CN106928239B - Graphene-porphyrin type organic nano material and preparation method thereof - Google Patents
Graphene-porphyrin type organic nano material and preparation method thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 126
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 46
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 239000012286 potassium permanganate Substances 0.000 claims description 26
- 229950003776 protoporphyrin Drugs 0.000 claims description 26
- 238000005119 centrifugation Methods 0.000 claims description 14
- 239000004317 sodium nitrate Substances 0.000 claims description 14
- 235000010344 sodium nitrate Nutrition 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KSFOVUSSGSKXFI-GAQDCDSVSA-N CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O Chemical compound CC1=C/2NC(\C=C3/N=C(/C=C4\N\C(=C/C5=N/C(=C\2)/C(C=C)=C5C)C(C=C)=C4C)C(C)=C3CCC(O)=O)=C1CCC(O)=O KSFOVUSSGSKXFI-GAQDCDSVSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- -1 graphite alkene Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- KFKRXESVMDBTNQ-UHFFFAOYSA-N 3-[18-(2-carboxylatoethyl)-8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-22,23-dihydroporphyrin-21,24-diium-2-yl]propanoate Chemical compound N1C2=C(C)C(C(C)O)=C1C=C(N1)C(C)=C(C(O)C)C1=CC(C(C)=C1CCC(O)=O)=NC1=CC(C(CCC(O)=O)=C1C)=NC1=C2 KFKRXESVMDBTNQ-UHFFFAOYSA-N 0.000 claims description 3
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 231100000167 toxic agent Toxicity 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000000654 additive Substances 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 18
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 5
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- 239000006228 supernatant Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- JOJPFQVZNUNZBO-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] JOJPFQVZNUNZBO-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910000471 manganese heptoxide Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- VXJPCEOTZNHHOA-UHFFFAOYSA-N [K].OC Chemical compound [K].OC VXJPCEOTZNHHOA-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
A kind of graphene-porphyrin type organic nano material and preparation method thereof.Preparation method includes: to heat after mixing graphene oxide water body dispersion liquid, porphyrin type organic and highly basic.Wherein, the pH value of the mixed solution of graphene oxide water body dispersion liquid, porphyrin type organic and highly basic is 9.5-11.This method does not add any surfactant, stabilizer and reducing agent newly, reduces influence of the toxic agent of addition to nano material performance itself, while reducing a possibility that introducing other impurities functional group.The material has good chemical property.
Description
Technical field
The present invention relates to graphene composite material fields, and in particular to a kind of graphene-porphyrin type organic nanometer material
Material and preparation method thereof.
Background technique
Graphene is a kind of two-dimensional graphitic carbon nano lamellar structure of monoatomic thickness.Due to its huge specific surface area
With outstanding electric conductivity performance, graphene presents very huge potentiality in terms of biomedical aspect and energy source use.It is logical
A large amount of scientific research effort is crossed, the technology in organic macromolecule functionalization to grapheme material is gradually found that this method is to pass through
The side chain of organic macromolecule is bonded to graphene surface, forms stable nanocomposite by chemical reaction.The nanometer is multiple
Condensation material has very excellent chemical property, for example the electrostatic for electronics transfer, enhancing and the electrode surface that can enhance is mutual
Effect, outstanding electrocatalytic effect, bionic catalysis performance and preparation method are simple etc..However, this kind of material is all logical
The method for crossing redox graphene is prepared, and is restored many toxic reagents in engineering and is participated such as hydrazine, sodium borohydride
Deng, and these methods are readily incorporated many other functional groups, have seriously affected the original performance characteristic of material, so development
It is a kind of it is nontoxic do not introduce other functional groups preparation method urgent need probed into and researched and developed.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene-porphyrin type organic nano material preparation methods, are not required to
In the case where wanting additional any surfactant, stabilizer and reducing agent, only it need to use highly basic and heating can rapid synthesis
Graphene-porphyrin type organic nanocomposite.
Another object of the present invention is to provide a kind of graphene-porphyrin type organic nano material, the nano material knots
Structure stablize, internal cavities be not occupied can good and complexing of metal ion, have good chemical property.
The present invention solves its technical problem and adopts the following technical solutions to realize:
The present invention proposes that a kind of preparation method of graphene-porphyrin type organic nano material includes: by graphene oxide
It is heated after water body dispersion liquid, porphyrin type organic and highly basic mixing.Wherein, graphene oxide water body dispersion liquid, porphyrin are organic
The pH value of the mixed solution of object and highly basic is 9.5-11.
The present invention proposes a kind of graphene-porphyrin type organic nano material, is prepared by above-mentioned preparation method.
The beneficial effect of graphene of the present invention-porphyrin type organic nano material preparation method is: the preparation method exists
Any surfactant, stabilizer and reduction are not added newly during preparing graphene-porphyrin type organic nano material
Agent, and only can quickly be closed by the pH value of proportion, solution to raw material, reaction temperature and the exploration in reaction time and research
At graphene-protoporphyrin nanocomposite.Reduce influence of the toxic agent of addition to nano material performance itself, simultaneously
Reduce a possibility that introducing other impurities functional group.And the nano material being prepared has a plurality of cavities, it can be with metal ion
Complexing can quickly, sensitively detect metal ion.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described.
Fig. 1 is graphene-protoporphyrin nano material uv absorption spectra that the embodiment of the present invention 1 is prepared；
Fig. 2 is graphene-protoporphyrin nano material transmission electron microscope picture that the embodiment of the present invention 1 is prepared；
Fig. 3 is graphene-porphyrin type organic nano material transmission electron microscope picture that the embodiment of the present invention 1 is prepared.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In the description of the present invention, it should be noted that term " first ", " second " etc. are only used for distinguishing description, without
It can be interpreted as indication or suggestion relative importance.
Below to the graphene of the embodiment of the present invention-porphyrin type organic nano material preparation method and graphene-
Porphyrin type organic nano material is specifically described.
A kind of graphene provided in an embodiment of the present invention-porphyrin type organic nano material preparation method, with parts by weight
Meter:
S1, graphene oxide water body dispersion liquid is prepared；
S1.1, the 13-16 concentrated sulfuric acid, 3-5 parts of graphite, 1.5-3 parts of sodium nitrate and 13-16 parts of potassium permanganate are mixed and heated
Obtain the first mixed solution；
The concentrated sulfuric acid, potassium permanganate, sodium nitrate and the graphite using aforementioned proportion, the concentrated sulfuric acid are proved through a large number of experiments
Expanded graphite production graphene oxide can be effectively aoxidized with potassium permanganate.If the concentrated sulfuric acid, potassium permanganate and expanded graphite
The ratio of addition cannot then obtain graphene oxide of good performance below or above the ratio.
Further, after graphite and sodium nitrate being added in the concentrated sulfuric acid at a temperature of 0-4 DEG C, it is slow added into permanganic acid
Potassium, meanwhile, the temperature of mixed solution is no more than 20 DEG C when control mixes.
Firstly, addition sodium nitrate cannot can not be even aoxidized completely because the concentrated sulfuric acid is insufficient to the oxidisability of graphite
Graphite, and the hydrogen ion of nitrate ion and the concentrated sulfuric acid after sodium nitrate is added, form nitric acid.Nitric acid is mixed with concentrated sulfuric acid formation
Acid, oxidisability is stronger, is conducive to graphite oxidation and generates graphene oxide.
Potassium permanganate is slowly added again after graphite, sodium nitrate and concentrated sulfuric acid mixing.Since graphite is with net-layer structure
Substance, therefore, this step substantially sulfuric acid molecule, potassium permanganate above-mentioned record at a temperature of enter be graphite linings carry out
Intercalation, and subsequent reaction then carries out between intercalation.Sulfate radical intercalation is abundant in the temperature range, is conducive to subsequent oxidation and reacts
Progress.
This also explains why adding potassium permanganate afterwards, and the rate for adding potassium permanganate is slow.According to chemical reaction
Dynamics is it is found that potassium permanganate is added in the concentrated sulfuric acid, and concentrated sulfuric acid content is high in reaction solution, thus the potassium permanganate energy being added
Graphite layers are enough immediately entered, provide necessary condition for subsequent oxidation reaction.And if the concentrated sulfuric acid is added in potassium permanganate,
Potassium permanganate content is high in reaction solution, then is the acid solution to form potassium permanganate, can not timely enter graphite layers into
Row reaction generates manganese heptoxide, and then influences the generation of graphene oxide.
Further, after low-temperature mixed, the mixture of above-mentioned four kinds of substances is carried out to be heated to 30- for the first time
40 DEG C and keep the temperature 20-30 minutes.This operation be so that oxidant reacted with graphite arrive graphene oxide, be specifically intercalation
Interior sulfate radical reacts to obtain the stronger manganese heptoxide of oxidisability with potassium permanganate, and manganese heptoxide carries out deep oxidation graphite
Obtain graphene oxide.
Further, after adding 200-250 parts of distilled water dilutions, it is warming up to 90-100 DEG C, and keep the temperature 10-15 minutes.
This step is mainly the hydrolysis of intercalation compound, to obtain the bigger graphene oxide of interlamellar spacing.At this point, oxidant with
The oxidation reaction of graphite has terminated, and hydrolysis is that the compound of interlayer is detached from into reaction solution, so that the interlayer of graphene oxide
There is not lewis' acid to occupy, enters interlayer for subsequent porphyrin type organic and necessary space is provided.Distilled water dilution is added, is
In order to further promote the expansion of graphene oxide, further expand the interlamellar spacing of graphene oxide.
It should be noted that mixing described in the embodiment of the present invention, using is existing motor machine stirring.
S1.2,198-245 parts of hydrogen peroxide are added in the first mixed solution until the first mixed solution becomes golden yellow；
The concentrated sulfuric acid can issue a large amount of heat when mixing with water, if adding water in the concentrated sulfuric acid, since the density of water is less than
The concentrated sulfuric acid, water level is in concentrated sulfuric acid solution upper layer, at this point, a large amount of heat released, it will be easy to splash out water, and then hurt experiment
Person.Therefore, it is necessary to which the first mixed solution is added in hydrogen peroxide, the wherein mass percent 3% of hydrogen peroxide.
It is to remove remaining sulfuric acid and potassium permanganate that hydrogen peroxide, which is added, while hydrogen peroxide and sulfuric acid, potassium permanganate are anti-
Gas should be generated, further supports the molecule hole of graphene oxide greatly, restores gained graphene convenient for later period graphene oxide
It reacts to obtain nano material with porphyrin type organic.The color of first mixed solution becomes golden yellow and shows that potassium permanganate is gone
Except complete.
Potassium permanganate can be removed just using the hydrogen peroxide of aforementioned proportion, without adding extra hydrogen peroxide, broken
The structure of bad graphene oxide influences its performance.
S1.3, the first mixed solution is reacted to the second mixed solution standing for terminating to obtain with hydrogen peroxide after 24-36 hours
It is separated by solid-liquid separation；
First mixed solution reacts end with hydrogen peroxide and has obtained pure single graphene oxide, and graphene oxide is solid
Body can be deposited to the bottom of the second mixed solution, and what is contained in the second mixed solution is then remaining impurity.Therefore, it adopts
Removal supernatant is separated by solid-liquid separation convenient for the later period and is obtained so that graphene oxide is all deposited to the second mixed solution bottom with standing
To graphene oxide.
It is centrifuged and adjusts pH after 2-4 parts of dilute hydrochloric acid, 800-1200 parts of deionized water mixing are added in S1.4, graphene oxide,
The range of pH value is 5.5-6.5；
It is separated by solid-liquid separation obtained surface of graphene oxide and manganese ion may be remained in its hole, dilute hydrochloric acid is added can
To remove manganese ion, graphene oxide is further purified.And use the dilute hydrochloric acid of aforementioned proportion can will be residual in graphene oxide
The manganese ion stayed all removes, and will not introduce new impurity, will not influence the property of generated graphene oxide.
The deionized water for adding aforementioned proportion simultaneously is diluted the dilute hydrochloric acid of above-mentioned addition and corresponding salt, just
These impurity are removed in subsequent centrifugation, turbid is graphene oxide water body dispersion liquid under obtained centrifugation.
It is further preferred that the revolving speed of centrifugation is 8500-9500r/min, centrifugation time is 15-20 minutes.Using above-mentioned
The centrifugal condition of record is centrifuged, and the graphene oxide water body dispersion liquid of purity is high, good dispersion property can be obtained.Dilute salt
The mass percent of acid is 7.4%.
It is further preferred that adding 800-1200 parts of deionized waters repeatedly after centrifugation completely and being rushed to graphene oxide
It washes and is centrifuged, until the pH value of supernatant is between 5.5-6.5.Acidic group this removal in this surface pH supernatant liquor is clean,
And then ensure that acid is substantially removed in graphite alkene solution, ensure that can be prepared nano material.It then filters and obtains
Graphene oxide, and 60 DEG C of graphene oxides obtained by drying in air dry oven.
S2, it is heated after mixing graphene oxide water body dispersion liquid, porphyrin type organic and highly basic；
The above-mentioned graphene oxide ultrasound being prepared is dissolved in ultrapure water and obtains graphene oxide water body dispersion liquid.Oxidation
Graphene water body dispersion liquid, porphyrin type organic provide necessary reaction to prepare graphene-porphyrin type organic nano material
Raw material, and highly basic cooperation heating is for redox graphene.
Preferably, the highly basic of addition is solution, avoids that strong basic solid heat release in course of dissolution is added, so that there is by-product
It generates, reduces the purity and generating rate of nano material.
Preferably, again with every 3 minutes dropwise addition 2ml highly basic after graphene oxide water body dispersion liquid, the mixing of porphyrin type organic
The rate of solution is slowly added to strong adjusting PH with base.It ensure that the accuracy of the pH value of test using the drop rate, if rate of addition
It is too fast, then it may cause the pH inaccuracy of detection, and then influence the generation of subsequent nano material.If drop rate is excessively slow, increase
Reaction time, it is possible to have other by-products generation.Similarly, addition highly basic is in order to adjust pH, if directly by three kinds of objects
Matter mixing, is equally unfavorable for the detection of pH value without order of addition.
Further, the range of the pH value of adjusting is 9.5-11.Graphene oxide can be reduced completely in the range
And the structure of porphyrin type organic is not destroyed.If pH value is too low, graphene oxide can not be restored thoroughly；And pH value it is too high when,
It is easily destroyed porphyrin type organic self structure.
It is further preferred that when graphene oxide water body dispersion liquid is mixed with porphyrin type organic, graphene oxide water body
The mass ratio of graphene oxide and porphyrin type organic is 1-1.2:1 in dispersion liquid.The graphene oxide water body of this proportional region
Graphene-porphyrin nano material structure that dispersion liquid and porphyrin type organic generate is best, purity is also most good.And if
When protoporphyrin amount is too many, since the protoporphyrin adhesion amount for starting surface of graphene oxide is too many, the generation of graphene is affected, into
And influence the generation of nano material.If graphene oxide excessively equally will affect the generation of nano material.
It is further preferred that using ultrasonic mixing when graphene oxide water body dispersion liquid is mixed with porphyrin type organic.Its
Shearing force is generated using the high-frequency vibration oxidation graphene water body dispersion liquid of ultrasound and the molecular level of porphyrin type organic,
So that the uniformity coefficient of mixed solution is higher, mixing is finer and smoother, more sufficiently.
Further, highly basic is organic alkali or inorganic strong alkali, and inorganic strong alkali is sodium hydroxide or potassium hydroxide, You Jiqiang
Alkali is sodium alkoxide or potassium alcoholate.Since the effect of alkali is to adjust pH, and the range of pH is 9.5-11, can not make solution using weak base
PH value reaches pH value required for the embodiment of the present invention, therefore is only capable of using highly basic.And Strong oxdiative sodium, potassium hydroxide are then common
Inorganic strong alkali, and the two is relatively inexpensive with respect to other highly basic prices.Organic alkali can also be used, pass through metal and corresponding alcohol
Reaction can be obtained.Above-mentioned sodium alkoxide is that metallic sodium reacts to obtain with alcohol, and specific alcohol can be methanol, ethyl alcohol, normal propyl alcohol, isopropyl
The substances such as alcohol.The alkalinity of organic alkali is even more than inorganic strong alkali, therefore, it can also be used to adjust the pH size of solution.
It is further preferred that porphyrin type organic is any one in protoporphyrin, porphyrin, tetraphenylporphyrin or haematoporphyrin.
Above-mentioned porphyrin organic matter contain there are four pyrrole ring big cyclophane aroma compounds have a bigger cavity structure, Neng Goujie
By the bonding of many metal ions, to form metal complex, there is good chemical property.Meanwhile above-mentioned porphyrin
Organic matter is a kind of phenolic compound, can be cross-linked with each other with graphene by π-πconjugation, is formed more stable
Graphene functionalized nano material.
It is further preferred that after the completion of pH is adjusted, to graphene oxide water body dispersion liquid, porphyrin type organic and strong
The third mixed solution that alkali is mixed to get is heated.It is that graphene makes stone simultaneously that heating, which promotes highly basic redox graphene,
Black alkene reacts to obtain graphene-porphyrin nano material of preparation of the embodiment of the present invention with porphyrin type organic.
It specifically, is to be heated in 90-110 DEG C of oil bath pan to third mixed solution in temperature.It, can due to directly heating
It can lead to mixture uneven heating, and then influence the generation of nano material, and use heat-insulated heating, mixture each section is added
The degree of heat is uniformly and consistent, ensure that the consistency that nano material generates.It meanwhile being the heating speed because of oil liquid using oil bath
Rate is faster than the heating rate of water, and heat insulation effect is better than water-bath.Reaction temperature can obtain electrochemistry in 90-110 DEG C
Can fabulous nano material, and if reaction temperature it is too low when, graphene oxide fails adequately to be restored, and receives obtained from
Rice material does not contain graphene oxide, influences the chemical property of nano material.If reaction temperature was crossed, porphyrin is organically big
Ring structure is destroyed, and with the raising of reaction temperature, extent of the destruction is bigger, will equally reduce nano material electrochemistry
Energy.
With the progress of reaction, the color of third mixed solution has rufous to gradually become black and by black suspension solid
It generates, obtains the dispersion liquid of black, which is required graphene-porphyrin nano material.
Further, after 1 hour to be heated or so, obtained dispersion liquid is transferred to centrifuge tube, is put into centrifuge, set from
Heart revolving speed is 10000-14000rpm, and centrifugation time is 15-25 minutes.Centrifugation moves back away supernatant liquid, the graphene-that can be crossed
Porphyrin type organic nano material is then repeatedly washed again with ultrapure water, is centrifuged, obtains pure product.
A kind of graphene that the embodiment of the present invention also provides-porphyrin type organic nano material.The composite material passes through upper
The preparation method stated is prepared.Obtained nano material is characterized using lens Electronic Speculum and UV-vis.The preparation method
It, can be quick only by adjusting pH value of solution and heating in the case where not outer plus any surfactant, stabilizer and reducing agent
Nano material is prepared.And the nano material has unappropriated porphyrin space, it can be with the good landform of metal ion
At complex compound, there is good chemical property.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of graphene-protoporphyrin nano material provided in this embodiment, mainly by graphene oxide water body dispersion liquid,
Protoporphyrin, sodium hydroxide solution are made to obtain.Wherein, in graphene oxide water body dispersion liquid graphene oxide and protoporphyrin matter
Amount is than being 1:1.
The present embodiment, which also provides, a kind of prepares graphene-protoporphyrin nano material method:
Under 4 DEG C of environment temperatures, by 5.0g graphite powder and 2.5gNaNO3It is added to the dense H of 15.0g2SO4In, in 0 DEG C of strength
15gKMnO is slowly added under stirring4(control temperature is no more than 20 DEG C).After adding, it is heated to 35 DEG C for the first time and keeps the temperature
Continue to stir 30min, then plus 230g distilled water dilutes, and carries out second of heating and temperature is risen to 98 DEG C, keeps 15min
Afterwards.It is subsequently added into 200g3%H2O2, it is golden yellow to solution, rear standing filters after 24 hours.Add 3g dilute hydrochloric acid, 900g is gone
It is centrifuged after ionized water, then is washed with 900g deionized water, solid is put into air dry oven after being 6 until supernatant liquor pH value
60 DEG C of graphene oxides obtained by drying.
Graphene oxide ultrasound is dissolved in ultrapure water and obtains graphene oxide dispersion.Then graphene oxide dispersion with
After protoporphyrin ultrasonic mixing is uniform, with every 3 minutes be added dropwise 2ml rate be added dropwise Strong oxdiative sodium adjust pH, until pH be 10, stop
Sodium hydroxide is added.Then third mixed solution is heated 1 hour or so in 100 DEG C of oil bath pans, obtains black dispersion liquid.Most
Afterwards, resulting dispersion liquid is transferred to centrifuge tube, is put into centrifuge, 20mi n is centrifuged under 12000rpm revolving speed, removes upper liquid
Body can be obtained graphene-protoporphyrin nanocomposite.
The graphene that the present embodiment is prepared-protoporphyrin nano material is characterized by UV-vi s, as shown in Figure 1.
A is graphene oxide in Fig. 1, occurs a very strong absorption peak and a broad peak, this point respectively in 235nm and 300nm
π-π * the transition of armaticity C=C and the n- π * transition of C=O key are not attributed to the fact that.B is graphene in Fig. 1, in the strong of 260nm
Caused by absorption peak is also the π-π * transition of armaticity C=C.C is graphene-protoporphyrin nano material graphene oxide in Fig. 1
At absorption peak red shift to 258nm at 235nm, this coincide with the absorption peak at 260nm in graphene, it was demonstrated that graphene oxide
It is reduced into graphene；Occurs a new strong absworption peak at 421nm simultaneously, this corresponds to the Soret band of protoporphyrin.By
We can demonstrate again that the successful synthesis of graphene-protoporphyrin nano material for this.
The graphene that the present embodiment is prepared-protoporphyrin nano material obtains its microstructure using lens Electronic Speculum, such as
Shown in Fig. 2 and Fig. 3.The original fold of graphene is vanished from sight in Fig. 2, while the black object of many irregular distributions occurs
Matter is that ferriporphyrin is had accumulated due to graphene surface, and ferriporphyrin molecule is evenly dispersed in graphene table by π-πconjugation
Face.Fig. 3 is exaggerated graphene-protoporphyrin nano material surface texture, it can be found that the distribution of protoporphyrin is all that strip is presented,
This may be caused by protoporphyrin is distributed at graphene fold.We demonstrate graphene-protoporphyrin nano materials as a result,
Success synthesizes.
Embodiment 2
The present embodiment provides a kind of graphene-porphyrin nano materials, mainly by graphene oxide water body dispersion liquid, porphin
Quinoline, potassium hydroxide solution are made to obtain.Wherein, the mass ratio of graphene oxide and porphyrin is in graphene oxide water body dispersion liquid
1.1:1.
The preparation method that graphene provided in this embodiment-porphyrin nano material preparation method and embodiment 1 provide
Operating process is almost the same, and difference is that the ratio of reaction raw materials and operating condition change.
The graphite that the present embodiment uses is 3g, sodium nitrate 1.5g, concentrated sulfuric acid 16g, potassium permanganate 16g.Temperature when mixing
Degree is 2 DEG C, and the temperature of heating is 40 DEG C and keeps the temperature 25min for the first time, and distilled water additive amount is 250g, the temperature of second of heating
It is 90 DEG C for heating temperature, the retention time is 10 minutes, and hydrogen peroxide additive amount is 220g.Time of repose is 28 hours, dilute hydrochloric acid
Additive amount is 2g, and deionized water additive amount is 1100g, pH value 6.3.
The value of pH is 9.5 after addition Strong oxdiative potassium, and the temperature of oil bath pan is 110 DEG C, and the revolving speed of centrifugation is 10000rpm, from
The heart time is 15 minutes.
Embodiment 3
The present embodiment provides a kind of graphene-haematoporphyrin nano materials, mainly by graphene oxide water body dispersion liquid, blood
Porphyrin, sodium methoxide solution are made to obtain.Wherein, in graphene oxide water body dispersion liquid graphene oxide and haematoporphyrin mass ratio
For 1.2:1.
The preparation method that graphene provided in this embodiment-haematoporphyrin nano material preparation method and embodiment 1 provide
Operating process it is almost the same, difference be that the ratio of reaction raw materials and operating condition change.
The graphite that the present embodiment uses is 4g, sodium nitrate 3g, concentrated sulfuric acid 13g, potassium permanganate 14g.Temperature when mixing
It is 0 DEG C, the temperature of heating is 30 DEG C and keeps the temperature 25min for the first time, and distilled water additive amount is 200g, and the temperature of second of heating is
Heating temperature is 95 DEG C, and the retention time is 12 minutes, and hydrogen peroxide additive amount is 260g.Time of repose is 36 hours, and dilute hydrochloric acid adds
Dosage is 4g, and deionized water additive amount is 1000g, pH value 5.5.
The value of pH is 10.5 after addition Strong oxdiative potassium, and the temperature of oil bath pan is 90 DEG C, and the revolving speed of centrifugation is 14000rpm, from
The heart time is 18 minutes.
Embodiment 4
The present embodiment provides a kind of graphene-tetraphenylporphyrin nano materials, are mainly dispersed by graphene oxide water body
Liquid, tetraphenylporphyrin, methanol potassium solution are made to obtain.Wherein, graphene oxide and four benzene in graphene oxide water body dispersion liquid
The mass ratio of base porphyrin is 1:1.
The preparation that graphene provided in this embodiment-tetraphenylporphyrin nano material preparation method and embodiment 1 provide
The operating process of method is almost the same, and difference is that the ratio of reaction raw materials and operating condition change.
The graphite that the present embodiment uses is 4g, sodium nitrate 2g, concentrated sulfuric acid 14g, potassium permanganate 16g.Temperature when mixing
It is 3 DEG C, the temperature of heating is 37 DEG C and keeps the temperature 20min for the first time, and distilled water additive amount is 220g, and the temperature of second of heating is
Heating temperature is 92 DEG C, and the retention time is 13 minutes, and hydrogen peroxide additive amount is 250g.Time of repose is 32 hours, and dilute hydrochloric acid adds
Dosage is 3g, and deionized water additive amount is 1200g, pH value 6.5.
The value of pH is 11 after addition Strong oxdiative potassium, and the temperature of oil bath pan is 95 DEG C, and the revolving speed of centrifugation is 13000rpm, centrifugation
Time is 23 minutes.
Embodiment 5
The present embodiment provides a kind of graphene-porphyrin nano materials, mainly by graphene oxide water body dispersion liquid, porphin
Quinoline, ethyl alcohol potassium solution are made to obtain.Wherein, the mass ratio of graphene oxide and porphyrin is in graphene oxide water body dispersion liquid
1.1:1.
The preparation method that graphene provided in this embodiment-porphyrin nano material preparation method and embodiment 1 provide
Operating process is almost the same, and difference is that the ratio of reaction raw materials and operating condition change.
The graphite that the present embodiment uses is 5g, sodium nitrate 2.2g, concentrated sulfuric acid 14g, potassium permanganate 13g.Temperature when mixing
Degree is 4 DEG C, and the temperature of heating is 32 DEG C and keeps the temperature 23min for the first time, and distilled water additive amount is 240g, the temperature of second of heating
It is 100 DEG C for heating temperature, the retention time is 11 minutes, and hydrogen peroxide additive amount is 240g.Time of repose is 25 hours, dilute hydrochloric acid
Additive amount is 2g, and deionized water additive amount is 800g, pH value 5.8.
The value of pH is 10 after addition Strong oxdiative potassium, and the temperature of oil bath pan is 105 DEG C, and the revolving speed of centrifugation is 11000rpm, from
The heart time is 17 minutes.
Embodiment 6
The present embodiment provides a kind of graphene-protoporphyrin nano materials, mainly by graphene oxide water body dispersion liquid, original
Porphyrin, propyl alcohol sodium solution are made to obtain.Wherein, in graphene oxide water body dispersion liquid graphene oxide and protoporphyrin mass ratio
For 1.1:1.
The preparation method that graphene provided in this embodiment-protoporphyrin nano material preparation method and embodiment 1 provide
Operating process it is almost the same, difference be that the ratio of reaction raw materials and operating condition change.
The graphite that the present embodiment uses is 3g, sodium nitrate 2.7g, concentrated sulfuric acid 16g, potassium permanganate 13g.Temperature when mixing
Degree is 4 DEG C, and the temperature of heating is 40 DEG C and keeps the temperature 28min for the first time, and distilled water additive amount is 200g, the temperature of second of heating
It is 93 DEG C for heating temperature, the retention time is 14 minutes, and hydrogen peroxide additive amount is 210g.Time of repose is 31 hours, dilute hydrochloric acid
Additive amount is 4g, and deionized water additive amount is 1200g, pH value 6.
The value of pH is 9.5 after addition Strong oxdiative potassium, and the temperature of oil bath pan is 107 DEG C, and the revolving speed of centrifugation is 12000rpm, from
The heart time is 21 minutes.
Experimental example
Experimental example 1: using the preparation for carrying out composite material with the consistent preparation method of embodiment 1 and step, difference exists
In graphene oxide water body dispersion liquid, porphyrin type organic and highly basic mixed solution pH value be 13.
The nano material Central Plains porphyrin structure being prepared is destroyed, and does not have complete cavity, chemical property is basic
It disappears.
Experimental example 2: using the preparation for carrying out composite material with the consistent preparation method of embodiment 1 and step, difference exists
The mass ratio of graphene oxide and porphyrin type organic is 1:2 in graphene oxide water body dispersion liquid.
The nano material purity being prepared is extremely low, and yield is also extremely low, and there are a large amount of graphene oxide and protoporphyrinogens
Expect unreacted, meanwhile, the chemical property of obtained nano material reduces.
In conclusion graphene-porphyrin type organic nano material preparation method that 1-6 of the embodiment of the present invention is provided is logical
Graphene-porphyrin type organic can be prepared by crossing porphyrin type organic, graphene oxide water body dispersion liquid and highly basic reaction
Nano material.In the case where in whole preparation process without adding any surfactant, stabilizer and reducing agent, only need to visit
Proportion, the pH value of solution, reaction temperature and the reaction time of rope starting material, can rapid synthesis graphene-protoporphyrin receive
Nano composite material.Entire preparation method is easy to operate, at low cost, the period is short, easy to industrialized production.And the graphite being prepared
Porphyrin ring in alkene-porphyrin type organic nano material does not have coordination of metal ion, this causes its cavity not to be occupied, can
Other metal ions are complexed with it, can be used for detecting metal ion.Meanwhile the nano material has good electrochemistry
Can, it can be further used for detecting certain metal ions.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (9)
1. a kind of graphene-porphyrin type organic nano material preparation method characterized by comprising
90-110 DEG C is heated to after graphene oxide water body dispersion liquid, porphyrin type organic and highly basic are mixed, wherein the oxygen
The pH value of the mixed solution of graphite alkene water body dispersion liquid, the porphyrin type organic and the highly basic is 9.5-11.
2. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that institute
It states and is aoxidized in the graphene oxide water body dispersion liquid when graphene oxide water body dispersion liquid is mixed with the porphyrin type organic
The mass ratio of graphene and the porphyrin type organic is 1-1.2:1.
3. graphene according to claim 2-porphyrin type organic nano material preparation method, which is characterized in that institute
It states when graphene oxide water body dispersion liquid is mixed with the porphyrin type organic and is mixed using ultrasound.
4. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that institute
Stating highly basic is organic alkali or inorganic strong alkali, and the inorganic strong alkali is sodium hydroxide or potassium hydroxide, and the organic alkali is alcohol
Sodium or potassium alcoholate.
5. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that institute
Stating porphyrin type organic is any one in protoporphyrin, porphyrin, tetraphenylporphyrin or haematoporphyrin.
6. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that add
The mixed solution of the heat graphene oxide water body dispersion liquid, the porphyrin type organic and the highly basic is in temperature
To heat the mixed solution in 90-110 DEG C of oil bath pan.
7. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that add
The mixed solution of the heat graphene oxide water body dispersion liquid, the porphyrin type organic and the highly basic is to reacting knot
The mixed solution is centrifuged after beam, centrifugal rotational speed 10000-14000rpm, centrifugation time is 15-25 minutes.
8. graphene according to claim 1-porphyrin type organic nano material preparation method, which is characterized in that with
Parts by weight meter, the graphene oxide water body dispersion liquid are by the 13-16 concentrated sulfuric acid, 3-5 parts of graphite, 1.5-3 parts of sodium nitrate and 13-
16 parts of potassium permanganate mix after being mixed and heated with 200-260 parts of hydrogen peroxide, 2-4 parts of dilute hydrochloric acid and 800-1200 parts of deionized waters
After be centrifuged and pH to 5.5-6.5 adjusted to be prepared.
9. graphene according to claim 8-porphyrin type organic nano material preparation method, which is characterized in that institute
Stating the concentrated sulfuric acid, the graphite, the sodium nitrate and the potassium permanganate and being mixed and heated is at a temperature of 0-4 DEG C by the stone
After being first heated to 30-40 DEG C after black, the described sodium nitrate, the concentrated sulfuric acid and potassium permanganate mixing and keep the temperature 20-30 minutes,
It is warming up to 90-100 DEG C again, and keeps the temperature 10-15 minutes.
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