CN104730121A - Multi-wall carbon nano-tube bridged 3D graphene conductive network and preparation method thereof - Google Patents
Multi-wall carbon nano-tube bridged 3D graphene conductive network and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carboxylation multi-wall carbon nano-tube bridged 3D graphene conductive network and a preparation method thereof. The method comprises the steps of preparing graphite oxide, preparing cyclodextrin functionalized graphene and preparing the carboxylated multi-wall carbon nano-tube bridged 3D graphene conductive network. The covalence organic decoration technology and the non-covalence organic decoration technology are scientifically combined, a nano hybridized material responding to electrochemical promotion of dopamine, ascorbic acid, purine trione and tryptophan is established, and the electrochemical performance of a nano material is adjusted by changing the type of cyclodextrin and the content of the carboxylated multi-wall nano-tube; the 3D functionalized nano material is simple in synthesis step, efficient, simple in after-treatment and easy for mass preparation; moreover, by adopting the 3D functionalized nano material, DA, AA, UA and Trp can be sensitively detected in a complicated environment in the presence of other interference substances; the defect that CDs is likely to drop can be effectively solved, and the conductivity of the system and the CDs selectivity can be remarkably improved by virtue of the non-covalence bridging of the carboxylated carbon nano-tube.
Description
Technical field
3D graphene conductive network that the present invention relates to a kind of multi-walled carbon nano-tubes bridging and preparation method thereof, particularly there is nano-hybrid material dopamine, ascorbic acid, uric acid and tryptophane galvanochemistry being strengthened to response, can the field of material preparation of physiological selectivity Electrochemical Detection and quantification in clinical diagnosis and neurochemistry research field in early days.
Background technology
Dopamine (3,4-dihydroxyphenylethylamine, DA), as most typical Neurotransmitter, plays key effect at control mammalian metabolism, cardiovascular system, nervous centralis, kidney and hormone function.DA concentration abnormality is the sensitive indicator of some pathological state.As, schizophrenia, senile dementia, Parkinson's disease and psychopathic disorder etc.Because DA is electroactive, can be detected by electrochemical techniques.And because the response of this technology is fast, highly sensitive, selectivity is good, simple to operate, low cost, lack the advantages such as interference and cause huge research interest.DA and ascorbic acid (AA), uric acid (UA) and tryptophane (Trp) co-exist in our body fluid, as having overlapping volt-ampere response on naked glass-carbon electrode (GCE), being difficult to detect, therefore needing development of new material effectively to modify GCE.Research and develop effective sensing material and physiological selectivity Electrochemical Detection and quantification in early clinical diagnosis and neurochemistry research field seemed most important, develop a kind of easy method come selective determination analyze thing remain a challenge.
Reversible and the adaptivity that Subjective and Objective molecular recognition chemistry is intrinsic, from multiple non-covalent interaction, opens the new platform building stimuli responsive material type.Introduce host-guest chemistry and not only enriched responsive materials field, also give their new wide application prospects.Various main body such as cyclodextrin (CDs), crown ether, calixarenes, melon ring (CB), post aromatic hydrocarbons have developed structure responsive materials.As a main body the most extensively studied, CDs, can interact with multiple organic and inorganic and biological guest molecule, stable host-guest coordination compound can be formed, as long as they have fully suitable polarity and size can form host and guest's body complex, present supramolecular selectivity and charming Supramolecular Recognition ability.Meanwhile, CDs is environmental protection, water miscible, and can improve dissolubility and the stability of decorative material.But, these modified layer poorly conductives.Therefore, development of new can improve above problem based on the modified electrode of CDs.
Because have significant electrocatalysis characteristic and larger specific surface area, carbon nano-tube (CNTs) and Graphene have been widely used in the sensitivity improving sensor, effectively can improve object and interelectrode Direct electron transfer speed.In addition, it also increases the surface area of electrode indirectly, and causing increases object and interelectrode contact area.Up to the present, many application that CDs functionalized carbon sill analyzes thing for difference in electrochemical sensor are in the news, but, wherein for detecting the fewer of dopamine.On the other hand, the individual character of the allotrope of these carbon, namely carbon nano-tube (one dimension) and Graphene (two dimension) monomer can Synthesis three-dimensional porous structure bodies, will significantly increase the application potential preparing biological and chemical sensor.In a word, the reinforcement Detection results of nanotube and CDs is not obvious; The system of Graphene and CDs is all much non-covalent systems.The CDs amount needed is very large, and CDs easily comes off.(1.G.Alarcón-Angelesa,B.Pérez-Lópeza,M.Palomar-Pardave,et al.Enhanced host–guest electrochemical recognition of dopamine using cyclodextrin in thepresence of carbon nanotubes.Carbon,2008,46(6):898～906.2.María TeresaRamírez-Silva,Manuel Palomar-Pardavé,Silvia Corona-
et al.Guest-HostComplex Formed between Ascorbic Acid andβ-Cyclodextrin Immobilized on the Surfaceof an Electrode.Molecules,2014,19(5),5952-5964.)。
Summary of the invention
The present invention is directed to complex operation that prior art exists, the deficiency such as step is various, detection sensitivity is low; Provide a kind of 3D graphene conductive network of multi-walled carbon nano-tubes bridging.
Another object of the present invention is to provide the preparation method of the 3D graphene conductive network of multi-walled carbon nano-tubes bridging.
The technical solution realizing the object of the invention is: a kind of 3D graphene conductive network of multi-walled carbon nano-tubes bridging, and its general structure is as follows:
The 3D graphene conductive network of above-mentioned multi-walled carbon nano-tubes bridging is by obtaining oxidation graphite solid by the process of natural graphite powder degree of depth Strong oxdiative, warp is at N again, ultrasonic disperse in dinethylformamide (DMF), obtain graphene oxide DMF dispersion liquid, after activated carboxylic, prepare the graphene oxide (GO-CDs) of cyclodextrin (CDs) functionalization, after adding carboxylated carbon nano-tube (MWNTs) further, after heat reduction, filtration, washing and drying, obtain the 3D graphene conductive network of multi-walled carbon nano-tubes bridging.
Its concrete technique comprises the following steps:
Step 1, prepare oxidation graphite solid with natural flake graphite powder;
Step 2, ultrasonic preparation graphene oxide DMF suspending liquid;
The graphene oxide GO-CDs of step 3, preparation CDs functionalization;
Step 4, prepare the DMF suspending liquid of GO-CDs and the DMF suspending liquid of carboxylated carbon nano-tube respectively;
Step 5, by after the mixing of two of step 4 kinds of suspending liquid, add reductive agent stirring reaction at 50 ~ 80 DEG C;
Namely the 3D graphene conductive network of multi-walled carbon nano-tubes bridging is obtained after step 6, filtration under diminished pressure, washing, drying.
Oxidation graphite solid described in step 1 adopts the preparation of the Hummers method after improving.
The ratio of GO-CDs and the DMF described in step 4 is (1:10 ~ 5:1) mg/mL; The ratio of MWNTs and DMF is (1:10 ~ 5:1) mg/mL; Ultrasonic time is 1 ~ 10h.
Reductive agent described in step 5 is the potpourri of hydrazine hydrate and ammoniacal liquor, and the ratio of GO-CDs and hydrazine hydrate is (5:1 ~ 1:10) mg/ μ L; The ratio of ammoniacal liquor and hydrazine is (5:1 ~ 20:1) μ L/ μ L; Wherein, ammonia concn is 25-28wt%, and the stirring reaction time is 1 ~ 24h.
Compared with prior art, the present invention utilizes covalent functionalization after GO edge grappling CDs, adds carboxylated nanotube and carries out interlayer bridging.GO-CDs synchronously reduce and with the non-covalent self assembly of MWNTs after, build 3D conductive network.Save a lot of human and material resources and financial resources by one kettle way preparation in this building-up process, and fundamentally protect environment, and be conducive to large-scale production.Organic covalency and non-covalent chemical combine by this nano material, establish the electrical-conductive nanometer network that multiple interaction is integrated.Wherein, comprise the hydrogen bond action of the remaining oxy radical of carboxylated nanotube and Graphene, π-π interacts, Host-guest Recognition etc.Adding the electric conductivity of reinforcing material of nanotube, the 3D porous structure founded will be conducive to the effective collision of detection molecules and CDs.Nano-sensor based on this material shows good catalytic activity to AA, DA, UA and Trp, and synthesis step is simple, efficiently, sensitive, physiological selectivity Electrochemical Detection and quantize that there is important popularization, using value in clinical diagnosis and neurochemistry research field in early days.Preparation method of the present invention presses close to the requirement of Green Chemistry, and simple to operate, is easy to control, and is conducive to industrialized mass.
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail.
Accompanying drawing explanation
Fig. 1 is the 3D graphene conductive network preparation process schematic diagram of multi-walled carbon nano-tubes bridging prepared by the present invention.
Fig. 2 is the infrared spectrogram of the 3D graphene conductive network of the multi-walled carbon nano-tubes bridging of synthesis in the embodiment of the present invention 1.
Fig. 3 detects CV curve based on the nano-probe of the 3D graphene conductive network struction of the multi-walled carbon nano-tubes bridging of synthesis in the embodiment of the present invention 1 to DA.a,GCE；b,GO-CDs；c,GN-CDs；d,GN-CDs-MWNTs.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are described in further detail; the present embodiment is implemented under with technical solution of the present invention prerequisite; give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
As shown in Figure 1, a kind of 3D graphene conductive network of multi-walled carbon nano-tubes bridging and one pot preparation method, the method comprises the following steps:
Step 1, prepare oxidation graphite solid with natural flake graphite powder; Described oxidation graphite solid adopts the preparation of the Hummers method after improving;
Step 2, ultrasonic preparation graphene oxide DMF suspending liquid;
The graphene oxide (GO-CDs) of step 3, preparation CDs functionalization;
Step 4, respectively prepare GO-CDs and carboxylic carbon nano-tube DMF suspending liquid, wherein, the ratio of described GO-CDs and DMF is (1:10 ~ 5:1) mg/mL; The ratio of MWNTs and DMF is (1:10 ~ 5:1) mg/mL; Ultrasonic time is 1 ~ 10h;
Step 5, by after the mixing of two of step 4 kinds of suspending liquid, add the 3D graphene conductive network that reductive agent builds multi-walled carbon nano-tubes bridging; Described reductive agent is the potpourri of hydrazine hydrate and ammoniacal liquor; The ratio of GO-CDs and hydrazine hydrate is (5:1 ~ 1:10) mg/ μ L; The ratio of ammoniacal liquor and hydrazine hydrate is (5:1 ~ 20:1) μ L/ μ L; Temperature of reaction is 50 ~ 80 DEG C; The stirring reaction time is 1 ~ 24h;
Namely the 3D graphene conductive network of multi-walled carbon nano-tubes bridging is obtained after step 6, filtration under diminished pressure, washing, drying.
Embodiment 1
The first step, the preparation of oxidation graphite solid;
At 80 DEG C, with the 30mL concentrated sulphuric acid, 10g potassium persulfate and 10g phosphorus pentoxide by after the pre-oxidation of 20g native graphite, be washed to pH=7, air drying spends the night stand-by;
The 460mL concentrated sulphuric acid is cooled to about 0 DEG C, then the graphite of 20g pre-oxidation is joined wherein, slowly add 60g potassium permanganate, make system temperature be no more than 20 DEG C, after interpolation, be warmed up to 35 DEG C, after stirring 2h, and slowly add 920mL deionized water in batches, make system temperature be no more than 98 DEG C, then after stirring 15 minutes, add 2.8L deionized water and 50mL 30% hydrogen peroxide.By the glassy yellow suspending liquid decompress filter obtained, washing.Until there is no sulfate ion in filtrate, and in time neutral, product dried in 60 DEG C of vacuum, obtains oxidation graphite solid;
Second step, loads round-bottomed flask by 200mg graphite oxide powder, then adds 15mLN, dinethylformamide (DMF) solvent, after ultrasonic 5h, obtain the suspending liquid of graphene oxide; Add 40mL thionyl chloride (SOCl
2), react 24h at 70 DEG C after, decompression distillation is to remove unnecessary SOCl
2, finally add the 4g β-CDs being dissolved in 22mL DMF, at 90 DEG C, oil bath reacts 2 days, obtains GO-CDs.
3rd step, by the carboxylated MWNTs of 20mg second step product GO-CDs and 20mg respectively ultrasonic 5h to be scattered in 20mL DMF (DMF) inner.Then by after two of fine dispersion kinds of suspending liquid mixing, 600 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 60 DEG C of stirring reaction 3.5h.
4th step, the crude product the 3rd step obtained is through suction filtration, and washing, after drying, obtains product.
Infrared spectrum as shown in Figure 2, proves that this nano-hybrid material successfully synthesizes.
CV curve as shown in Figure 3, proves that the detecting device of the graphene conductive network struction of carboxylic carbon nano-tube bridging has significant response to DA.
Embodiment 2
The first to two step, with the step one in embodiment 1 to two;
3rd step, by the carboxylated MWNTs of 20mg second step product GO-CDs and 20mg respectively ultrasonic 7h to be scattered in 20mL DMF (DMF) inner.Then by after two of fine dispersion kinds of suspending liquid mixing, 600 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 60 DEG C of stirring reaction 3.5h.
4th step, with the step 4 in embodiment 1.
Embodiment 3
The first to two step, with the step one in embodiment 1 to two;
3rd step, is scattered in 1mL DMF by the ultrasonic 10h of 5mg second step product GO-CDs; The ultrasonic 1h of the carboxylated MWNTs of 5mg is scattered in 50mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 250 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 50 DEG C of stirring reaction 10h.
4th step, with the step 4 in embodiment 1.
Embodiment 4
The first to two step, with the step one in embodiment 1 to two;
3rd step, by carboxylated for 20mg second step product GO-CDs and 20mg MWNTs, ultrasonic disperse 5h is in 20mLN respectively, and dinethylformamide (DMF) is inner.Then by after two of fine dispersion kinds of suspending liquid mixing, 600 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 80 DEG C of stirring reaction 3.5h.
4th step, with the step 4 in embodiment 1.
Embodiment 5
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 5mg second step product GO-CDs ultrasonic disperse in 50mL DMF; The carboxylated MWNTs of 10mg is scattered in 2mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 20 μ L ammoniacal liquor and 1 μ L hydrazine hydrate is added, 60 DEG C of stirring reaction 10h.
4th step, with the step 4 in embodiment 1.
Embodiment 6
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 5mg second step product GO-CDs ultrasonic disperse in 50mL DMF; The carboxylated MWNTs of 10mg is scattered in 2mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 40 μ L ammoniacal liquor and 5 μ L hydrazine hydrates are added, 60 DEG C of stirring reaction 5h.
4th step, with the step 4 in embodiment 1.
Embodiment 7
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 5mg second step product GO-CDs ultrasonic disperse in 40mL DMF; The carboxylated MWNTs of 10mg is scattered in 5mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 40 μ L ammoniacal liquor and 6 μ L hydrazine hydrates are added, 70 DEG C of stirring reaction 6h.
4th step, with the step 4 in embodiment 1.
Embodiment 8
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 5mg second step product GO-CDs ultrasonic disperse in 30mL DMF; The carboxylated MWNTs of 10mg is scattered in 10mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 100 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 60 DEG C of stirring reaction 1h.
4th step, with the step 4 in embodiment 1.
Embodiment 9
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 20mg second step product GO-CDs ultrasonic disperse in 20mL DMF; The carboxylated MWNTs of 2mg is scattered in 10mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 100 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 60 DEG C of stirring reaction 24h.
4th step, with the step 4 in embodiment 1.
Embodiment 9
The first to two step, with the step one in embodiment 1 to two;
3rd step, by 20mg second step product GO-CDs ultrasonic disperse in 20mL DMF; The carboxylated MWNTs of 2mg is scattered in 10mL DMF.Then by after two of fine dispersion kinds of suspending liquid mixing, 100 μ L ammoniacal liquor and 50 μ L hydrazine hydrates are added, 65 DEG C of stirring reaction 12h.
4th step, with the step 4 in embodiment 1.
Claims (9)
1. a 3D graphene conductive network for multi-walled carbon nano-tubes bridging, it is characterized in that, its general structure is as follows:
2. the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 1, it is characterized in that, described 3D graphene conductive network is prepared by following steps:
Step 1, prepare oxidation graphite solid with natural flake graphite powder;
Step 2, ultrasonic preparation graphene oxide DMF suspending liquid;
The graphene oxide GO-CDs of step 3, preparation CDs functionalization;
Step 4, prepare the DMF suspending liquid of GO-CDs and the DMF suspending liquid of carboxylated carbon nano-tube respectively;
Step 5, by after the mixing of two of step 4 kinds of suspending liquid, add reductive agent stirring reaction at 50 ~ 80 DEG C;
Namely the 3D graphene conductive network of multi-walled carbon nano-tubes bridging is obtained after step 6, filtration under diminished pressure, washing, drying.
3. the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 2, is characterized in that, the oxidation graphite solid described in step 1 adopts the preparation of the Hummers method after improving.
4. the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 2, it is characterized in that, the ratio of GO-CDs and the DMF described in step 4 is (1:10 ~ 5:1) mg/mL; Carboxylated carbon nano-tube and the ratio of DMF are (1:10 ~ 5:1) mg/mL; , ultrasonic time is 1 ~ 10h.
5. the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 2, it is characterized in that, the reductive agent described in step 5 is the potpourri of hydrazine hydrate and ammoniacal liquor, and the ratio of GO-CDs and hydrazine hydrate is (5:1 ~ 1:10) mg/ μ L; The volume ratio of ammoniacal liquor and hydrazine hydrate is 5:1 ~ 20:1; Wherein, ammonia concn is 25-28wt%, and the stirring reaction time is 1 ~ 24h.
6. a preparation method for the 3D graphene conductive network of multi-walled carbon nano-tubes bridging, is characterized in that, comprise the steps:
Step 1, prepare oxidation graphite solid with natural flake graphite powder;
Step 2, ultrasonic preparation graphene oxide DMF suspending liquid;
The graphene oxide GO-CDs of step 3, preparation CDs functionalization;
Step 4, prepare the DMF suspending liquid of GO-CDs and the DMF suspending liquid of carboxylated carbon nano-tube respectively;
Step 5, by after the mixing of two of step 4 kinds of suspending liquid, add reductive agent stirring reaction at 50 ~ 80 DEG C;
Namely the 3D graphene conductive network of multi-walled carbon nano-tubes bridging is obtained after step 6, filtration under diminished pressure, washing, drying.
7. the preparation method of the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 6, is characterized in that, the oxidation graphite solid described in step 1 adopts the preparation of the Hummers method after improving.
8. the preparation method of the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 6, it is characterized in that, the ratio of GO-CDs and the DMF described in step 4 is (1:10 ~ 5:1) mg/mL; Carboxylated carbon nano-tube and the ratio of DMF are (1:10 ~ 5:1) mg/mL; , ultrasonic time is 1 ~ 10h.
9. the preparation method of the 3D graphene conductive network of multi-walled carbon nano-tubes bridging as claimed in claim 6, it is characterized in that, reductive agent described in step 5 is the potpourri of hydrazine hydrate and ammoniacal liquor, and the ratio of GO-CDs and hydrazine hydrate is (5:1 ~ 1:10) mg/ μ L; The volume ratio of ammoniacal liquor and hydrazine hydrate is 5:1 ~ 20:1; Wherein, ammonia concn is 25-28wt%, and the stirring reaction time is 1 ~ 24h.
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| CN107381546A (en) * | 2017-07-25 | 2017-11-24 | 常州大学 | The method that one step hydro thermal method prepares carbon nano tube/graphene hydridization conductive material |
| CN109959688A (en) * | 2017-12-25 | 2019-07-02 | 南京理工大学 | The method for detecting dopamine and uric acid simultaneously based on poly- l-Glutathione modified glassy carbon electrode |
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| CN109682871A (en) * | 2019-01-16 | 2019-04-26 | 扬州大学 | β-CD@CdS nanometer rods and preparation method thereof applied to photoelectricity bio-sensing |
| CN109682871B (en) * | 2019-01-16 | 2021-04-16 | 扬州大学 | beta-CD @ CdS nanorod applied to photoelectric biosensing and preparation method thereof |
| CN114364311A (en) * | 2019-08-20 | 2022-04-15 | 波士顿科学国际有限公司 | Non-covalent modification of graphene-based chemical sensors |
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