CN107963671B - Support type composite and its preparation method and application - Google Patents
Support type composite and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 26
- 239000010439 graphite Substances 0.000 claims abstract description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 24
- 238000002604 ultrasonography Methods 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 230000005588 protonation Effects 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000002114 nanocomposite Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- 239000011540 sensing material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 9
- 238000007306 functionalization reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- -1 graphite alkene Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of support type composites and its preparation method and application, to protonate carbonitride as nanometer bridge, it is loaded on graphite alkenyl nanometer materials and obtains the composite material, it the steps include: to prepare the water slurry of graphene oxide using oxidation graphite solid under (1) ultrasound；(2) it is uniform that protonation carbonitride ultrasound into the water slurry of graphene oxide is added；(3) FeCl is added3·6H2O and polyvinylpyrrolidone are stirred evenly into step (2) described suspension；(4) hydro-thermal reaction is carried out rapidly；It (5) is to obtain the nanocomposite after washing, being dry.The nanocomposite is a kind of one pot of hydro-thermal assemble method for utilizing science integration nano-metal-oxide growth in situ and graphene oxide to synchronize reduction and protonation carbonitride self-assembling technique synchronous with graphene, synthesis step is simple, efficient, it is easy to largely prepare, is particularly suitable for application as the electrochemical catalysis detecting and analysis of nitrite.
Description
Technical field
The present invention relates to a kind of functionalization graphene nano materials and its preparation method and application, and especially one kind can be made
For electrochemical sensing material protonation carbonitride as the support type composite of nanometer bridge and its preparation
Method belongs to field of material preparation.
Background technique
With the continuous improvement of economic level, environmental problem is also at the puzzlement in for people's lives.In daily life, empty
Gas and water, food are the necessitys of human survival, and there are a large amount of harmful substances in water and food, therefore for wherein nuisance
The detection of matter is necessary.Nitrite is widely used in agriculture, industrial, food manufacturing, therefore to the essence of its content
Really quickly detection becomes prevention and eliminates the most important thing of harm.
It is intuitive can to convert electric signal for the chemical reaction occurred in electrode surface for electrochemical sensor detection technique
It shows, plays the role of sensing, to the high sensitivity of particular chemicals.Relative to other existing detection means, electrification
Learning sensor has apparent superiority.Common bare electrode is unable to satisfy people to the need of highly sensitive detection many kinds of substance
It asks, in electrode face finish different activities substance to improve electrode for the catalytic effect of particular chemicals, so that sensor
It is whole more sensitive.Since the introducing of nano material can greatly improve the performance of electrochemical sensor.Construct novel nano material
The electrochemical sensor of material modification has become the research hotspot of this field.
Graphene (Graphene) possesses high conductivity, wide electrochemical window, most as novel two-dimension nano materials
Possess good chemical stability in number electrolyte and the advantages of surface easily regenerates, this is provided to seek ideal nanostructure
Important channel.Carbonitride (g-C3N4) possess higher chemical stability.g-C3N4It is by three s-triazine or s-triazine structure
The laminated structure that unit is polymerized by amino group.C3N4With a large amount of Cation adsorption sites.But it is in terms of electrochemistry
Using less, this is because the disadvantages of material scatter is poor, size is larger, electric conductivity is poor, seriously limits it in electricity
The application of chemical aspect.And the carbonitride Jing Guo nitric acid treatment is expressed as H-C3N4, there is small size, and there is certain conduction
Property, composite substrate can be coupled as with graphene.
Bloodstone (Fe2O3), the n-type metal oxide semiconductor material relatively narrow as a kind of band gap (eV of Eg=2.2), by
In at low cost, non-toxic, it is readily produced and is had been a great concern the characteristics of storage.Catalyst, fuel, magnetic material,
Have in gas sensor, biosensor and lithium ion battery extensive use and by research on deeply process.Graphene, H-C3N4
With Fe2O3Synergistic effect can assign material new characteristic material is had for different demands and different potentially answer
With.And in the prior art, building trielement composite material generally requires complicated technique, manpower has been wasted largely, material resources, and three
It is useless higher.Thus, realize that multicomponent mixture building nanosensor also becomes most important at present and most challenges using simple technique
One of work.(1. L. Cui, T. Pu, Y. Liu, X. He, Electrochim. Acta, 88 (2013) 559-
564. 2. J. Jiang, W. Fan, X. Du, Biosens. Bioelectron., 51 (2014) 343-348).
But in the above-mentioned methods, synthesis step is cumbersome, needs multistep complex operations, it is difficult to which industrialization is extensive raw
It produces, and the three wastes are more.
Summary of the invention
The present invention provides a kind of protonation nitrogen for the deficiencies of of the existing technology cumbersome, complicated, the three wastes are larger
Change support type composite and preparation method thereof of the carbon as nanometer bridge.
Realizing the technical solution of the object of the invention is: support type composite, to protonate nitrogen
Change carbon as nanometer bridge, is loaded on graphite alkenyl nanometer materials and obtain the composite material.
The preparation method of above-mentioned support type composite includes the following steps: to use under (1) ultrasound
Oxidation graphite solid prepares the water slurry of graphene oxide；(2) protonation carbonitride (H-C is added3N4) arrive graphene oxide
Ultrasound is uniform in water slurry；(3) FeCl is added3·6H2O and polyvinylpyrrolidone (PVP) arrive step (2) described suspension
In stir evenly；(4) hydro-thermal reaction is carried out rapidly；It (5) is to obtain the nanocomposite after washing, being dry.
Further, in step (1), oxidation graphite solid uses improved Hummers method with natural graphite
Powder preparation；Ultrasonic time is 1 ~ 24 h.
Further, in step (1), the ratio of graphite oxide and water is 1:1 ~ 1:4 mg/ml.
Further, in step (2), the ratio of graphite oxide as described in step (1) and protonation carbonitride is 5:1 ~ 1:2
mg/mg；Ultrasonic time is 0.1 ~ 4 h.
Further, in step (3), graphite oxide and FeCl as described in step (1)3·6H2The ratio of O is 1:1 ~ 1:40
mg/mg；The ratio of graphite oxide and PVP as described in step (1) is 1:1 ~ 1:40 mg/mg；Mixing time is 10 ~ 60 min.
Further, in step (4), hydrothermal temperature is 120 ~ 200 DEG C；The hydro-thermal reaction time is 6 ~ 24 h.
Application of the above-mentioned support type composite as the electrochemical sensor for being used in nitrite.
Compared with prior art, the invention has the advantages that
(1) preparation method of the present invention avoids cumbersome multicomponent material synthesis step, it is only necessary to mixed by stirring
After conjunction, it can be synthesized using one pot of hydrothermal synthesis technology.
(2) as long as the present invention is environmentally protective by routine operations, simple processes such as simple centrifuge washing, filterings.
(3) functionalization graphene nano hybridization sensing material prepared by the present invention can be easily by adjusting reaction
Temperature and burden control Fe2O3In H-C3N4With the load capacity and size on graphene, and then adjust hybrid material catalytic
Energy.
(4) preparation method of the invention close to Green Chemistry requirement, it is easily controllable, be conducive to industrialized mass production.
The embodiment of the present invention is described in further detail with reference to the accompanying drawing.
Detailed description of the invention
Fig. 1 is support type composite of the protonation carbonitride prepared by the present invention as nanometer bridge
Preparation process schematic diagram.
Fig. 2 is the Principle of Process schematic diagram of support type composite prepared by the present invention.
Fig. 3 is the infrared spectrogram of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 4 is the TEM photo of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 5 is the XRD diagram of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 6 is the nano combined sensing material modified glassy carbon electrode pair of functionalization graphene in invention embodiment 1
In the i-t curve of nitrite.
Specific embodiment
The embodiment of the present invention is described in further detail with reference to the accompanying drawing, the present embodiment is with the technology of the present invention side
Implemented under the premise of case, the detailed implementation method and specific operation process are given, but protection scope of the present invention is unlimited
In following embodiments.
As depicted in figs. 1 and 2, support type graphene-based nanometer of the protonation carbonitride of the present invention as nanometer bridge
The preparation method of composite material, method includes the following steps:
Step 1 prepares carbonitride；
Step 2, preparation protonation carbonitride；
Step 3 uses improved Hummers method to prepare oxidation graphite solid with natural graphite powder；
Under step 4, ultrasound, the water slurry of graphene oxide is prepared using oxidation graphite solid；Graphite oxide and water
Than for 1:1 ~ 1:4 mg/ml；Ultrasonic time is 1 ~ 24 h.
Step 5, the protonation carbonitride (H-C that will be prepared in step 23N4) be added in the suspension of step 4 and ultrasound
It is even；Graphite oxide and H-C3N4Ratio be 5:1 ~ 1:2 mg/mg；Ultrasonic time is 0.1 ~ 4 h.
FeCl is added in step 63·6H2O and polyvinylpyrrolidone (PVP) are stirred evenly into the suspension of step 5；Oxygen
Graphite and FeCl3·6H2The ratio of O is 1:1 ~ 1:40 mg/mg；The ratio of graphite oxide and PVP are 1:1 ~ 1:40 mg/mg；Stirring
Time is 10 ~ 60 min.
The suspension of step 6 is carried out rapidly hydro-thermal reaction by step 7；Hydrothermal temperature is 120 ~ 200 DEG C；When reaction
Between be 6 ~ 24 h.
The nanocomposite is obtained after step 8, washing, drying.
Wherein, the structural formula of carbonitride is as follows:
。
Embodiment 1
The first step is weighed 5 g melamines in crucible, is calcined in Muffle furnace using temperature programming: P1 T=
350 DEG C, the min of t=10；P2T=550 DEG C, the min of t=240, natural cooling, obtains yellow blocks of solid after the reaction was completed.
Grind into powder is up to g-C3N4;
Second step weighs g-C3N410 mL HNO are added in 100 mg in 50 mL round-bottomed flasks3(65 wt%), 80 DEG C cold
It is solidifying to flow back, 5 h are reacted under magnetic agitation.Room temperature is cooling after reaction, and NaHCO is added dropwise into reaction solution3In solution and solution
To faintly acid.Decompression filters, and is used ethanol washing 3 times, 70 DEG C of 12 h of vacuum drying afterwards for several times with deionized water washing, grinding
It is acidified g-C to obtain the final product at powder3N4(H-C3N4).
Third step, the preparation of oxidation graphite solid；
It is with the 30 mL concentrated sulfuric acids, 10 g potassium peroxydisulfates and 10 g phosphorus pentoxides that 20 g natural graphites are pre- at 80 DEG C
After oxidation, pH=7 are washed to, air drying is stand-by overnight；
The 460 mL concentrated sulfuric acids are cooled to 0 DEG C or so, then by 20 g pre-oxidize graphite be added thereto, slowly plus
Enter 60 g potassium permanganate, so that system temperature is no more than 20 DEG C, 35 DEG C are warming up to after addition, after stirring 2 h, and point
It criticizes and is slowly added into 920 mL deionized waters, so that system temperature is no more than 98 DEG C, be stirred for after 15 minutes, 2.8 L are added and go
30 % hydrogen peroxide of ionized water and 50 mL.Obtained glassy yellow suspension is depressurized and is filtered, washing.Until not having in filtrate
Sulfate ion, and when being in neutrality, product is dried in 60 DEG C of vacuum, obtains oxidation graphite solid；
25 mg graphite oxide powder under ultrasonic, be packed into round-bottomed flask, add 50 mL water, 1.5 h of ultrasound by the 4th step
Afterwards, the suspension of graphene oxide (GO) is obtained；
40 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4
And 0.5 h of ultrasound is uniformly mixed；
6th step takes 250 mg FeCl3·6H2O and 250 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water
Afterwards, which is added to and stirs 30 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 160 DEG C；Reaction time is 12
h。
8th step is filtered the crude product that the 7th step obtains, washing, after dry, obtains graphene after washing, drying
Nanocomposite.
Infrared spectroscopy such as Fig. 3 institute of the graphene nanocomposite material (the nano combined sensing material of functionalization graphene)
Show, it was demonstrated that the nano-hybrid material successfully synthesizes.
The TEM figure of the nano combined sensing material of functionalization graphene is as shown in Figure 4, it was demonstrated that the nano-hybrid material has succeeded
Synthesis.
The XRD diagram of the nano combined sensing material of functionalization graphene is as shown in Figure 5；
I-t curve such as Fig. 6 institute of the nano combined sensing material modified glassy carbon electrode of functionalization graphene for nitrite
Show, it was demonstrated that the nano-hybrid material responds nitrite with good electro-catalysis.H-C3N4A large amount of defective bit is conducive to
Fe2O3Growth, significantly improve chemical property.The range of linearity of detection are as follows: 25 nmol/L -3000 μm of ol/L, detection
It is limited to 18.43 nmol/L.
Embodiment 2
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxide powder under ultrasonic, be packed into round-bottomed flask, add 25 mL water, 24 h of ultrasound by the 4th step
Afterwards, the suspension of graphene oxide (GO) is obtained；
5 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4 simultaneously
0.1 h of ultrasound is uniformly mixed；
6th step takes 25 mg FeCl3·6H2After O and 25 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water,
The solution is added to and stirs 60 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 160 DEG C；Reaction time is 24
h。
8th step, with step 8 in embodiment 1.
Embodiment 3
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxide powder under ultrasonic, be packed into round-bottomed flask, add 100 mL water, 1 h of ultrasound by the 4th step
Afterwards, the suspension of graphene oxide (GO) is obtained；
50 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4
And 4 h of ultrasound are uniformly mixed；
6th step takes 50 mg FeCl3·6H2After O and 50 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water,
The solution is added to and stirs 50 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 160 DEG C；Reaction time is 15
h。
8th step, with step 8 in embodiment 1.
Embodiment 4
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxide powder under ultrasonic, be packed into round-bottomed flask, add 80 mL water, 1 h of ultrasound by the 4th step
Afterwards, the suspension of graphene oxide (GO) is obtained；
40 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4
And 4 h of ultrasound are uniformly mixed；
6th step takes 25 mg FeCl3·6H2After O and 25 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water,
The solution is added to and stirs 10 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 120 DEG C；Reaction time is 15
h。
8th step, with step 8 in embodiment 1.
Embodiment 6
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxide powder under ultrasonic, be packed into round-bottomed flask, add 25 mL water, 12 h of ultrasound by the 4th step
Afterwards, the suspension of graphene oxide (GO) is obtained；
15 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4
And 2 h of ultrasound are uniformly mixed；
6th step takes 30 mg FeCl3·6H2After O and 30 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water,
The solution is added to and stirs 50 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 160 DEG C；Reaction time is 20
h。
8th step, with step 8 in embodiment 1.
Embodiment 7
First to fourth step, with step 1 in embodiment 1 to four.
5 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4 simultaneously
0.5 h of ultrasound is uniformly mixed；
6th step, with step 6 in embodiment 1.；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 120 DEG C；Reaction time is 12
h。
8th step, with step 8 in embodiment 1.
Embodiment 8
First to fourth step, with step 1 in embodiment 1 to four.
50 mg prepared in the first step are protonated carbonitride (H-C by the 5th step3N4) be added in the suspension of step 4
And 4 h of ultrasound are uniformly mixed；
6th step, with step 6 in embodiment 1.；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 200 DEG C；Reaction time is 12
h。
8th step, with step 8 in embodiment 1.
Embodiment 9
The first to five step, with step 1 in embodiment 1 to five.
6th step takes 1000 mg FeCl3·6H2O and 1000 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water
In after, which is added to and stirs 30 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 200 DEG C；Reaction time is 6
h。
8th step, with step 8 in embodiment 1.
Embodiment 10
The first to five step, with step 1 in embodiment 1 to five.
6th step takes 500 mg FeCl3·6H2O and 1000 mg polyvinylpyrrolidones (PVP) are dissolved in 30 ml water
Afterwards, which is added to and stirs 20 min in the suspension of the 5th step and is uniformly mixed；
The suspension of 6th step is carried out rapidly hydro-thermal reaction by the 7th step；Reaction temperature is 160 DEG C；Reaction time is 10
h。
8th step, with step 8 in embodiment 1.
The invention avoids cumbersome multicomponent material synthesis steps, it is only necessary to after mixing by stirring, utilize one pot of hydro-thermal
Synthetic technology can synthesize.The preparation of the nanocomposite is a kind of science integration nano-metal-oxide growth in situ, oxygen
One pot of hydro-thermal assemble method of the synchronous reduction of graphite alkene and protonation carbonitride self-assembling technique synchronous with graphene.Synthesis
Afterwards, as long as can be prepared by routine operations such as simple centrifuge washing, filterings.Functionalization prepared by the present invention simultaneously
Graphene nano hydridization sensing material can be easily by adjusting reaction temperature and burden control Fe2O3In protonation nitrogen
Change carbon and load capacity and size on graphene, and then adjusts the catalytic performance of hybrid material.Preparation method of the invention close to
The requirement of Green Chemistry, it is easily controllable, be conducive to industrialized mass production.
Claims (9)
1. support type composite, which is characterized in that protonate carbonitride as nanometer bridge, loaded
The composite material is obtained on to graphite alkenyl nanometer materials, is prepared by following steps: (1) under ultrasound, using graphite oxide
Solid prepares graphene oxide water slurry；(2) it is uniform that protonation carbonitride ultrasound into graphene oxide water slurry is added；
(3) FeCl is added3·6H2O and polyvinylpyrrolidone are stirred evenly into step (2) described suspension；(4) water is carried out rapidly
Thermal response, hydrothermal temperature are 120 ~ 200 DEG C；The hydro-thermal reaction time is 6 ~ 24 h；It (5) is to obtain institute after washing, being dry
The nanocomposite stated.
2. the preparation method of support type composite includes the following steps: under (1) ultrasound, using oxidation stone
Black solid prepares graphene oxide water slurry；(2) it is equal that protonation carbonitride ultrasound into graphene oxide water slurry is added
It is even；(3) FeCl is added3·6H2O and polyvinylpyrrolidone are stirred evenly into step (2) described suspension；(4) it carries out rapidly
Hydro-thermal reaction, hydrothermal temperature are 120 ~ 200 DEG C；The hydro-thermal reaction time is 6 ~ 24 h；It (5) is to obtain after washing, being dry
The nanocomposite.
3. preparation method as claimed in claim 2, which is characterized in that in step (1), oxidation graphite solid is using improved
Hummers method is prepared with natural graphite powder；Ultrasonic time is 1 ~ 24 h.
4. preparation method as claimed in claim 2, which is characterized in that in step (1), the ratio of graphite oxide and water is 1:1 ~ 1:
4 mg/ml。
5. preparation method as claimed in claim 2, which is characterized in that in step (2), graphite oxide as described in step (1)
Ratio with protonation carbonitride is 5:1 ~ 1:2 mg/mg；Ultrasonic time is 0.1 ~ 4 h.
6. preparation method as claimed in claim 2, which is characterized in that in step (3), graphite oxide as described in step (1)
And FeCl3·6H2The ratio of O is 1:1 ~ 1:40 mg/mg.
7. preparation method as claimed in claim 2, which is characterized in that in step (3), graphite oxide as described in step (1)
Ratio with polyvinylpyrrolidone is 1:1 ~ 1:40 mg/mg.
8. preparation method as claimed in claim 2, which is characterized in that in step (3), mixing time is 10 ~ 60 min.
9. the electrochemical sensor of support type composite as described in claim 1 as nitrite
Using.
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