CN102279215A - 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
The invention relates to a preparation method of a graphene oxide composite material. The preparation method comprises the step of stirring an organic amine reagent and graphene oxide collosol at the temperature of 30-129 DEG C for 3-72 hours in the presence of a solvent. The method further provides an amido-functionalized graphene oxide composite material prepared through the preparation method and an application of the amido-functionalized graphene oxide composite material in the detection of heavy metal ions. The amido-functionalized graphene oxide composite material provided by the invention has a large effective contact area, good electron conduction and has a good capability for capturing the heavy metal ions.
Description
Technical field
The present invention relates to a kind of preparation method of functional amido graphene oxide compound substance, also relate to functional amido graphene oxide compound substance and the application in detecting heavy metal ion thereof according to this method preparation.
Background technology
Along with China's industrialization and quickening of 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 finally is detrimental to health by modes such as drinking-water, biological concentration and food chains.The stream pollution that some mining areas relied 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.Though the trace detection to pollutant has had a lot of proven technique to be applied, but generally these detection methods all need high-precision instrument and equipment to realize, not only cost an arm and a leg, and all be in the laboratory applications stage basically, life is rough with hook with people.Thereby electrochemical detection method cheap, simple to operate becomes the key of dealing with problems.
The galvanochemistry dissolving-out method is widely used for detecting the trace heavy metal ion, and a key factor of influence detection effect promptly is the preenrichment to heavy metal ion, and this can be by adopting the functional material modified electrode improve.The effect of functional material is selectively to catch heavy metal ion, and serves as the good electron transmission medium.Conducting polymer is because the existence of organo-functional group and good conductivity itself become the research focus that detects 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 to make contact to greatest extent in order limiting with heavy metal ion in the solution and to detect the bottleneck that effect further promotes.Having the researchist to propose with the porous silica material is carrier, is applied to the detection of heavy metal ion after organic molecule is modified, received preferably 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 the material and heavy metal ion, but meanwhile, the inertia of porous silicon itself and the existence in complicated duct, the conduction of electronics and freely spreading of metallic ion have been influenced, 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 simultaneously it become a kind of precursor of desirable synthesizing organic-inorganic compound substance.
Summary of the invention
It is limited to the objective of the invention is to overcome the existing effective contact area of electrode modified material that is used to detect the aqueous phase heavy metal ion, electronic conduction is bad, the defective of heavy metal ion trapping ability difference, a kind of preparation method of functional amido graphene oxide compound substance is provided, functional amido graphene oxide compound substance and the application in detecting heavy metal ion thereof by this method preparation also are 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, the organic amine molecule is combined with graphene oxide, and the introducing of amidine functional group can promote the heavy metal ion trapping ability of material greatly 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 compound substance of the present invention, this preparation method are included in solvent and have the stirring 3-72h under 30-120 ℃ with organic amine reagent and described graphene oxide colloidal sol down.
The present invention also provides the functional amido graphene oxide compound substance by above-mentioned preparation method's preparation, and the application of this material in detecting heavy metal ion.
The present invention utilizes graphene oxide as carrier material, when big contact area is provided, also helps electronic conduction; A large amount of oxygen-containing functional groups are rich on the graphene oxide surface in addition, and this had both helped the seizure of counterweight metallic ion, also make it be easy to by the organic molecule functionalization; Functional amido graphene oxide compound substance 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 the infrared spectrogram, X-ray diffraction spectrogram, transmission electron microscope photo and the atomic force microscope photo that obtain as can be known, the amido molecule combines with the graphene oxide lamella by the effect of chemical bond, has formed the graphene oxide compound substance of functional amido.
In addition, the present invention modifies and different heavy metal ion is detected glass-carbon electrode by the galvanochemistry dissolving-out method, the process simple controllable, and obtain highly sensitive detection effect, good reproducibility, the organic amine molecule is incorporated on the graphene oxide sheet surfaces, to Pb by chemical bonded refractory in the material
2+, Cu
2+Or Cd
2+The detection effect is all arranged, 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 is carried out on-line monitoring.
In addition, the present invention is that raw material prepares graphene oxide by chemical oxidation with graphite, and raw materials cost is low, and technology is simple, is suitable for large-scale industrial production;
Description of drawings
Fig. 1 is the infrared spectrogram of the prepared functional amido graphene oxide compound substance of embodiment 1.
Fig. 2 is the X-ray diffractogram of the prepared functional amido graphene oxide compound substance of embodiment 1.
Fig. 3 is the transmission electron microscope picture of the prepared functional amido graphene oxide compound substance of embodiment 1.
Fig. 4 is the atomic force microscope figure of the prepared functional amido graphene oxide compound substance of embodiment 1.
Fig. 5 is that embodiment 1 prepared functional amido graphene oxide compound substance is used to detect 10
-13M Pb
2+The stripping volt-ampere curve figure of ion.
Fig. 6 is that embodiment 2 prepared functional amido graphene oxide compound substances are used to detect 10
-8M Cd
2+The stripping volt-ampere curve figure of ion.
Fig. 7 is that embodiment 3 prepared functional amido graphene oxide compound substances are used to detect 10
-8M Cu
2+The stripping volt-ampere curve figure of ion.
Fig. 8 is that embodiment 4 prepared functional amido graphene oxide compound substances are used to detect 10
-12M Pb
2+The stripping volt-ampere curve figure of ion.
Fig. 9 is that embodiment 5 prepared functional amido graphene oxide compound substances are used to detect 10
-6M Hg
2+The stripping volt-ampere curve figure of ion.
Figure 10 is that embodiment 6 prepared functional amido graphene oxide compound substances are used to detect 10
-11M Pb
2+The stripping volt-ampere curve figure of ion.
Figure 11 is that embodiment 7 prepared functional amido graphene oxide compound substances are used to detect 10
-10M Pb
2+The stripping volt-ampere curve figure of ion.
Embodiment
The invention provides a kind of preparation method of graphene oxide compound substance, this preparation method is included in solvent and has the stirring 3-72h under 30-120 ℃ with organic amine reagent and described graphene oxide colloidal sol down.
In the present invention, the consumption of described solvent gets final product for dissolving organic amine reagent, but in the preferred case, the weight ratio of described organic amine reagent and organic solvent is 1: 120-400.The graphene oxide in the 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 aromatic amine, peptide and the alkyl diamine one or more.Under the preferable case, described organic amine reagent is one or more in p-phenylenediamine (PPD), aniline, cystine, glycocoll, glycylglycine and the ethylenediamine.
In the present invention, described solvent can use 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 for use, but is preferably 2-6mg/ml.
Under the preferable case, the preparation method of described graphene oxide colloidal sol comprises, crystalline flake graphite with 1 weight portion, the concentrated sulphuric acid of the potassium permanganate of 2-5 weight portion and 20-50 weight portion mixes, and with the gained potpourri successively after 0 ℃ to 5 ℃ and 20-40 ℃ stir 4-12h and 8-48h down, add the 50-200 weight parts water, be warming up to 70-90 ℃ afterwards and stir 0.5-1h, adding 3-15 weight portion concentration is the hydrogen peroxide of 10-40 weight %, stirring the back filters, be that hydrochloric acid and the deionized water of 3-15 weight % carries out centrifuge washing with concentration respectively with the filter cake that obtains then, the gluey product that obtains after the washing is mixed with water and carry out ultrasonic dispersion.When described gluey product was mixed with water, the consumption of water had no particular limits, and can suitably select according to different needs.Described concentrated sulphuric acid preferred concentration is more than the 90 weight %.
Under the preferable case, preparation method of the present invention comprises that also the potpourri that will obtain behind the stirring 3-72h filters, and the gained filter cake is carried out drying.
The present invention also provides the functional amido graphene oxide compound substance by method for preparing.
The present invention also provides the application process of functional amido graphene oxide compound substance, and its preferred process is as follows: at first 0.5-3mg functional amido graphene oxide compound substance is dispersed among the 1ml 1 weight %nafion, drips and to be coated with 20-40 μ l to 28mm
2The glass-carbon electrode surface on; Then electrode is immersed in the solution that contains heavy metal ion and adsorb 2-30mins; To take out electrode afterwards and insert in three electrode electrolysers of the electrolysis of hydrochloric acid liquid that contains 0.01M with behind the distilled water flushing 3 times, the control sedimentation potential is-1.8～-1.0V, time are that 60-300s makes heavy metal ion deposit to electrode surface; Last galvanochemistry stripping, the kind of aqueous phase heavy metal ion is relevant with output spike potential and peak height with content.Described galvanochemistry stripping is meant that the heavy metal that the electric potential scanning by forward makes electrode surface be reduced is oxidized to ionic condition again, and stripping is in electrolytic solution.Functional amido graphene oxide compound substance 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.
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment 1
(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 weight %, 0 ℃ ice bath stirs 12h down, add 3g potassium permanganate afterwards, 35 ℃ are stirred 24h, present soil Red to mixed liquor, add 50ml water dilution back control temperature at 90 ℃ and stir 0.5h, adding 5ml concentration is the hydrogen peroxide of 30 weight %, solution becomes golden yellow, be 5 weight % hydrochloric acid centrifuge washings (200ml * 3 time) under the rotating speed of 5000r/min with concentration then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, gluey product after the washing is added to the water, and ultrasonic dispersion obtains the graphene oxide colloidal sol that concentration is 2mg/ml.
(2) functional amido of graphene oxide
The 600mg p-phenylenediamine (PPD) is dissolved in the 100ml ethanol, be that the graphene oxide colloidal sol of 2mg/ml mixes with the described concentration of 100ml step 1 then, the ultrasonic back that is uniformly dispersed is stirred 24h down at 30 ℃, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (volume ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time), through 60 ℃ of dryings, obtain the functional amido graphene oxide compound substance of black.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result such as Fig. 1-shown in Figure 4.
The p-phenylenediamine (PPD) molecule successfully is connected on the graphene oxide lamella as seen from Figure 1.Obtain the compound substance peak position as seen from Figure 2 among the embodiment 1 and taken place obviously to move to low-angle, the graphene oxide interlamellar spacing strengthens, and the p-phenylenediamine (PPD) molecule has been inserted in the 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 functional amido graphene oxide compound substance that 1.5mg is made is dispersed among the nafion of 1 weight % of 1ml, drips to be coated with 20 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-13M Pb
2+Adsorb 5min in the ion solution, take out electrode afterwards and insert in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential makes heavy metal ion deposit to electrode surface for-1.2V, time are 120s, last galvanochemistry stripping, recording of output signals.The result as shown in Figure 5.
As shown in Figure 5, the functional amido graphene oxide compound substance of the present invention preparation has highly sensitive response to lead ion, and signal peak goes out the peak position about-0.6V, 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, 0 ℃ ice bath stirs 4h down, add 5g potassium permanganate afterwards, 20 ℃ are stirred 48h, present soil Red to mixed liquor, add 100ml water dilution back control temperature at 70 ℃ and stir 1h, the hydrogen peroxide that adds 15ml 10 weight %, solution becomes golden yellow, use 3% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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
The 600mg p-phenylenediamine (PPD) is dissolved in the 200ml ethanol, be that the graphene oxide colloidal sol of 2mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 24h down at 80 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 80 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 1.5mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 40 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-8M Cd
2+Adsorb 15min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 300s makes heavy metal ion deposit to electrode surface for-1.0V, time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 6, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-8The M cadmium ion has response, and signal peak goes out the peak position about-0.85V.
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, 0 ℃ ice bath stirs 8h down, add 2g potassium permanganate afterwards, 40 ℃ are stirred 8h, present soil Red to mixed liquor, add 200ml water dilution back control temperature at 80 ℃ and stir 0.5h, add 3ml 40 weight % hydrogen peroxide, solution becomes golden yellow, use 10% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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
The 600mg glycocoll is dissolved in the 300ml ethylene glycol, be that the graphene oxide colloidal sol of 2mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 24h down at 120 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 60 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 0.5mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 30 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-8M Cu
2+Adsorb 30min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 200s makes heavy metal ion deposit to electrode surface for-1.2V and time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 7, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-8The M copper ion has response, and signal peak goes out the peak position about-0.1V.
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, 0 ℃ ice bath stirs 10h down, add 4g potassium permanganate afterwards, 30 ℃ are stirred 36h, present soil Red to mixed liquor, add 150ml water dilution back control temperature at 85 ℃ and stir 1h, the hydrogen peroxide that adds 10ml 20 weight %, solution becomes golden yellow, use 15% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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
The 600mg cystine is dissolved in the 300ml ethanol, be that the graphene oxide colloidal sol of 3mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 12h down at 30 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 70 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 3mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 20 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-12M Pb
2+Adsorb 2min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 60s makes heavy metal ion deposit to electrode surface for-1.0V and time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 8, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-12The M lead ion has response, and the 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, 5 ℃ ice bath stirs 6h down, add 3g potassium permanganate afterwards, 35 ℃ are stirred 8h, present soil Red to mixed liquor, add 50ml water dilution back control temperature at 75 ℃ and stir 0.5h, the hydrogen peroxide that adds 5ml 30 weight %, solution becomes golden yellow, use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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 the 200ml ethanol, be that the graphene oxide colloidal sol of 6mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 48h down at 30 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (volume ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 80 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 2mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 20 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-6M Hg
2+Adsorb 25min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 250s makes heavy metal ion deposit to electrode surface for-1.8V and time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 9, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-6The M mercury ion has response, and signal peak goes out the peak position about 0.3V.
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, 3 ℃ ice bath stirs 5h down, add 3g potassium permanganate afterwards, 30 ℃ are stirred 12h, present soil Red to mixed liquor, add 50ml water dilution back control temperature at 80 ℃ and stir 1h, the hydrogen peroxide that adds 5ml 30 weight %, solution becomes golden yellow, use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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
The 600mg ethylenediamine is dissolved in the 200ml ethanol, be that the graphene oxide colloidal sol of 2mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 3h down at 30 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (volume ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 70 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 1mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 30 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-11M Pb
2+Adsorb 20min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 90s makes heavy metal ion deposit to electrode surface for-1.5V and time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 10, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-11The M lead ion has response, and the 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, 2 ℃ ice bath stirs 4h down, add 3g potassium permanganate afterwards, 30 ℃ are stirred 8h, present soil Red to mixed liquor, add 50ml water dilution back control temperature at 85 ℃ and stir 0.5h, the hydrogen peroxide that adds 10ml 30 weight %, solution becomes golden yellow, use 5% hydrochloric acid centrifuge washing (200ml * 3 time) under the rotating speed of 5000r/min then, with deionized water centrifuge washing (200ml * 3 time) under the rotating speed of 15000r/min, the gluey product after the 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
The 600mg glycylglycine is dissolved in the 200ml water, be that the graphene oxide colloidal sol of 2mg/ml mixes with the described concentration of 100ml step 1 then, ultrasonic being uniformly dispersed, stir 72h down at 30 ℃ at last, rotating speed centrifuging with 5000r/min, with the washing of the mixed liquor (volume ratio of ethanol and water is 1: 1) of ethanol and water (200ml * 3 time),, obtain the functional amido graphene oxide compound substance of black through 60 ℃ of dryings.By infrared spectrum, X-ray diffraction, transmission electron microscope and atomic force microscope this functional amido graphene oxide compound substance is detected, testing result is similar to Example 1.
(3) detection of heavy metal ion
The functional amido graphene oxide compound substance that 2.5mg is made is dispersed among the 1%nafion of 1ml, drips to be coated with 20 μ l and to modify on the glass-carbon electrode surface, electrode is immersed to contain 10 then
-10M Pb
2+Adsorb 20min in the ion solution, taking out electrode afterwards inserts in three electrode electrolysers that contain 0.01M electrolysis of hydrochloric acid liquid with behind the distilled water flushing 3 times, the control sedimentation potential is that 150s makes heavy metal ion deposit to electrode surface for-1.2V and time, last galvanochemistry stripping, recording of output signals.
As shown in Figure 11, the functional amido graphene oxide compound substance of the present invention's preparation is to 10
-10The M lead ion has response, and the signal peak peak height is higher than example 1.
Claims (10)
1. the preparation method of a graphene oxide compound substance is characterized in that, this preparation method is included in solvent and has the stirring 3-72h under 30-120 ℃ with organic amine reagent and described graphene oxide colloidal sol down.
2. preparation method according to claim 1, wherein, the weight ratio of described organic amine reagent and solvent is 1: 120-400, the graphene oxide in the described graphene oxide colloidal sol and the weight ratio of organic amine reagent are 1: 1-3.
3. preparation method according to claim 1 and 2, wherein, described organic amine reagent is to be selected from aromatic amine, peptide and the alkyl diamine one or more.
4. preparation method according to claim 3, wherein, described organic amine reagent is one or more in p-phenylenediamine (PPD), aniline, cystine, glycocoll, glycylglycine and the ethylenediamine.
5. preparation method according to claim 1 and 2, wherein, described solvent is one or more in ethanol, ethylene glycol and the water.
6. preparation method according to claim 1 and 2, wherein, described graphene oxide collosol concentration is 2-6mg/ml.
7. preparation method according to claim 1, wherein, the preparation method of described graphene oxide colloidal sol comprises, crystalline flake graphite with 1 weight portion, the concentrated sulphuric acid of the potassium permanganate of 2-5 weight portion and 20-50 weight portion mixes, and with the gained potpourri successively after 0 ℃ to 5 ℃ and 20-40 ℃ stir 4-12h and 8-48h down, add the 50-200 weight parts water, be warming up to 70-90 ℃ afterwards and stir 0.5-1h, adding 3-15 weight portion concentration is the hydrogen peroxide of 10-40 weight %, stirring the back filters, be respectively hydrochloric acid and the deionized water wash of 3-15 weight % with concentration with the filter cake that obtains then, the gluey product that obtains after the washing is mixed with water and carry out ultrasonic dispersion.
8. preparation method according to claim 1, wherein, this preparation method comprises that also the potpourri that will obtain behind the stirring 3-72h filters, and the gained filter cake is carried out drying.
9. a functional amido graphene oxide compound substance is characterized in that, this functional amido graphene oxide compound substance is by any described method preparation among the claim 1-8.
10. the application of the described functional amido graphene oxide of claim 9 compound substance in detecting heavy metal ion.
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Cited By (12)
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| CN102602915A (en) * | 2012-03-02 | 2012-07-25 | 北京化工大学 | Method for reducing graphene oxide and preparing conductive nanometer composite material |
| CN102879431A (en) * | 2012-10-15 | 2013-01-16 | 苏州大学 | Gas sensor based on reduced graphene oxide and preparation method thereof |
| CN103007886A (en) * | 2012-12-25 | 2013-04-03 | 复旦大学 | Synthetic method of magnetic graphene mesoporous material used for separation and enrichment in peptideomics |
| CN103420363A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Preparation method and application of graphene paper |
| CN103466610A (en) * | 2013-09-25 | 2013-12-25 | 中国科学院理化技术研究所 | Graphene chemical modification method |
| CN103675065A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Salicylic acid functionalized graphene modified electrode and heavy metal detection method thereof |
| CN104761753A (en) * | 2015-03-31 | 2015-07-08 | 南京理工大学 | Diaminobenzene-functionalized graphene nanomaterial and preparation method thereof |
| CN105733145A (en) * | 2015-08-03 | 2016-07-06 | 河南科技大学 | Glycine-modified graphene oxide, polyvinyl alcohol halogen-free flame-retarding material and preparation method thereof |
| CN105990031A (en) * | 2015-03-31 | 2016-10-05 | 南京大学 | Diaminobenzene functionalized graphene-doped active carbon composite electrode, preparation method thereof and application of diaminobenzene-functionalized graphene-doped active carbon composite electrode to electric adsorption desalination |
| CN106241783A (en) * | 2016-07-29 | 2016-12-21 | 新乡学院 | A kind of synthetic method of amido Graphene sewage-treating agent |
| 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 |
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| CN102602915A (en) * | 2012-03-02 | 2012-07-25 | 北京化工大学 | Method for reducing graphene oxide and preparing conductive nanometer composite material |
| CN103420363A (en) * | 2012-05-25 | 2013-12-04 | 海洋王照明科技股份有限公司 | Preparation method and application of graphene paper |
| CN102879431A (en) * | 2012-10-15 | 2013-01-16 | 苏州大学 | Gas sensor based on reduced graphene oxide and preparation method thereof |
| CN103007886B (en) * | 2012-12-25 | 2014-12-03 | 复旦大学 | Synthetic method of magnetic graphene mesoporous material used for separation and enrichment in peptideomics |
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| CN103675065A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Salicylic acid functionalized graphene modified electrode and heavy metal detection method thereof |
| CN103675065B (en) * | 2013-12-18 | 2016-03-09 | 天津工业大学 | A kind of salicylic acid functionalization graphene modified electrode and heavy metal detection method thereof |
| CN104761753A (en) * | 2015-03-31 | 2015-07-08 | 南京理工大学 | Diaminobenzene-functionalized graphene nanomaterial and preparation method thereof |
| CN105990031A (en) * | 2015-03-31 | 2016-10-05 | 南京大学 | Diaminobenzene functionalized graphene-doped active carbon composite electrode, preparation method thereof and application of diaminobenzene-functionalized graphene-doped active carbon composite electrode to electric adsorption desalination |
| CN105733145A (en) * | 2015-08-03 | 2016-07-06 | 河南科技大学 | Glycine-modified graphene oxide, polyvinyl alcohol halogen-free flame-retarding material and preparation method thereof |
| CN106241783A (en) * | 2016-07-29 | 2016-12-21 | 新乡学院 | A kind of synthetic method of amido Graphene sewage-treating agent |
| 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 |
| WO2023236352A1 (en) * | 2022-06-07 | 2023-12-14 | 苏州大学 | Amine-compound-modified graphene film and preparation method therefor |
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