CN102279215B - Amido-functionalized graphene oxide composite material and preparation method and application thereof - Google Patents
Amido-functionalized graphene oxide composite material and preparation method and application thereof Download PDFInfo
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Abstract
本发明涉及一种氧化石墨烯复合材料的制备方法，该制备方法包括在溶剂存在下将有机胺试剂与所述氧化石墨烯溶胶在30-120℃下搅拌3-72h。本发明还提供通过该制备方法得到的胺基功能化氧化石墨烯复合材料及其在检测重金属离子中的应用。本发明的胺基功能化氧化石墨烯复合材料不仅有效接触面积大，电子传导良好，而且具有良好的重金属离子捕集能力。
The invention relates to a preparation method of a graphene oxide composite material. The preparation method comprises stirring an organic amine reagent and the graphene oxide sol at 30-120° C. for 3-72 hours in the presence of a solvent. The invention also provides the amine functionalized graphene oxide composite material obtained by the preparation method and its application in detecting heavy metal ions. The amine functionalized graphene oxide composite material of the present invention not only has a large effective contact area, good electron conduction, but also has good heavy metal ion trapping ability.
Description
Technical field
The present invention relates to a kind of preparation method of amido-functionalized graphene oxide composite material, also relate to amido-functionalized graphene oxide composite material and the application in detecting heavy metal ion thereof according to the method, prepared.
Background technology
Along with the quickening of China's industrialization and urbanization process, more outstanding of the problem that environmental pollution brings.Water pollution in recent years and air pollution have had a strong impact on daily life.A large amount of sanitary sewages and industrial waste water enter water body, and the heavy metal that enters water body is finally detrimental to health by modes such as drinking-water, biological concentration and food chains.The stream pollution that some mining areas rely on is serious, and pathological phenomenons such as " itai-itais " once appearred in the resident of two sides, river in various degree, and cancer morbidity, mortality ratio are also quite high.Although had a lot of proven technique to be applied to the trace detection of pollutant, but generally these detection methods all need high-precision instrument and equipment to realize, not only expensive, and substantially all in the laboratory applications stage, life is rough with hook with people.Thereby electrochemical detection method cheap, simple to operate becomes the key of dealing with problems.
Electrochemical Stripping method is widely used for detecting trace heavy metal ion, and a key factor of impact detection effect is the preenrichment to heavy metal ion, and this can be by adopting functional material modified electrode improve.The effect of functional material is selectively to catch heavy metal ion, and serves as good electric transmission medium.Conducting polymer is because the existence of organo-functional group and good conductivity itself become the study hotspot detecting with functional material, as polyaniline (Electroanalysis, 2005,17,685-693).But then, a shortcoming that forms conducting polymer thin film at electrode surface is effective contact area that it is limited, can not make contact to greatest extent with the heavy metal ion in solution the bottleneck that detects the further lifting of effect in order to limit.Have researchist to propose take porous silica material as carrier, after organic molecule is modified, be applied to the detection of heavy metal ion, received good effect (Electroanalysis, 2009,21,1731-1742).The introducing of porous silicon has improved the specific surface area of material greatly, and then increased contacting and then the probability of enrichment of avtive spot in material and heavy metal ion, but meanwhile, the inertia of porous silicon itself and the existence in complicated duct, the conduction of electronics and the free diffusing of metallic ion have been affected, so, its by the more excellent material be replaced to of performance for inevitable.
Graphene (Graphene) is by a kind of carbonaceous nano material of the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape crystalline network, has good conductivity and chemical stability, high-specific surface area (2600m
2/ g).And as a kind of derivant of Graphene, graphene oxide be rich in a large amount of oxygen-containing functional groups (as-OH ,-COOH), this makes itself to have certain ion enrichment ability, also makes it become a kind of precursor of desirable synthesizing organic-inorganic compound substance simultaneously.
Summary of the invention
The object of the invention is to overcome the effective contact area of the existing electrode modified material for detection of heavy metal ion in water limited, electronic conduction is bad, the defect that heavy metal ion trapping ability is poor, a kind of preparation method of amido-functionalized graphene oxide composite material is provided, amido-functionalized graphene oxide composite material and the application in detecting heavy metal ion thereof by the method, prepared are also provided.
The present inventor finds that graphene oxide provides the specific surface area of super large to be beneficial to reactive group and catches with contacting of metallic ion, organic amine molecule is combined with graphene oxide, and the introducing of amidine functional group can greatly promote the heavy metal ion trapping ability of material on the basis of graphene oxide itself; And the two-dimension plane structure of graphene oxide is the desirable passage of electronic conduction.
The preparation method of a kind of graphene oxide composite material of the present invention, this preparation method is included under solvent existence organic amine reagent and described graphene oxide colloidal sol is stirred to 3-72h at 30-120 ℃.
The present invention also provides the amido-functionalized graphene oxide composite material of preparing by above-mentioned preparation method, and the application of this material in detecting heavy metal ion.
The present invention utilizes graphene oxide as carrier material, when large contact area is provided, also helps electronic conduction; Graphene oxide rich surface is containing a large amount of oxygen-containing functional groups in addition, and this had both been conducive to the seizure of counterweight metallic ion, also made it be easy to by organic molecule functionalization; Amido-functionalized graphene oxide composite material is compared with organic polymer, and its monomolecular excellent mobility has improved the contact probability with heavy metal ion, is more conducive to the enrichment of metallic ion in liquid phase.From infrared spectrogram, X-ray diffraction spectrogram, transmission electron microscope photo and the atomic force microscopy obtaining, amido molecule is combined with graphene oxide lamella by the effect of chemical bond, has formed the graphene oxide composite material of functional amido.
In addition, the present invention, by Electrochemical Stripping method, modifies and different heavy metal ion is detected glass-carbon electrode, process is simply controlled, and obtains highly sensitive detection effect, reproducible, in material, organic amine molecule is incorporated on graphene oxide sheet layer surface, to Pb by chemical bonded refractory
2+, Cu
2+or Cd
2+there is detection effect, lead ion especially, Pb under-1.2V deposition 120s condition
2+detect and be limited to 10
-13m.Be suitable for the higher water body of water quality requirement to carry out on-line monitoring.
In addition, the present invention be take graphite and by chemical oxidation, is prepared graphene oxide as raw material, and raw materials cost is low, and technique is simple, is suitable for large-scale industrial production;
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the prepared amido-functionalized graphene oxide composite material of embodiment 1.
Fig. 2 is the X-ray diffractogram of the prepared amido-functionalized graphene oxide composite material of embodiment 1.
Fig. 3 is the transmission electron microscope picture of the prepared amido-functionalized graphene oxide composite material of embodiment 1.
Fig. 4 is the atomic force microscope figure of the prepared amido-functionalized graphene oxide composite material of embodiment 1.
Fig. 5 is that the prepared amido-functionalized graphene oxide composite material of embodiment 1 is for detection of 10
-13m Pb
2+the Stripping Voltammetry curve map of ion.
Fig. 6 is that the prepared amido-functionalized graphene oxide composite material of embodiment 2 is for detection of 10
-8m Cd
2+the Stripping Voltammetry curve map of ion.
Fig. 7 is that the prepared amido-functionalized graphene oxide composite material of embodiment 3 is for detection of 10
-8m Cu
2+the Stripping Voltammetry curve map of ion.
Fig. 8 is that the prepared amido-functionalized graphene oxide composite material of embodiment 4 is for detection of 10
-12m Pb
2+the Stripping Voltammetry curve map of ion.
Fig. 9 is that the prepared amido-functionalized graphene oxide composite material of embodiment 5 is for detection of 10
-6m Hg
2+the Stripping Voltammetry curve map of ion.
Figure 10 is that the prepared amido-functionalized graphene oxide composite material of embodiment 6 is for detection of 10
-11m Pb
2+the Stripping Voltammetry curve map of ion.
Figure 11 is that the prepared amido-functionalized graphene oxide composite material of embodiment 7 is for detection of 10
-10m Pb
2+the Stripping Voltammetry curve map of ion.
Embodiment
The invention provides a kind of preparation method of graphene oxide composite material, this preparation method is included under solvent existence organic amine reagent and described graphene oxide colloidal sol is stirred to 3-72h at 30-120 ℃.
In the present invention, the consumption of described solvent is for can dissolve organic amine reagent, but in the preferred case, the weight ratio of described organic amine reagent and organic solvent is 1: 120-400.Graphene oxide in described graphene oxide colloidal sol and the weight ratio of organic amine reagent are preferably 1: 1-3.
In the present invention, described organic amine reagent is to be selected from one or more in aromatic amine, peptide and alkyl diamine.Under preferable case, described organic amine reagent is one or more in p-phenylenediamine (PPD), aniline, cystine, glycocoll, glycylglycine and ethylenediamine.
In the present invention, described solvent can be used lower aliphatic alcohols or water, and described lower aliphatic alcohols is preferably ethanol or ethylene glycol.
In the present invention, described graphene oxide colloidal sol can be selected variable concentrations as required, but is preferably 2-6mg/ml.
Under preferable case, the preparation method of described graphene oxide colloidal sol comprises, by the crystalline flake graphite of 1 weight portion, the concentrated sulphuric acid of the potassium permanganate of 2-5 weight portion and 20-50 weight portion mixes, and gained potpourri is stirred after 4-12h and 8-48h successively at 0 ℃ to 5 ℃ and 20-40 ℃, add 50-200 weight parts water, be warming up to afterwards 70-90 ℃ and stir 0.5-1h, adding 3-15 weight portion concentration is the hydrogen peroxide of 10-40 % by weight, after stirring, filter, then the filter cake obtaining is carried out to centrifuge washing with hydrochloric acid and deionized water that concentration is 3-15 % by weight respectively, the gluey product that obtains after washing is mixed with water and carry out ultrasonic dispersion.When described gluey product is mixed with water, the consumption of water has no particular limits, and can suitably select according to different needs.Described concentrated sulphuric acid preferred concentration is more than 90 % by weight.
Under preferable case, preparation method of the present invention also comprises and filtering stirring the potpourri obtaining after 3-72h, and gained filter cake is dried.
The present invention also provides the amido-functionalized graphene oxide composite material of preparing by said method.
The present invention also provides the application process of amido-functionalized graphene oxide composite material, and its preferred process is as follows: first 0.5-3mg amido-functionalized graphene oxide composite material is dispersed in 1ml 1 % by weight nafion, drips and be coated with 20-40 μ l to 28mm
2glass-carbon electrode surface on; Then electrode is immersed containing in the solution of heavy metal ion and adsorbs 2-30mins; Take out afterwards electrode with in three electrode electrolysers of inserting after distilled water flushing 3 times containing the electrolysis of hydrochloric acid liquid of 0.01M, controlling sedimentation potential is-1.8～-1.0V, time to be that 60-300s makes heavy metal ion deposit to electrode surface; Last Electrochemical Stripping, in water, the kind of heavy metal ion is relevant to output spike potential and peak height with content.Described Electrochemical Stripping refers to that the electric potential scanning by forward makes the heavy metal that electrode surface is reduced again be oxidized to ionic condition, and stripping is in electrolytic solution.Amido-functionalized graphene oxide composite material of the present invention is to Pb
2+, Cu
2+, Hg
2+or Cd
2+can both detect, especially Pb
2+, Pb under-1.2V deposition 120s condition
2+detect and be limited to 10
-13m.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
(1) preparation of graphene oxide
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in the concentrated sulphuric acid that 30ml concentration is 98 % by weight, under the ice bath of 0 ℃, stir 12h, add afterwards 3g potassium permanganate, 35 ℃ are stirred 24h, present soil Red to mixed liquor, after adding the dilution of 50ml water, control temperature at 90 ℃ and stir 0.5h, adding 5ml concentration is the hydrogen peroxide of 30 % by weight, solution becomes golden yellow, then by concentration, be 5 % by weight hydrochloric acid centrifuge washings (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
600mg p-phenylenediamine (PPD) is dissolved in 100ml ethanol, then the graphene oxide colloidal sol that is 2mg/ml with concentration described in 100ml step 1 mixes, after ultrasonic being uniformly dispersed, at 30 ℃, stir 24h, rotating speed centrifuging with 5000r/min, mixed liquor (volume ratio of ethanol and water is 1: 1) washing (200ml * 3 time) with ethanol and water, through 60 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result as Figure 1-Figure 4.
P-phenylenediamine (PPD) molecule is successfully connected on graphene oxide lamella as seen from Figure 1.In embodiment 1, obtain as seen from Figure 2 compound substance peak position, to low-angle, obvious movement has occurred, graphene oxide interlamellar spacing strengthens, and p-phenylenediamine (PPD) molecule has been inserted in graphene oxide sheet lamellar spacing.As shown in Figure 3, it is laminar structured that graphene oxide is, and compound substance nitrogen atom ratio is 5.0%.The introducing of p-phenylenediamine (PPD) has increased the thickness of graphene oxide lamella as seen from Figure 4, is about 2.5nm.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 1.5mg is made is dispersed in the nafion of 1 % by weight of 1ml, drips to be coated with 20 μ l and to modify on glass-carbon electrode surface, then electrode is immersed containing 10
-13m Pb
2+in the solution of ion, adsorb 5min, take out afterwards electrode and insert in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.2V, time are 120s, make heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.Result as shown in Figure 5.
As shown in Figure 5, amido-functionalized graphene oxide composite material prepared by the present invention has highly sensitive response to lead ion, and signal peak goes out peak position in-0.6V left and right, and detectability can be low to moderate 10
-13m.
Embodiment 2
(1) preparation of graphene oxide lamella
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 20ml 98% concentrated sulphuric acid, under the ice bath of 0 ℃, stir 4h, add afterwards 5g potassium permanganate, 20 ℃ are stirred 48h, present soil Red to mixed liquor, after adding the dilution of 100ml water, control temperature at 70 ℃ and stir 1h, the hydrogen peroxide that adds 15ml 10 % by weight, solution becomes golden yellow, then use 3% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
600mg p-phenylenediamine (PPD) is dissolved in 200ml ethanol, then the graphene oxide colloidal sol that is 2mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 80 ℃, stir 24h, rotating speed centrifuging with 5000r/min, with mixed liquor (ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 80 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 1.5mg is made is dispersed in the 1%nafion of 1ml, drips painting 40 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-8m Cd
2+in the solution of ion, adsorb 15min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.0V, time be that 300s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 6, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-8m cadmium ion has response, and signal peak goes out peak position in-0.85V left and right.
Embodiment 3
(1) preparation of graphene oxide lamella
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 50ml 98% concentrated sulphuric acid, under the ice bath of 0 ℃, stir 8h, add afterwards 2g potassium permanganate, 40 ℃ are stirred 8h, present soil Red to mixed liquor, after adding the dilution of 200ml water, control temperature at 80 ℃ and stir 0.5h, add 3ml 40 % by weight hydrogen peroxide, solution becomes golden yellow, then use 10% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
600mg glycocoll is dissolved in 300ml ethylene glycol, then the graphene oxide colloidal sol that is 2mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 120 ℃, stir 24h, rotating speed centrifuging with 5000r/min, with mixed liquor (ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 60 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 0.5mg is made is dispersed in the 1%nafion of 1ml, drips painting 30 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-8m Cu
2+in the solution of ion, adsorb 30min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.2V and time be that 200s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 7, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-8m copper ion has response, and signal peak goes out peak position in-0.1V left and right.
Embodiment 4
(1) preparation of graphene oxide
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 40ml 98% concentrated sulphuric acid, under the ice bath of 0 ℃, stir 10h, add afterwards 4g potassium permanganate, 30 ℃ are stirred 36h, present soil Red to mixed liquor, after adding the dilution of 150ml water, control temperature at 85 ℃ and stir 1h, the hydrogen peroxide that adds 10ml 20 % by weight, solution becomes golden yellow, then use 15% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 3mg/ml.
(2) functional amido of graphene oxide
600mg cystine is dissolved in 300ml ethanol, then the graphene oxide colloidal sol that is 3mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 30 ℃, stir 12h, rotating speed centrifuging with 5000r/min, with mixed liquor (ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 70 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 3mg is made is dispersed in the 1%nafion of 1ml, drips painting 20 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-12m Pb
2+in the solution of ion, adsorb 2min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.0V and time be that 60s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 8, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-12m lead ion has response, and signal peak peak height is higher than example 1.
Embodiment 5
(1) preparation of graphene oxide lamella
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 30ml 98% concentrated sulphuric acid, under the ice bath of 5 ℃, stir 6h, add afterwards 3g potassium permanganate, 35 ℃ are stirred 8h, present soil Red to mixed liquor, after adding the dilution of 50ml water, control temperature at 75 ℃ and stir 0.5h, the hydrogen peroxide that adds 5ml 30 % by weight, solution becomes golden yellow, then use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 6mg/ml.
(2) functional amido of graphene oxide
600mg aniline is dissolved in 200ml ethanol, then the graphene oxide colloidal sol that is 6mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 30 ℃, stir 48h, rotating speed centrifuging with 5000r/min, with mixed liquor (volume ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 80 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 2mg is made is dispersed in the 1%nafion of 1ml, drips painting 20 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-6m Hg
2+in the solution of ion, adsorb 25min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.8V and time be that 250s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 9, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-6m mercury ion has response, and signal peak goes out peak position in 0.3V left and right.
Embodiment 6
(1) preparation of graphene oxide lamella
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 30ml 98% concentrated sulphuric acid, under the ice bath of 3 ℃, stir 5h, add afterwards 3g potassium permanganate, 30 ℃ are stirred 12h, present soil Red to mixed liquor, after adding the dilution of 50ml water, control temperature at 80 ℃ and stir 1h, the hydrogen peroxide that adds 5ml 30 % by weight, solution becomes golden yellow, then use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
600mg ethylenediamine is dissolved in 200ml ethanol, then the graphene oxide colloidal sol that is 2mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 30 ℃, stir 3h, rotating speed centrifuging with 5000r/min, with mixed liquor (volume ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 70 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 1mg is made is dispersed in the 1%nafion of 1ml, drips painting 30 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-11m Pb
2+in the solution of ion, adsorb 20min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.5V and time be that 90s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 10, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-11m lead ion has response, and signal peak peak height is higher than example 1.
Embodiment 7
(1) preparation of graphene oxide lamella
Getting 1g natural flake graphite (particle diameter is 10-100 μ m) joins in 30ml 98% concentrated sulphuric acid, under the ice bath of 2 ℃, stir 4h, add afterwards 3g potassium permanganate, 30 ℃ are stirred 8h, present soil Red to mixed liquor, after adding the dilution of 50ml water, control temperature at 85 ℃ and stir 0.5h, the hydrogen peroxide that adds 10ml 30 % by weight, solution becomes golden yellow, then use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after washing is added to the water, ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
600mg glycylglycine is dissolved in 200ml water, then the graphene oxide colloidal sol that is 2mg/ml with concentration described in 100ml step 1 mixes, ultrasonic being uniformly dispersed, finally at 30 ℃, stir 72h, rotating speed centrifuging with 5000r/min, with mixed liquor (volume ratio of ethanol and water is 1: the 1) washing (200ml * 3 time) of ethanol and water, through 60 ℃ dry, obtain the amido-functionalized graphene oxide composite material of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope, this amido-functionalized graphene oxide composite material is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The amido-functionalized graphene oxide composite material that 2.5mg is made is dispersed in the 1%nafion of 1ml, drips painting 20 μ l and modifies on glass-carbon electrode surface, then electrode is immersed containing 10
-10m Pb
2+in the solution of ion, adsorb 20min, taking out afterwards electrode inserts in three electrode electrolysers containing 0.01M electrolysis of hydrochloric acid liquid with after distilled water flushing 3 times, control sedimentation potential for-1.2V and time be that 150s makes heavy metal ion deposit to electrode surface, last Electrochemical Stripping, recording of output signals.
As shown in Figure 11, the amido-functionalized graphene oxide composite material that prepared by the present invention is to 10
-10m lead ion has response, and signal peak peak height is higher than example 1.
Claims (8)
1. the preparation method of a graphene oxide composite material, it is characterized in that, this preparation method is included under solvent existence organic amine reagent and described graphene oxide colloidal sol is stirred to 3-72h at 30-120 ℃, described organic amine reagent is to be selected from one or more in aromatic amine, peptide and alkyl diamine, wherein, the weight ratio of described organic amine reagent and solvent is 1:120-400, and the graphene oxide in described graphene oxide colloidal sol and the weight ratio of organic amine reagent are 1:1-3.
2. preparation method according to claim 1, wherein, described organic amine reagent is one or more in p-phenylenediamine (PPD), aniline, cystine, glycocoll, glycylglycine and ethylenediamine.
3. preparation method according to claim 1, wherein, described solvent is one or more in ethanol, ethylene glycol and water.
4. preparation method according to claim 1, wherein, described graphene oxide collosol concentration is 2-6mg/ml.
5. preparation method according to claim 1, wherein, the preparation method of described graphene oxide colloidal sol comprises, by the crystalline flake graphite of 1 weight portion, the concentrated sulphuric acid of the potassium permanganate of 2-5 weight portion and 20-50 weight portion mixes, and gained potpourri is stirred after 4-12h and 8-48h successively at 0 ℃ to 5 ℃ and 20-40 ℃, add 50-200 weight parts water, be warming up to afterwards 70-90 ℃ and stir 0.5-1h, adding 3-15 weight portion concentration is the hydrogen peroxide of 10-40 % by weight, after stirring, filter, then by the filter cake obtaining, by concentration, be respectively hydrochloric acid and the deionized water washing of 3-15 % by weight, the gluey product that obtains after washing is mixed with water and carry out ultrasonic dispersion.
6. preparation method according to claim 1, wherein, this preparation method also comprises and filtering stirring the potpourri obtaining after 3-72h, and gained filter cake is dried.
7. an amido-functionalized graphene oxide composite material, is characterized in that, this amido-functionalized graphene oxide composite material is to prepare by the method described in any one in claim 1-6.
8. the application of amido-functionalized graphene oxide composite material claimed in claim 7 in detecting heavy metal ion.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010202948.7A CN102279215B (en) | 2010-06-10 | 2010-06-10 | Amido-functionalized graphene oxide composite material and preparation method and application thereof |
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| CN102879431B (en) * | 2012-10-15 | 2014-07-16 | 苏州大学 | Gas sensor based on reduced graphene oxide and preparation method thereof |
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| CN103466610B (en) * | 2013-09-25 | 2015-05-20 | 中国科学院理化技术研究所 | Graphene chemical modification method |
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| CN108828026A (en) * | 2018-06-25 | 2018-11-16 | 哈尔滨工业大学 | A kind of preparation method of the highly sensitive detection nitrogen dioxide gas sensor of room temperature |
| CN115072714B (en) * | 2022-06-07 | 2023-10-13 | 苏州大学 | Amine compound modified graphene film and preparation method thereof |
| CN116285395A (en) * | 2022-12-08 | 2023-06-23 | 广西路建工程集团有限公司 | A kind of amino functionalized graphene modified asphalt and preparation method thereof |
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