~ 130 DEG C, reducing the control of reaction condition, is a kind of Hummers method of optimization.CN103332670A discloses and a kind ofly adds the preparation method preparing graphene oxide without the need to strong acid and strong oxidizer.It is oxidant that CN104591175A discloses a kind of employing potassium chlorate, carries out the preparation method of oxidation reaction under ultrasonic state.Graphene oxide not only has Graphene individual layer laminated structure and relevant nature, makes Graphene have better dispersiveness, the performance such as water-soluble simultaneously.
Capillary Electrophoresis (CE) technology is a kind of is split tunnel with capillary column, and high-voltage dc is driving force, the new and effective analytical technology be separated according to the difference and carrying out analyzing thing migration rate in sample.But CE technology has the shortcomings such as detection sensitivity is low, separation reappearance is poor.CN200610044550.9A discloses a kind of coated capillary electrophoresis column adopting new polymers coating, obtain coated capillary electrophoresis column by the large molecule of branching through the mode of physical absorption and chemical bonds, effectively can be separated basic protein, organic basic Small molecular, inorganic cation etc., improve the separating power of capillary column.
Graphene class material has that surface area is large, π-πconjugation is strong and hydrophobic feature, and can at room temperature be fixed on as Stationary liquid in capillary by the effect of covalent bond using GO, the oxy radical utilizing GO to show be to improve the separating power of capillary column.
Because GO surface has different oxy radicals, capillary tube inner wall can not only be modified as Stationary liquid, also can provide action site for the separation analyzing thing simultaneously, therefore modify with GO the direction that capillary column becomes people's research gradually.
Summary of the invention
A kind of graphene oxide that the invention provides that graphene oxide modifies post modifies the preparation method of post, specifically comprises the modification of the preparation of graphene oxide solution, the pretreatment of quartz capillary column and graphene oxide.
The preparation method of described graphene oxide (GO):
(1) by graphite: the ratio of concentrated sulfuric acid 1:50 part is in mass ratio added in there-necked flask, is placed in ice-water bath and is cooled to 0 DEG C, ultrasonic Keep agitation 1.5h;
(2) under ultrasonic treatment conditions, slowly add 35 parts of potassium permanganate, control temperature does not surpass 25 DEG C, continues to stir 3h;
(3) in there-necked flask, add 120 parts of deionized waters, temperature is increased to 100 DEG C, ultrasonic agitation 1h, closes ultrasonic;
(4) in reaction system, 30 parts of deionized waters are added and hydrogen peroxide leaves standstill reductase 12 0h;
(5) finally extremely neutral with the potassium hydroxide solution washing of 4%, spend deionized water repeatedly.
Described ultrasound condition is 1000W.
Poured into by washed colloid in clean surface plate, 70 DEG C of oven dry, grinding, sealing is preserved.
By gained graphene oxide ultrasonic dissolution in DMF (DMF), be mixed with the GO/DMF solution of 5mg/mL, then add 1, the 3-dicyclohexylcarbodiimide (DCC) of 0.5mg.
The pretreatment of quartz capillary column:
(1) 35min, then deionized water rinsing 10min is rinsed with the NaOH of 0.1mol/L;
(2) rinse 20min, then deionized water rinsing 10min, washed with methanol 10min with APTES (the APTES)/acetone soln of 2% (V/V), make capillary column inwall with amino;
(3) capillary column 1h is rinsed with the glutaraldehyde/borax soln of 10% (V/V).
The modification of graphene oxide: rinse pretreated capillary column 2h with GO/DMF solution, then use deionized water rinsing 5min.
The graphene oxide of preparation is modified post left at room temperature 24h.
Effective effect of the present invention: utilize the covalent bond effect of graphene oxide to modify the inwall of quartz capillary column, capillary tube inner wall can not only be modified as Stationary liquid, also can provide action site for the separation analyzing thing simultaneously, can be used for the separating power improving capillary column.
Figure of description
Fig. 1 is the infrared spectrogram of the GO of preparation.
Fig. 2 is the Raman collection of illustrative plates that GO, GO modify post and unmodified post.
Fig. 3 is the constituent content that unmodified post and GO modify column wall surface.
Wherein, 1 is GO, and 2 is GO modification post, and 3 is unmodified post.
Detailed description of the invention
The preparation of graphene oxide:
(1) by graphite: the ratio of concentrated sulfuric acid 1:50 part is in mass ratio added in there-necked flask, is placed in ice-water bath and is cooled to 0 DEG C, ultrasonic Keep agitation 1.5h;
(2) under ultrasonic treatment conditions, slowly add 35 parts of potassium permanganate, control temperature does not surpass 25 DEG C, continues to stir 3h;
(3) in there-necked flask, add 120 parts of deionized waters, temperature is increased to 100 DEG C, ultrasonic agitation 1h, closes ultrasonic;
(4) in reaction system, 30 parts of deionized waters are added and hydrogen peroxide leaves standstill reductase 12 0h;
(5) finally extremely neutral with the potassium hydroxide solution washing of 4%, spend deionized water repeatedly.
Described ultrasound condition is 1000W.
Poured into by washed colloid in clean surface plate, 70 DEG C of oven dry, grinding, sealing is preserved.
By gained graphene oxide ultrasonic dissolution in DMF (DMF), be mixed with the GO/DMF solution of 5mg/mL, then add 1, the 3-dicyclohexylcarbodiimide (DCC) of 0.5mg.
The pretreatment of quartz capillary column:
(1) 35min, then deionized water rinsing 10min is rinsed with the NaOH of 0.1mol/L;
(2) rinse 20min, then deionized water rinsing 10min, washed with methanol 10min with APTES (the APTES)/acetone soln of 2% (V/V), make capillary column inwall with amino;
(3) capillary column 1h is rinsed with the glutaraldehyde/borax soln of 10% (V/V).
The modification of graphene oxide: rinse pretreated capillary column 2h with GO/DMF solution, then use deionized water rinsing 5min.
The graphene oxide of preparation is modified post left at room temperature 24h.
Infrared spectrum analysis is carried out to the GO of preparation, sees Fig. 1.Fig. 1 is known, and the GO of preparation contains a large amount of hydrophilic radical, wherein 3435cm
-1peak, place is that the asymmetric stretching vibration of O-H absorbs, 1718cm
-1for the stretching vibration peak of carbonyl C=O, 1610cm
-1for the stretching vibration peak of C=C, 1050cm
-1for the absworption peak of C-O, the GO of preparation has the typical infrared signature of graphene oxide, shows that the present invention has successfully prepared graphene oxide.
Raman collection of illustrative plates is one of effective technology characterizing carbonaceous material, and GO has two obvious characteristic peaks under Raman spectrum, is respectively D band and G band, carries out the detection of Raman collection of illustrative plates respectively, see Fig. 2 to GO, GO modification post, unmodified post.As can be seen from Figure 1, unmodified post does not have two characteristic peaks of GO, modifies two characteristic peaks that post then detects GO, show that GO is successfully modified on capillary column inwall at GO, GO.
Adopt energy dispersion X-ray spectrometer to carry out elementary analysis to the surface of capillary column inwall, see Fig. 3.Result shows, GO modifies the inwall that the inner wall surface of post contains C element and unmodified post and shows not containing C element, and then illustrates that GO has successfully been fixed on capillary tube inner wall.
Claims (5)
1. graphene oxide modifies the preparation method of post, it is characterized in that: the modification comprising the preparation of graphene oxide solution, the pretreatment of quartz capillary column and graphene oxide.
2. a kind of graphene oxide according to claim 1 modifies the preparation method of post, it is characterized in that: the preparation of described graphene oxide solution comprises the following steps:
(1) by graphite: the ratio of concentrated sulfuric acid 1:50 part is in mass ratio added in there-necked flask, is placed in ice-water bath and is cooled to 0 DEG C, ultrasonic Keep agitation 1.5h;
(2) under ultrasonic treatment conditions, slowly add 35 parts of potassium permanganate, control temperature does not surpass 25 DEG C, continues to stir 3h;
(3) in there-necked flask, add 120 parts of deionized waters, temperature is increased to 100 DEG C, ultrasonic agitation 1h, closes ultrasonic;
(4) in reaction system, 30 parts of deionized waters are added and hydrogen peroxide leaves standstill reductase 12 0h;
(5) finally extremely neutral with the potassium hydroxide solution washing of 4%, spend deionized water repeatedly;
(6) poured into by washed colloid in clean surface plate, 70 DEG C of oven dry, grinding, sealing is preserved;
(7) by gained graphene oxide ultrasonic dissolution in DMF, be mixed with the solution of 5mg/mL, then add 1, the 3-dicyclohexylcarbodiimide of 0.5mg.
3. a kind of graphene oxide according to claim 1 modifies the preparation method of post, it is characterized in that: the pretreatment of described quartz capillary column comprises the following steps:
(1) 35min, then deionized water rinsing 10min is rinsed with the NaOH of 0.1mol/L;
(2) rinse 20min, then deionized water rinsing 10min, washed with methanol 10min with the APTES/acetone soln of 2%, make capillary column inwall with amino;
(3) capillary column 1h is rinsed with the glutaraldehyde/borax soln of 10%.
4. a kind of graphene oxide according to claim 1 modifies the preparation method of post, it is characterized in that: graphene oxide/N is used in being modified to of described graphene oxide, N-dimethylformamide solution rinses pretreated capillary column 2h, then uses deionized water rinsing 5min, left at room temperature 24h.
5. a kind of graphene oxide according to claim 2 modifies the preparation method of post, it is characterized in that: described ultrasonic process is 1000W.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| CN109647362A (en) * | 2019-02-28 | 2019-04-19 | 洛阳理工学院 | A kind of preparation method and application of graphene oxide grafting monolithic silica column |
| WO2019211813A1 (en) * | 2018-05-03 | 2019-11-07 | Qi Diagnostics Limited | Chemical sensing device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN103341355A (en) * | 2013-06-18 | 2013-10-09 | 大连理工大学 | Preparation method for molecularly imprinted monolithic column solid-phase microextraction fiber |
| CN103611511A (en) * | 2013-12-02 | 2014-03-05 | 武汉大学 | Preparation method for grapheme open-tube electric chromatographic column |
| CN104591175A (en) * | 2015-01-27 | 2015-05-06 | 长沙罗斯科技有限公司 | Preparation method for oxidized graphene |
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2015
- 2015-12-10 CN CN201510916387.XA patent/CN105498287A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225754A (en) * | 2011-05-11 | 2011-10-26 | 中国科学技术大学 | Preparation method of graphene oxide and preparation method of graphene |
| CN103341355A (en) * | 2013-06-18 | 2013-10-09 | 大连理工大学 | Preparation method for molecularly imprinted monolithic column solid-phase microextraction fiber |
| CN103611511A (en) * | 2013-12-02 | 2014-03-05 | 武汉大学 | Preparation method for grapheme open-tube electric chromatographic column |
| CN104591175A (en) * | 2015-01-27 | 2015-05-06 | 长沙罗斯科技有限公司 | Preparation method for oxidized graphene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| WO2019211813A1 (en) * | 2018-05-03 | 2019-11-07 | Qi Diagnostics Limited | Chemical sensing device |
| CN109647362A (en) * | 2019-02-28 | 2019-04-19 | 洛阳理工学院 | A kind of preparation method and application of graphene oxide grafting monolithic silica column |
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Application publication date: 20160420 |