CN104777207B - A kind of three-dimensional nitrogen-doped graphene composite and its preparation method and application - Google Patents
A kind of three-dimensional nitrogen-doped graphene composite and its preparation method and application Download PDFInfo
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Abstract
Application the invention discloses a kind of three-dimensional nitrogen-doped graphene composite and preparation method thereof and in electrochemical biosensor.The present invention by three-dimensional nitrogen-doped graphene high-specific surface area, good biocompatibility, high conductivity characteristic, construct three-dimensional nitrogen-doped graphene composite, first using foamed material as substrate, under containing inert gas, hydrogen and carbon source and nitrogen conditions, chemical gaseous phase depositing process is utilized（CVD）, obtain the three-dimensional nitrogen-doped graphene containing substrate；Then three-dimensional nitrogen-doped graphene is performed etching, cleaning treatment obtains three-dimensional nitrogen-doped graphene composite.Three-dimensional nitrogen-doped graphene and enzyme/non-enzymatic material progress is compound, obtain corresponding three-dimensional nitrogen-doped graphene composite；Electrode is made in these three-dimensional nitrogen-doped graphene composites, the detection to different kinds of molecules such as glucose, dopamine, paracetamols, there is the corresponding high sensitivity of electric current, stability is good, the characteristics of having a wide range of application.
Description
Technical field
The invention belongs to electrochemical biosensor field, is related to a kind of three-dimensional nitrogen-doped graphene composite and its preparation
Methods and applications.
Background technology
In modern society, electrochemica biological sensor is highly sensitive in clinical medicine, bioengineering, environmental monitoring, molecule
There is important application meaning in degree detection or even biological fuel cell field.Detection sensitivity and detectable limit are to weigh electrochemical student
The important indicator of thing sensor performance.Whether electrochemica biological sensor has good detection sensitivity and detectable limit, closes
Can what key was electrochemical electrode have good electrical conductivity, specific surface area and biocompatibility.However, traditional glass-carbon electrode
Poorly conductive, poor biocompatibility and the shortcomings such as specific surface area is low be present so that electrochemica biological sensor is to biomolecule
Detection sensitivity is low, specific selectivity is poor.
Graphene is since 2004 are reported by An Deliehaimu and Constantine Nuo Woxiao loves, with its high ratio
Surface area, high electron mobility and excellent physics, chemistry, optically and mechanically performance is widely studied, and it is two
There is boundless application prospect in the fields such as dimension thin-film material, electronic device, composite and high-efficiency energy-storage device.Wherein
Graphene modified glass-carbon electrode has widely been studied in bio-sensing field, such as multi-walled carbon nanotube, graphene oxide
Detection (S.Cheemalapati, S.Palanisamy, V.Mani and of the glass-carbon electrode of modification to dopamine etc.
S.M.Chen, Talanta, 2013,117,297~304.) and Nafion, Nano silver grain, redox graphene modification
Glass-carbon electrode Ascorbic Acid etc. detection (B.Kaur, T.Pandiyan, B.Satpatiand and R.Srivastava,
Colloids and Surfaces B, 2013,111,97~106.).But repaiied at these based on oxidation/reduction graphene oxide
In the electrode material of decorations, graphene generally requires basal electrode (glass-carbon electrode) support, and electrode material structure is complex,
And graphene is easily reunited, thus the characteristic that graphene specific surface area is big, conductance is high can not be given full play to.
Three-dimensional nitrogen-doped graphene can independently be used as an electrode material without base material and fixed material using self-supporting
Material, makes electrode material structure largely be simplified.In addition, porous structure makes it have very big specific surface area,
The corresponding area increase of electrochemical reaction can occur, make it have the corresponding sensitivity of very high electrochemistry.In addition, nitrogen
Introducing also makes it have good biocompatibility while its conductive capability is increased, and can be used as electrochemica biological sensor
Good electrode material.
The content of the invention
It is an object of the invention to provide a kind of preparation method of three-dimensional nitrogen-doped graphene composite and in electrochemical student
The application of thing sensing.
A kind of preparation method of three-dimensional nitrogen-doped graphene composite, comprises the following steps：Using foamed material as substrate,
Using vapor deposition method, first in hydrogen and inert atmosphere, after foam substrate is risen into annealing temperature annealing by room temperature, then it is passed through
Carbon source and nitrogen source grow N doping three-dimensional grapheme under growth temperature in foam substrate surface catalysis, are then cooled to room temperature,
The N doping three-dimensional grapheme containing substrate is taken out, then the three-dimensional nitrogen-doped graphene containing substrate is performed etching, cleaning treatment
Obtain three-dimensional nitrogen-doped graphene.
Described foamed material is nickel, cobalt, iron, aluminium, gold, silver, copper, zinc, molybdenum, tungsten, titanium, vanadium, chromium, ruthenium, rhodium, platinum, palladium bubble
At least one of foam and polymeric foamed material, preferably nickel foam；The size of the foam substrate be 0.1 × 0.1cm~100 ×
100cm, preferably 1 × 1cm；The carbon source is carbon monoxide, methane, ethane, propane, butane, pentane, hexane, butine, hexamethylene
Alkane, ethene, propylene, butadiene, amylene, cyclopentadiene, acetylene, methanol, ethanol, benzene, at least one of toluene and phthalocyanine, preferably
Methane；The nitrogen source is ammonia, hydrazine, nitric oxide, nitrogen dioxide, the preferably at least one of nitrogen, ammonia；Other, carbon source
With nitrogen source from least one that same substance is nitrobenzene, aminobenzene, amino acid, propionitrile.
Described chemical vapour deposition technique is in hydrogen and inert atmosphere, and foam substrate is risen into annealing temperature by room temperature
After annealing, then carbon source and nitrogen source are passed through under growth temperature in substrate surface catalytic growth N doping three-dimensional grapheme, be cooled to
Room temperature, take out the N doping three-dimensional grapheme containing substrate；The heating-up time that the temperature of the annealing steps is risen to by room temperature is 10
~60min, preferably 20~40min, in the annealing steps, temperature is 700~1500 DEG C, preferably 1000 DEG C, the time is 1~
30min, preferably 5min；In the catalytic growth step, temperature be 700~1500 DEG C, preferably 900~1100 DEG C, more preferably
1000 DEG C, the time is 1~25min, preferably 4~6min；In the cooling step, the time is 1~100min, preferably 25~
35min；The flow velocity of the hydrogen is 20~1000sccm, preferably 50~500sccm, more preferably 200sccm；The inert gas
Flow velocity be 20~1000sccm, preferably 400~600sccm, more preferably 500sccm；The flow velocity of the carbon source be 1~
100sccm, preferably 5~15sccm, more preferably 10sccm；The flow velocity of the nitrogen source is 1~200sccm, preferably 10~20sccm,
More preferably 14sccm；The ratio of the carbon source and nitrogen source is 1:2~1:1, more preferably 5:7.
Preferably, the nitrogen-doped graphene containing substrate obtained, which is transferred in etching liquid, to carry out being transferred to cleaning fluid after etching completely
In washed；Etching liquid used is at least one of iron chloride, nitric acid, the concentrated sulfuric acid, chloroazotic acid, potassium permanganate, preferably chlorine
Change iron or nitric acid, ferric chloride concn is 0.1~2.5mol/L, preferably 0.5~2.5mol/L, concentration of nitric acid 1:20~1:5, more
It is preferred that 1:10, etch period is 6~48h, preferably 11~13h；Cleaning cleaning fluid used is ethanol, ultra-pure water, acetone extremely
Few one kind, preferably ultra-pure water, cleaning process are to be soaked 6 times with cleaning fluid, and first 2 times each soak time is 5~60min, preferably
15~25min, latter 4 times each soak times are 5~30min, preferably 8~12min, are replaced and cleaned liquid before immersion every time.
A kind of three-dimensional nitrogen-doped graphene composite, by the preparation method of above-mentioned three-dimensional nitrogen-doped graphene composite
It is prepared.
Application of the above-mentioned three-dimensional nitrogen-doped graphene composite in electrochemical field.
A kind of three-dimensional nitrogen-doped graphene enzyme composites, are prepared by the method comprised the following steps：Will
Above-mentioned three-dimensional nitrogen-doped graphene composite carries out Combined Processing with dielectric material and obtains three-dimensional nitrogen-doped graphene medium material
Expect zymophore, then three-dimensional nitrogen-doped graphene dielectric material zymophore and enzyme are subjected to Combined Processing and obtain three-dimensional N doping graphite
Alkene enzyme composite.
Dielectric material be polyacrylic acid, polyethyleneimine, polyaniline, polyfructosan, starch, heparin, agar, Nafion,
Chitosan, Pt nano-particles, Zn nano-particles, Au nano-particles, at least one of ZnO, Ag nano-particle, preferably chitosan and
Nafion；Enzyme material be glucose oxidase, catalase, myoglobins, hemoglobin, porphyrin, DNA methylation enzyme extremely
Few one kind, preferably glucose oxidase and myoglobins；The process of Combined Processing is ultrasound, soaks, be overcritical, vibrating, chemistry
Bonding, stirring, at least one of centrifugation, preferably ultrasound and immersion；It is molten that obtained three-dimensional nitrogen-doped graphene is placed in dielectric material
The time that liquid carries out Combined Processing is 20~200min, preferably 110~130min；Three-dimensional nitrogen-doped graphene dielectric material enzyme carries
The time that body carries out Combined Processing with enzyme is 1~48h, preferably 23~25h.
A kind of three-dimensional nitrogen-doped graphene non-enzymatic composites, are prepared by the method comprised the following steps：
Above-mentioned three-dimensional nitrogen-doped graphene composite and non-enzyme material are subjected to Combined Processing；Described non-enzyme material is α-ring paste
Essence, beta-schardinger dextrin, gamma-cyclodextrin, amino cyclodextrin derivatives, Pt nano-particles, single-walled carbon nanotube, multi-walled carbon nanotube,
C60, Zn nano-particles, Au nano-particles, at least one of ZnO, Ag nano-particle, preferably beta-schardinger dextrin；The process of Combined Processing
For ultrasonic, immersion, overcritical, vibration, chemical bonding, stirring, the preferably at least one centrifuged, ultrasound and immersion；Combined Processing
Time be 0.5~24h, preferably 0.5~13h.
The three-dimensional nitrogen-doped graphene composite of gained is fabricated to electrode, electricity is carried out to biologic inorganic organic molecule
Chemical detection；Glucose, dopamine, paracetamol, chlorophenol, nitrophenol, uric acid, vitamin C, natrium nitrosum, cholesterol,
HIV-1gag genes, vanillic aldehyde, alpha-fetoprotein dissolving mycin, carcinomebryonic antigen, human body chorionic gonadotropin, tryptophan, blood coagulation
Enzyme, 5-methylcytosine adenine, thrombocytin, cysteine, hydrogen peroxide, bisphenol-A, water, luxuriant growth perfume (or spice) glycosides, ammonia, hydroquinones
It is at least one.
Above-mentioned three-dimensional nitrogen-doped graphene enzyme composites or three-dimensional nitrogen-doped graphene non-enzymatic composites
Application in electrochemical sensing field.
Compared with existing electrochemical biosensor technology, the present invention has following characteristics and advantage：
1st, the first public a kind of preparation method and application of three-dimensional nitrogen-doped graphene composite of the present invention, the material system
It is simple to make flow, technique is simple；
2nd, the structural property of three-dimensional nitrogen-doped graphene self-supporting prepared by the present invention can be directly as electrochemical student
The electrode of thing sensing is simple in construction without other binding supporting materials；
3rd, three-dimensional nitrogen-doped graphene prepared by the present invention has great specific surface area and excellent electric conductivity, electronics
Transmission rate is fast, and (the corresponding sensitivity to glucose, dopamine and paracetamol respectively reaches current-responsive high sensitivity
226.24μA·mM–1·m–2、5468.6μA·mM–1·cm–2With 2419.2 μ AmM–1·cm–2)；
4th, the introducing of three-dimensional nitrogen-doped graphene nitrogen prepared by the present invention makes it have more preferable biocompatibility, pole
Big specific surface area makes its abundant combination with enzyme/non-enzymatic material, and enzyme/non-enzymatic material is firmly combined with, and load capacity is high, stable
Property is good；
5th, the three-dimensional nitrogen-doped graphene composite for electrochemical biosensor prepared by the present invention is widely used, all
The biologic inorganic organic molecule that can be reacted or specifically bind with enzyme thereon/non-enzymatic material, can its progress electrification
Learn detection.
Brief description of the drawings
Fig. 1 is three-dimensional nitrogen-doped graphene X-ray diffractogram prepared by chemical vapour deposition technique.
Fig. 2 is the X ray electronic energy spectrum of three-dimensional nitrogen-doped graphene.
Fig. 3 is the thermogravimetric analysis figure of three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite in embodiment 4, embodiment 5.
Fig. 4 is three-dimensional nitrogen-doped graphene, three-dimensional nitrogen-doped graphene-Chitosan Composites, three-dimensional nitrogen in embodiment 2
The scanning electron microscope diagram of doped graphene-chitosan-glucose oxidase composite；Wherein, Fig. 4 (a), 4 (c), 4
(e) represent respectively three-dimensional nitrogen-doped graphene, three-dimensional nitrogen-doped graphene-chitosan, three-dimensional nitrogen-doped graphene-chitosan-
Glucose oxidase scanning electron microscopy under 200 μ m in size, Fig. 4 (b), 4 (d), 4 (f) represent three-dimensional N doping stone respectively
Black alkene, three-dimensional nitrogen-doped graphene-chitosan, three-dimensional nitrogen-doped graphene-chitosan-glucose oxidase are in 500nm sizes
Lower scanning electron microscopy.
Fig. 5 is that three-dimensional nitrogen-doped graphene, three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite are swept in embodiment 4
Retouch electron microscope picture；Wherein, Fig. 5 (a), 5 (c) represent three-dimensional nitrogen-doped graphene, three-dimensional nitrogen-doped graphene ring paste respectively
Scanning electron microscopy of the essence under 300 μm, Fig. 5 (b), 5 (d) represent three-dimensional nitrogen-doped graphene, three-dimensional N doping stone respectively
Scanning electron microscopy of the black alkene cyclodextrin under 500nm.
Fig. 6 is the cyclic voltammetric that three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite detects to dopamine in embodiment 5
Figure.
Fig. 7 is the circulation volt that three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite detects to paracetamol in embodiment 5
Antu.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
It is conventional method unless otherwise instructed to state method.The material can obtain from open commercial sources unless otherwise instructed.
Embodiment 1
(1) using nickel foam as substrate, in hydrogen (flow velocity 20sccm) and argon gas (flow velocity 20sccm), in tube furnace
Middle by substrate, by room temperature, the constant temperature 1min after 10min is heated to 900 DEG C is annealed, and is now closed hydrogen, is passed through carbon source methane
(flow velocity 1sccm) and nitrogen source ammonia (flow velocity 1sccm) stop 1min and grown, methane and the volume ratio of ammonia gas amount
For 1：1,1min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 0.1mol/L FeCl3Middle etching 48h, then
It is transferred in the glass culture dish for fill ultra-pure water and soaks, soaks 6 times, preceding 5min each twice, rear four each 5min altogether
In, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into the chitosan-acetic acid solution that mass fraction is 5%
Middle ultrasonic 20min, taking-up, which is placed in 10mg/mL glucose oxidases, soaks 1h, and taking-up is slightly cleaned with ultra-pure water and obtains three
Tie up nitrogen-doped graphene-chitosan-glucose oxidase composite；
(4) the three-dimensional nitrogen-doped graphene-chitosan-glucose oxidase composite obtained in step (3) is made
Electrode, electro-chemical test is carried out with this electrode pair glucose solution.
Embodiment 2
(1) using nickel foam as substrate, in hydrogen (flow velocity 200sccm) and argon gas (flow velocity 400sccm), in tubular type
By substrate, by room temperature, the constant temperature 5min after 30min is heated to 1000 DEG C is annealed in stove, is now closed hydrogen, is passed through carbon source first
Alkane (flow velocity 10sccm) and nitrogen source ammonia (flow velocity 14sccm) stop 4min and grown, methane and the body of ammonia gas amount
Product is than being 5：7,25min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 1mol/L FeCl3Middle etching 13h, then turn
Move on in the glass culture dish for fill ultra-pure water and soak, soak 6 times, preceding 20min each twice, rear four each 8min altogether
In, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into the chitosan-acetic acid solution that mass fraction is 5%
Middle ultrasonic 2h, taking-up, which is placed in 10mg/mL glucose oxidases, soaks 24h, and taking-up is slightly cleaned with ultra-pure water and obtains three-dimensional
Nitrogen-doped graphene-chitosan-glucose oxidase composite；
(4) the three-dimensional nitrogen-doped graphene-chitosan-glucose oxidase composite obtained in step (3) is made
Electrode, electro-chemical test is carried out with this electrode pair glucose solution.
Fig. 1 is three-dimensional nitrogen-doped graphene X-ray diffractogram, shows the peak sum of [002] crystal face of 26.5 ° of graphene
The characteristic peak of 54.6 ° [004] crystal face, show that obtained three-dimensional nitrogen-doped graphene has very high crystallinity (JCPDScard75
~1621).
Fig. 2 is the X ray electronic energy spectrum of three-dimensional nitrogen-doped graphene, shows the characteristic peak of N element, shows by effectively
Participate in three-dimensional grapheme crystal.
Fig. 4 is three-dimensional nitrogen-doped graphene, three-dimensional nitrogen-doped graphene-Chitosan Composites, three-dimensional N doping graphite
The contrast of the scanning electron microscope diagram of alkene-chitosan-glucose oxidase composite, show that chitosan and grape are glycoxidative
Enzyme is attached to the surface of three-dimensional nitrogen-doped graphene well.
Embodiment 3
(1) using nickel foam as substrate, in hydrogen (flow velocity 1000sccm) and argon gas (flow velocity 1000sccm), Yu Guan
By substrate, by room temperature, the constant temperature 5min after 60min is heated to 1500 DEG C is annealed in formula stove, is now closed hydrogen, is passed through carbon source
Methane (flow velocity 100sccm) and nitrogen source ammonia (flow velocity 200sccm) stop 25min and grown, methane and ammonia gas
The volume ratio of amount is 1：2,30min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 1:5 (analytically pure nitric acid：Ultra-pure water)
6h is etched in nitric acid, is then transferred in the glass culture dish for fill ultra-pure water and soaks, is soaked 6 times altogether, it is preceding each twice
In 60min, latter four times each 30min, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into the chitosan-acetic acid solution that mass fraction is 5%
Middle ultrasonic 200min, taking-up, which is placed in 10mg/mL glucose oxidases, soaks 48h, and taking-up is slightly cleaned with ultra-pure water and obtained
Three-dimensional nitrogen-doped graphene-chitosan-glucose oxidase composite；
(4) the three-dimensional nitrogen-doped graphene-chitosan-glucose oxidase composite obtained in step (3) is made
Electrode, electro-chemical test is carried out with this electrode pair glucose solution.
Embodiment 4
(1) using nickel foam as substrate, in hydrogen (flow velocity 200sccm) and argon gas (flow velocity 500sccm), in tubular type
By substrate, by room temperature, the constant temperature 5min after 30min is heated to 1000 DEG C is annealed in stove, is now closed hydrogen, is passed through carbon source first
Alkane (flow velocity 10sccm) and nitrogen source ammonia (flow velocity 14sccm) stop 5min and grown, methane and the body of ammonia gas amount
Product is than being 5：7,35min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 2.5mol/L FeCl3Middle etching 11h, then
It is transferred in the glass culture dish for fill ultra-pure water and soaks, soaks 6 times, preceding 20min each twice, latter four times altogether every time
In 10min, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into ultrasonic 30min in saturation beta-schardinger dextrin solution,
Taking-up, which is placed in saturation beta-schardinger dextrin solution, soaks 0h, taking-up slightly cleaned with ultra-pure water obtain three-dimensional nitrogen-doped graphene-
Beta-schardinger dextrin composite；
(4) electrode is made in the three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite obtained in step (3), with this electricity
Electro-chemical test extremely is carried out to dopamine solution.
Fig. 3 is the thermogravimetric analysis figure of three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite, by figure be computed showing β~
Cyclodextrin is effectively supported on three-dimensional nitrogen-doped graphene and load capacity is about 30%.
Fig. 5 is three-dimensional nitrogen-doped graphene, the scanning electron microscopy of three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite
Mirror figure contrasts, and further demonstrates that beta-schardinger dextrin is attached to three-dimensional nitrogen-doped graphene surface.
Fig. 6 is the cyclic voltammogram that three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite detects to dopamine, shows to make
Three-dimensional nitrogen-doped graphene-beta-schardinger dextrin the composite obtained has good response sensitivity to dopamine, is computed obtaining it
Sensitivity is 5468.6 μ AmM–1·cm–2。
Embodiment 5
(1) using nickel foam as substrate, in hydrogen (flow velocity 200sccm) and argon gas (flow velocity 600sccm), in tubular type
By substrate, by room temperature, the constant temperature 5min after 30min is heated to 1000 DEG C is annealed in stove, is now closed hydrogen, is passed through carbon source first
Alkane (flow velocity 10sccm) and nitrogen source ammonia (flow velocity 14sccm) stop 6min and grown, methane and the body of ammonia gas amount
Product is than being 5：7,30min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 1:10 (analytically pure nitric acid：Ultra-pure water)
12h is etched in nitric acid, is then transferred in the glass culture dish for fill ultra-pure water and soaks, is soaked 6 times altogether, it is preceding each twice
In 20min, latter four times each 12min, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into ultrasonic 30min in saturation beta-schardinger dextrin solution,
Taking-up, which is placed in saturation beta-schardinger dextrin solution, soaks 13h, taking-up slightly cleaned with ultra-pure water obtain three-dimensional nitrogen-doped graphene-
Beta-schardinger dextrin composite；
(4) electrode is made in the three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite obtained in step (3), with this electricity
Electro-chemical test extremely is carried out to paracetamol solution.
As shown in fig. 7, the cyclic voltammetric that the three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite detects to paracetamol
The bright obtained three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite of chart has good response sensitivity to paracetamol,
Be computed its response sensitivity is 2419.2 μ AmM–1·cm–2。
Embodiment 6
(1) using nickel foam as substrate, in hydrogen (flow velocity 500sccm) and argon gas (flow velocity 500sccm), in tubular type
By substrate, by room temperature, the constant temperature 5min after 20min is heated to 700 DEG C is annealed in stove, is now closed hydrogen, is passed through carbon source first
Alkane (flow velocity 15sccm) and nitrogen source ammonia (flow velocity 20sccm) stop 5min and grown, methane and the body of ammonia gas amount
Product is than being 3：4,100min is to room temperature for cooling, obtains the three-dimensional nitrogen-doped graphene containing substrate；
(2) the three-dimensional nitrogen-doped graphene obtained in step (1) is transferred to 1:20 (analytically pure nitric acid：Ultra-pure water)
20h is etched in nitric acid, is then transferred in the glass culture dish for fill ultra-pure water and soaks, is soaked 6 times altogether, it is preceding each twice
In 15min, latter four times each 20min, that is, obtain three-dimensional nitrogen-doped graphene；
(3) the three-dimensional nitrogen-doped graphene obtained in step (2) is put into ultrasonic 30min in saturation beta-schardinger dextrin solution,
Taking-up, which is placed in saturation beta-schardinger dextrin solution, soaks 24h, taking-up slightly cleaned with ultra-pure water obtain three-dimensional nitrogen-doped graphene-
Beta-schardinger dextrin composite；
(4) electrode is made in the three-dimensional nitrogen-doped graphene-beta-schardinger dextrin composite obtained in step (3), with this electricity
Electro-chemical test extremely is carried out to paracetamol solution.
In summary, the three-dimensional nitrogen-doped graphene composite produced by the present invention for electrochemical biosensor has
Good biocompatibility, excellent electron transport ability, the pole in the detection to matched biologic inorganic organic molecule
High sensitivity, there is important application meaning in electrochemical biosensor field.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (6)
- A kind of 1. three-dimensional nitrogen-doped graphene non-enzymatic composites, it is characterised in that the method system by comprising the following steps It is standby to obtain：Three-dimensional nitrogen-doped graphene composite and non-enzyme material are subjected to Combined Processing, that is, obtain three-dimensional N doping graphite Alkene non-enzymatic composites；Described non-enzyme material is alpha-cyclodextrin, beta-schardinger dextrin, gamma-cyclodextrin, Tanabe Seiyoku derivative At least one of thing；The process of Combined Processing is ultrasonic, soaks, be overcritical, vibrates, is chemically bonded, stirs, centrifuged at least It is a kind of；The time of Combined Processing is 0.5~24h；Described three-dimensional nitrogen-doped graphene composite is prepared in the following manner：Using foamed material as substrate, containing Under inert gas, hydrogen and carbon source and nitrogen conditions, using chemical gaseous phase depositing process, the three-dimensional nitrogen containing substrate is prepared and mixes Miscellaneous graphene；Then the three-dimensional nitrogen-doped graphene containing substrate is performed etching, cleaning treatment obtains three-dimensional nitrogen-doped graphene.
- 2. three-dimensional nitrogen-doped graphene non-enzymatic composites according to claim 1, it is characterised in that：Described change Learning vapour deposition process is：In hydrogen and inert atmosphere, after foam substrate is risen into annealing temperature annealing by room temperature, then carbon is passed through Source and nitrogen source grow N doping three-dimensional grapheme under growth temperature in foam substrate surface catalysis, are then cooled to room temperature, take Go out the N doping three-dimensional grapheme containing substrate.
- 3. three-dimensional nitrogen-doped graphene non-enzymatic composites according to claim 1, it is characterised in that：The foam Material be nickel foam, cobalt foam, iron foam, aluminum foam, golden foam, silver-colored foam, copper foam, zinc foam, molybdenum foam, tungsten foam, At least one of titanium foam, vanadium foam, chromium foam, ruthenium foam, rhodium foam, platinum foam, palladium foam, polymeric foam；The size of the foam substrate is 0.1 × 0.1cm~100 × 100cm；The carbon source is carbon monoxide, methane, ethane, propane, butane, pentane, hexane, butine, hexamethylene, ethene, propylene, fourth In diene, amylene, cyclopentadiene, acetylene, methanol, ethanol, benzene, toluene, phthalocyanine, nitrobenzene, aminobenzene, amino acid, propionitrile It is at least one；The nitrogen source be ammonia, hydrazine, nitric oxide, nitrogen dioxide, nitrogen, nitrobenzene, aminobenzene, amino acid, in propionitrile extremely Few one kind；The flow velocity of the hydrogen is 20~1000sccm；The flow velocity of the inert gas is 20~1000sccm；The flow velocity of the carbon source is 1~100sccm；The flow velocity of the nitrogen source is 1~200sccm；The ratio of the carbon source and nitrogen source is 1:2~1:1.
- 4. three-dimensional nitrogen-doped graphene non-enzymatic composites according to claim 3, it is characterised in that：By what is obtained Nitrogen-doped graphene containing substrate is transferred in etching liquid be transferred in cleaning fluid after etching completely and washed.
- 5. three-dimensional nitrogen-doped graphene non-enzymatic composites according to claim 4, it is characterised in that：The etching In step, the etching liquid that uses is iron chloride, at least one of nitric acid, the concentrated sulfuric acid, chloroazotic acid, potassium permanganate, etch period 6 ~48h；In the cleaning step, cleaning fluid used is cleaned as at least one of ethanol, ultra-pure water, acetone, cleaning step is Soaked 6 times with cleaning fluid, first 2 times each soak times are 5~60min, and latter 4 times each soak time is 5~30min.
- 6. the answering in electrochemical sensing field of the three-dimensional nitrogen-doped graphene non-enzymatic composites described in claim 1 With.
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