CN106115787A - A kind of MnO2/ graphene nanocomposite material and the electrode prepared thereof - Google Patents
A kind of MnO2/ graphene nanocomposite material and the electrode prepared thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 45
- QAIPRVGONGVQAS-DUXPYHPUSA-N trans-caffeic acid Chemical compound OC(=O)\C=C\C1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-DUXPYHPUSA-N 0.000 claims abstract description 60
- 238000001514 detection method Methods 0.000 claims abstract description 34
- ACEAELOMUCBPJP-UHFFFAOYSA-N (E)-3,4,5-trihydroxycinnamic acid Natural products OC(=O)C=CC1=CC(O)=C(O)C(O)=C1 ACEAELOMUCBPJP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229940074360 caffeic acid Drugs 0.000 claims abstract description 30
- 235000004883 caffeic acid Nutrition 0.000 claims abstract description 30
- QAIPRVGONGVQAS-UHFFFAOYSA-N cis-caffeic acid Natural products OC(=O)C=CC1=CC=C(O)C(O)=C1 QAIPRVGONGVQAS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 24
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003814 drug Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 235000013305 food Nutrition 0.000 claims abstract description 6
- 235000013361 beverage Nutrition 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- -1 graphite Alkene Chemical class 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229950000845 politef Drugs 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000000840 electrochemical analysis Methods 0.000 abstract description 3
- 230000036039 immunity Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000000523 sample Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000004365 square wave voltammetry Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 208000032843 Hemorrhage Diseases 0.000 description 2
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229960000304 folic acid Drugs 0.000 description 2
- 235000019152 folic acid Nutrition 0.000 description 2
- 239000011724 folic acid Substances 0.000 description 2
- 235000001727 glucose Nutrition 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229960001031 glucose Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229940116315 oxalic acid Drugs 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000141 square-wave voltammogram Methods 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- 229940117960 vanillin Drugs 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000007271 Substance Withdrawal Syndrome Diseases 0.000 description 1
- 108090000190 Thrombin Proteins 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003451 Vitamin B1 Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 208000034158 bleeding Diseases 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 229940121657 clinical drug Drugs 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 235000021539 instant coffee Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
- 229960004072 thrombin Drugs 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 239000011691 vitamin B1 Substances 0.000 description 1
- 235000010374 vitamin B1 Nutrition 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to material preparation and electrochemical analysis techniques field, specifically disclose a kind of MnO2/ graphene nanocomposite material and the electrode prepared thereof.The preparation method of described material comprises the steps of: S11. is by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 8 ~ 24h, obtains suspension；S12. in suspension, add concentrated sulphuric acid, continue stirring 0.5 ~ 3h, obtain mixture；S13. heat the mixture to 70 ~ 90 DEG C, maintain constant temperature 0.5 ~ 3h, obtain reactant liquor；S14. reactant liquor deionized water is diluted 3 ~ 8 times, be cooled to room temperature, produce precipitation；S15. the filter membrane that precipitation aperture is 0.20 ~ 0.5mm of generation is collected, wash, be drying to obtain described MnO2/ graphene nanocomposite material.The electrode utilizing this material to prepare may be used for the caffeic acid content in detection by quantitative beverage, food or medicine, and have that detection limit is low, highly sensitive, the advantage such as good stability and strong interference immunity.
Description
Technical field
The present invention relates to material preparation and electrochemical analysis techniques field, be specifically related to a kind of MnO2/ graphene nano is multiple
Condensation material and the electrode prepared thereof.
Background technology
Nano material have excellence catalytic action, utilize its modified electrode prepared be widely used in food safety,
In the analysis detection in the fields such as bio-pharmaceuticals, clinical medicine and environmental monitoring；This is because nanometer material modified electrode is the cleverest
Sensitivity is high, detection limit is low, but also have preparation be simple and convenient to operate, the shortest and low cost and other advantages, can realize fast,
Economic analysis detection.
Caffeic acid has another name called Caffeic acid, is a kind of organic acid, phenolic compound.Caffeic acid is widely present in sky
So in herbaceous plant, as a kind of important medicine intermediate, its pharmacological action is notable, mainly shows as having antibacterial, disease-resistant
The functions such as poison, removing toxic substances, blood coagulation, mutation are anticancer, are shrinking reinforcement blood capillary, are improving thrombin, leukocyte increasing and platelet
Etc. aspect also can play its effect.Caffeic acid is except, in addition to various, outside the hemorrhage prevention of internal medicine and treatment, being used clinically
In the treatment of the diseases such as gynecological bleeding, tumor disease chemotherapy, radiotherapy, evident in efficacy.Relevant report also show the most biological
Movable have dependency with caffeic acid, and human body can be caused damage by heavy dose of or life-time service caffeic acid, and particularly it has necessarily
Additive, once disable and there will be down in spirits, the from head to foot various withdrawal symptoms such as tired weak.Therefore, carry out caffeic acid
Detection by quantitative not only contribute to clinical drug safety, moreover it is possible to content caffeinic in commercial beverage, food is carried out daily prison
Control, is conducive to ensureing human physical and mental health.At present, domestic report detects caffeinic method and is mainly chromatography.Compare electrification
Learning detection method, chromatographic instrument and equipment is expensive, it is relative complex to operate, and remains to be further improved.And needed for electrochemical detection method
Equipment is simple, speed is fast, highly sensitive, Site Detection can be used for；Particularly caffeic acid contains the most oxidized unsaturated double-bond
And hydroxyl, it is possible to use the signal of telecommunication that its oxidizing process produces carries out detection by quantitative to it.At present, electrochemical method detection is related to
In caffeinic report, utilize single-walled nanotube Modified graphite electrode and siloxane molecule trace electrode that caffeic acid is carried out electricity
Chemical detection, but these methods remain to be further improved at aspects such as detection limit, sensitivity, stability and anti-interferences.Ratio
As, the detection of nanometer gold/Graphene electrodes disclosed in existing document is limited to 5 × 10-8Mol/L(Zhang Y, Liu Y, He
J, Pang P, Gao Y, Hu Q, Electroanalysis, 193 (2014) 238-246), siloxane molecule trace electricity
The detection of pole is limited to 1.5 × 10-7Mol/L(Leite F R, Santo W J, Kubota L T, Sensors and
Actuators B, 128 (2007) 30-37).
Summary of the invention
To be solved by this invention primarily technical problem is that, in order to overcome caffeic acid detecting electrode in prior art to there is inspection
The problem going out limit for height, it is provided that a kind of MnO for preparing caffeic acid detecting electrode2/ graphene nanocomposite material.By this material
The electrode prepared has low-down detection limit for caffeinic detection.
Another technical problem to be solved by this invention is to provide a kind of MnO2/ graphene composite film modified electrode and
Preparation method.
Above-mentioned technical problem to be solved by this invention, is achieved by the following technical programs:
A kind of MnO2The preparation method of/graphene nanocomposite material, it is characterised in that comprise the steps of:
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 8 ~ 24h, obtains suspension；
S12. in suspension, add concentrated sulphuric acid, continue stirring 0.5 ~ 3h, obtain mixture；
S13. heat the mixture to 70 ~ 90 DEG C, maintain constant temperature 0.5 ~ 3h, obtain reactant liquor；
S14. reactant liquor deionized water is diluted 3 ~ 8 times, be cooled to room temperature, produce precipitation；
S15. the filter membrane that precipitation aperture is 0.20 ~ 0.5mm of generation is collected, wash, be drying to obtain described MnO2/ stone
Ink alkene nano composite material；
Mesoporous carbon described in step S11, KMnO4It is 1g:8 ~ 12g:400 ~ 600mL with the amount ratio of deionized water；
Concentrated sulphuric acid described in step S12 is the H that mass fraction is more than or equal to 70%2SO4Aqueous solution；The volume of described concentrated sulphuric acid
Consumption is 0.5% ~ 3% of the suspension vol described in step S11.
Preferably, the mesoporous carbon described in step S11, KMnO4With the amount ratio of deionized water be 1g:10 ~ 12g:400 ~
500mL；
Most preferably, the mesoporous carbon described in step S11, KMnO4It is 1g:12g:450mL with the amount ratio of deionized water.
The reaction equation that this step is carried out: 4MnO4 − + 3C + H2O = 4 MnO2 + CO3 2− + 2HCO3 −。
Preferably, the mixing time in step S11 is 10 ~ 12h.
Preferably, the concentrated sulphuric acid described in step S12 is the H that mass fraction is more than or equal to 90%2SO4Aqueous solution.
Most preferably, the concentrated sulphuric acid described in step S12 be mass fraction be the H of 96%2SO4Aqueous solution.
Preferably, the volumetric usage of described concentrated sulphuric acid is 0.5% ~ 2% of the suspension vol described in step S11.
It is further preferred that the volumetric usage of described concentrated sulphuric acid is the suspension vol described in step S11 0.5% ~
1%。
Most preferably, the volumetric usage of described concentrated sulphuric acid is 0.8% of the suspension vol described in step S11.
Preferably, the mixing time described in step S12 is 0.5 ~ 1.5h.
Most preferably, the mixing time described in step S12 is 1.2h.
Preferably, step S13 heats the mixture to 75 ~ 85 DEG C, maintain constant temperature 0.5 ~ 1.5h.
Most preferably, step S13 heats the mixture to 85 DEG C, maintain constant temperature 1.5h.
Preferably, reactant liquor deionized water is diluted 3 ~ 5 times by step S14.
Most preferably, reactant liquor deionized water is diluted 5 times by step S14.
Preferably, the filter membrane that precipitation aperture is 0.20 ~ 0.25mm of generation is collected by step S14.
Most preferably, the filter membrane that precipitation aperture is 0.25mm of generation is collected by step S14.
Preferably, the filter membrane described in step S14 is poly tetrafluoroethylene.
Nano composite material the physicochemical characteristic of comprehensive monocomponent nanocomposite material can strengthen its concerted catalysis performance.Such as
Utilize inorganic nano material functionalization graphene can reduce the interaction of graphene film interlayer, strengthen the dispersibility of composite
Can, improve its electricity, optics and catalytic performance.Inorganic, metal oxide/Graphene is to be modified by transition metal oxide material
Or the novel nanocomposite materials that holdfast is prepared on graphene sheet layer, the conductivity of material can be effectively improved, make material
Crystal structure is more stable, the MnO that the present invention provides2/ graphene nanocomposite material belongs to this kind of material.
Additionally, for the electrode using nano composite material formation determination certain chemical composition content concrete, then need to send out
A person of good sense prepares different nano composite materials according to the character of chemical substance the most to be determined.The electrode prepared is to survey
The quality of the effects such as the detection limit of fixed material, sensitivity, stability and anti-interference is main by the preparation of nano composite material
Method determines.The preparation method of nano composite material mainly includes raw-material selection, raw-material proportioning, and each step
Reaction condition etc..For the nano composite material as electrode, raw-material selection in its preparation method, proportioning and each step
The difference of rapid reaction condition all can cause the greatest differences of the follow-up electrode electrical property prepared, thus causes detection limit, spirit
The greatest differences of the effects such as sensitivity, stability and anti-interference.
Caffeic acid contains the most oxidized unsaturated double-bond and hydroxyl, it is easy to be electrochemically oxidized；But it is the most modified
Working electrode or one pack system graphene modified electrode on also exist that electrochemical response signal is weak, can not detect low concentration coffee
The deficiencies such as the content of coffee acid.
According to caffeinic characteristic, for obtaining the caffeic acid detecting electrode with low detection limit, inventor passes through
Substantial amounts of experiment, constantly adjusts the technological parameter in raw material composition, proportioning and preparation process, draws above-mentioned MnO2/ Graphene
Nano composite material, the MnO prepared with this composite2/ graphene composite film modified electrode has the electrochemistry of excellence
Response performance, can significantly reduce caffeinic detection limit in sample, and improve the sensitivity of detection, stability with anti-interference
Property.
The present invention provides a kind of MnO prepared by above-mentioned preparation method2/ graphene nanocomposite material.
The present invention provides a kind of MnO2The preparation method of/graphene composite film modified electrode, comprises the steps of:
Pretreatment glass-carbon electrode；
By described MnO2/ graphene nanocomposite material solvent dissolves, and fully dispersed dispersion liquid；
Dispersant liquid drop is added in the glassy carbon electrode surface handled well, the most i.e. obtains MnO2/ graphene composite film modified electrode.
Preferably, pretreatment glass-carbon electrode method particularly includes: take glass-carbon electrode, at Al2O33 ~ 10 are first roughly ground on powder
Min, then fine grinding 3 ~ 10 min on polishing powder, clean, stand-by.
Most preferably, pretreatment glass-carbon electrode method particularly includes: take glass-carbon electrode, at Al2O3First roughly grind on powder
5min, then fine grinding 5 min on polishing powder, clean, stand-by.
Preferably, MnO2/ graphene nanocomposite material DMF(dimethylformamide) dissolve, MnO2/ graphene nano
Composite is 1 ~ 3mg:1mL with the amount ratio of DMF；Described dispersion uses ultrasonic disperse.
Most preferably, MnO2/ graphene nanocomposite material DMF dissolves, MnO2/ graphene nanocomposite material and DMF
Amount ratio be 1.8mg:1mL；Described dispersion uses ultrasonic disperse.
The present invention provides a kind of MnO prepared by above-mentioned preparation method2/ graphene composite film modified electrode.
Above-mentioned MnO2/ graphene composite film modified electrode is the application of caffeic acid content in detection beverage, food and medicine.
Beneficial effect: (1) present invention solve chromatography instrument and equipment of also existing during caffeic acid measures expensive,
Operate the problems such as complicated, time-consuming length, it is provided that a kind of brand-new MnO for preparing electrode2/ graphene nanocomposite material；
(2) electrode utilizing this material to prepare may be used for the caffeic acid in detection by quantitative beverage, food and medicine, and has inspection
The advantages such as rising limit is low, highly sensitive, good stability and strong interference immunity；(3) embodiment data show, this electrode is to caffeinic
Detection limit is calculated as 2.71 × 10–10Mol/L, is greatly lowered than the detection limit of the electrode of prior art report；(4) this electrode
Re-using in preserving one month in refrigerator, peak current is up to the 92% of first measured value, it was demonstrated that its storage stability is good；(5) should
Electrode under the conditions of the exotic such as ascorbic acid, folic acid, oxalic acid, vanillin, glucose and vitamin B1 of 10 times of concentration to coffee
Coffee acid oxidation peak signal without substantially interfering with, common inorganic ions such as H+、K+、Na+、NH4 +、Ca2+、Mg2+、OH–、Cl–、SO4 2–、
H2PO4 –Deng to caffeinic detection also without substantially interfering with.
Accompanying drawing explanation
Fig. 1 is Graphene (A) and MnO2The scanning electron microscope (SEM) photograph of/graphene nanocomposite material (B), and MnO2/ Graphene
The infrared spectrogram (C) of nano composite material.
Fig. 2 is glass-carbon electrode (a), Graphene/glass-carbon electrode (b) and MnO2/ graphene composite film modified electrode (c) exists
0.01 mol/L K3[Fe(CN)6] and 0.20 mol/L KCl at the bottom of cyclic voltammogram (A) in liquid and AC impedance figure (B).
Fig. 3 is glass-carbon electrode (a), Graphene/glass-carbon electrode (b) and MnO2/ graphene composite film modified electrode (c) 1.0 ×
10-3Square wave voltammogram in mol/L caffeic acid solution.
Fig. 4 is 1.0 × 10-3Mol/L caffeic acid is at MnO2On/graphene composite film modified electrode under different pH condition
Square wave volt-ampere curve figure (pH value of curve a ~ g is 2.0 ~ 8.0).
Fig. 5 is MnO2/ graphene composite film modified electrode square wave volt-ampere curve figure (A) in variable concentrations caffeic acid with
And the linear relationship chart (B) of caffeic acid concentration and its oxidation peak current.
Detailed description of the invention
The present invention is explained further below in conjunction with specific embodiment, but the present invention is not done any type of limit by embodiment
Fixed.
Embodiment 1 MnO2The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, comprises the steps of:
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 12h, obtains suspension；
S12. in suspension, add concentrated sulphuric acid, continue stirring 1.2h, obtain mixture；
S13. heat the mixture to 85 DEG C, maintain constant temperature 1.5h, obtain reactant liquor；
S14. reactant liquor deionized water is diluted 5 times, be cooled to room temperature, produce precipitation；
S15. the filter membrane that precipitation aperture is 0.25mm of generation is collected, wash, be drying to obtain described MnO2/ Graphene
Nano composite material；
Mesoporous carbon described in step S11, KMnO4The amount ratio of mixing and deionized water is 1g:12g:450mL；
Concentrated sulphuric acid described in step S12 be mass fraction be the H of 96%2SO4Aqueous solution；The volumetric usage of described concentrated sulphuric acid is
0.8% of suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
MnO prepared by the present embodiment2Pattern and the optical signature of/graphene nanocomposite material are as follows: Tu1AHe
Figure 1B is Graphene and the MnO of ultrasonic disperse2The scanning electron microscope (SEM) photograph of/graphene nanocomposite material, can be observed stone from Figure 1A
Ink alkene has typical fold, laminar structured.Figure 1B can be clearly observed the most spherical MnO2Granule is attached to bending
On the flake graphite alkene lamella of fold, major part MnO2The particle diameter of granule is about about 450nm, shows MnO2/ graphene nano is multiple
Condensation material is successfully prepared.At 530cm seen from from the infrared spectrogram of Fig. 1 C-1Neighbouring there is an obvious MnO2Spy
Levy peak, further illustrate MnO2Successfully it is supported on Graphene.
Embodiment 2 MnO2The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, comprises the steps of:
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 8h, obtains suspension；
S12. in suspension, add concentrated sulphuric acid, continue stirring 2h, obtain mixture；
S13. heat the mixture to 90 DEG C, maintain constant temperature 2h, obtain reactant liquor；
S14. reactant liquor deionized water is diluted 6 times, be cooled to room temperature, produce precipitation；
S15. the filter membrane that precipitation aperture is 0.20mm of generation is collected, wash, be drying to obtain described MnO2/ Graphene
Nano composite material；
Mesoporous carbon described in step S11, KMnO4It is 1g:10g:600mL with the amount ratio of deionized water；
Concentrated sulphuric acid described in step S12 be mass fraction be the H of 90%2SO4Aqueous solution；The volumetric usage of described concentrated sulphuric acid is
2% of suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
Embodiment 3 MnO2The preparation of/graphene nanocomposite material
A kind of MnO2The preparation method of/graphene nanocomposite material, comprises the steps of:
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 24h, obtains suspension；
S12. in suspension, add concentrated sulphuric acid, continue stirring 0.5h, obtain mixture；
S13. heat the mixture to 75 DEG C, maintain constant temperature 0.5h, obtain reactant liquor；
S14. reactant liquor deionized water is diluted 3 times, be cooled to room temperature, produce precipitation；
S15. the filter membrane that precipitation aperture is 0.30mm of generation is collected, wash, be drying to obtain described MnO2/ Graphene
Nano composite material；
Mesoporous carbon described in step S11, KMnO4The amount ratio of mixing and deionized water is 1g:8g:400mL；
Concentrated sulphuric acid described in step S12 be mass fraction be the H of 70%2SO4Aqueous solution；The volumetric usage of described concentrated sulphuric acid is
3% of suspension vol described in step S11；
Filter membrane described in step S14 is poly tetrafluoroethylene.
Embodiment 4 MnO2/ graphene composite film modified electrode
MnO2The preparation method of/graphene composite film modified electrode is as follows:
Pretreatment glass-carbon electrode；Pretreatment glass-carbon electrode method particularly includes: take glass-carbon electrode, first at Al2O3Roughly grind on powder
5min, then fine grinding 5 min on polishing powder, clean, stand-by.
The MnO that embodiment 1 is prepared2/ graphene nanocomposite material DMF dissolves, and ultrasonic disperse 10min makes
Its fully dispersed dispersion liquid；MnO2/ graphene nanocomposite material is 1.8mg:1mL with the amount ratio of DMF；Again by dispersion liquid
Dropping is in the glassy carbon electrode surface handled well so that it is be uniformly distributed, drying MnO under infrared lamp2/ graphene composite film is repaiied
Decorations electrode.
Embodiment 5 MnO2/ graphene composite film modified electrode performance detects
The MnO that the present embodiment prepares with embodiment 42/ graphene composite film modified electrode is as experimental subject, by itself and platinum
Sheet auxiliary electrode, SCE reference electrode constitute three-electrode system, and (Shanghai China in morning instrument is limited to connect CHI660 electrochemical workstation
Company) carry out chemical property detection.
(1) Electrochemical Characterization of Different electrodes
With K3[Fe(CN)6] it is that probe utilizes cyclic voltammetric and AC impedence method to investigate the electrochemistry of different modifying electrode
Energy.Fig. 2 represents that probe ion is at glass-carbon electrode (a), Graphene/glass-carbon electrode (b) and MnO2/ graphene composite film modified electrode
Volt-ampere on (c) and impedance behavior.From Fig. 2 A and 2B, probe ion is at MnO2On/graphene composite film modified electrode
Oxidation peak current maximum (25.2 A), electrochemical impedance are minimum (1.2k Ω)；The MnO that the present invention prepares is described2/ Graphene
Complex film modified electrode has more preferable electrocatalysis characteristic.This is due to MnO2It is supported on graphenic surface, effectively increases multiple
Condensation material specific surface area, thus optimize the comprehensive electrochemical of composite modified electrode.
(2) caffeinic electrocatalysis characteristic is contrasted by Different electrodes
For embodying MnO more intuitively2/ graphene composite film modified electrode is to caffeinic electrocatalysis characteristic, by glass carbon electricity
Pole (a), Graphene/glass-carbon electrode (b) and MnO2Three kinds of Different electrodes of/graphene composite film modified electrode (c) are respectively placed in 1.0
×10-3In the caffeic acid solution of mol/L, measure its square wave voltammogram.As it is shown on figure 3, in isocyatic caffeic acid solution, this
The MnO that invention prepares2/ graphene composite film modified electrode shows optimal electrochemical response signal, its oxidation peak electricity
Stream maximum (7.5 A), peak type are preferable, illustrate the MnO that the present invention prepares2/ graphene composite film modified electrode can be effective
Ground improves the detection sensitivity of sensor.
(3) MnO that the present invention prepares2/ graphene composite film modified electrode under different pH condition to caffeic acid
Electrochemical response performance
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode be working electrode three-electrode system in
Square wave voltammetry has investigated caffeic acid oxidation peak current situation of change in different pH value supporting electrolytes, and result shows (figure
4) all occurring obvious peak in the range of pH value is 2.0 ~ 8.0, peak current first becomes larger along with the reduction of pH, until pH=
When 5.0, peak current reaches its maximum；Subsequently when pH value continues to reduce, there is reduction trend in peak current, and system of the present invention is described
Standby electrode has best electro-chemical test performance under conditions of pH value is 5.0 to caffeic acid.
(4) MnO that the present invention prepares2/ graphene composite film modified electrode is to caffeinic Electrochemical Detection performance
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode is in the three-electrode system of working electrode, with
PH be the Potassium Hydrogen Phthalate of 5.0 be end liquid, enrichment time is 120s, and the caffeic acid solution of a series of concentration is carried out square wave
Voltammetric scan, result shows that the caffeinic oxidation peak current of (see figure 5) increases with its concentration and increases, in two sections of concentration ranges
Good linear relationship occur, linear equation is respectively as follows:i p =1.24×10-2 c+4.0×10-7(R 2=0.973) andi p=4.46×
10-3 c+2.0×10-6 (R 2=0.980)；Detection limit is calculated as 2.71 × 10-10 mol/L.Illustrate that prepared electrode has well
Linear relationship, high sensitivity and low detection limit.
(5) MnO that the present invention prepares2The capacity of resisting disturbance of/graphene composite film modified electrode and stability.
The MnO prepared with the present embodiment 42/ graphene composite film modified electrode is the three-electrode system of working electrode
In, with Potassium Hydrogen Phthalate that pH is 5.0 for end liquid, enrichment time is 120s, utilizes square wave voltammetry to investigate simulation interference
Material is to 1.0 × 10-3The caffeinic oxidation peak current impact of mol/L.Result shows the MnO prepared with the present invention2/ stone
The ink complex film modified electrode of alkene is at ascorbic acid, folic acid, oxalic acid, vanillin, glucose and the vitamin B of 10 times of concentration1Outside Deng
Under material interference, caffeinic oxidation peak current to be had no significant effect；Common inorganic ions such as H+、K+、Na+、NH4 +、Ca2+、
Mg2+、OH–、Cl–、SO4 2–、H2PO4 –Deng to caffeinic detection also without substantially interfering with, thus confirm electrode tool prepared by the present invention
There is the selectivity of excellence, caffeinic detection in actual sample can be used for.
MnO is investigated with square wave voltammetry2The stability of/graphene composite film modified electrode.First by prepared electrode with
The three-electrode system that platinum plate electrode, SCE electrode are constituted connects electrochemical workstation, at the bottom of the Potassium Hydrogen Phthalate that pH is 5.0
In liquid, record 1.0 × 10 with 120s enrichment time-3Mol/L caffeinic oxidation peak current initial value.By this electrode in refrigerator
With similarity condition, the caffeic acid of same concentration is measured again in preserving one month, found that its peak point current is up to just
The 92% of measured value is it was confirmed electrode prepared by the present invention has good storage stability.
Embodiment 6 actual sample detects
Certain brand instant coffee is configured to 0.05g/mL solution to be measured, is the phthalic acid of 5.0 with pH after leaching insoluble matter
Hydrogen potassium solution is settled to 1L as actual measurement sample 1；500mg Radix Dauci Sativae is pulverized in juice extractor, after filtration by filtrate pH is
The Potassium Hydrogen Phthalate solution of 5.0 is settled to 1L as actual measurement sample 2；Certain tablet is taken 500mg, after pulverizing in grinding,
Filter after ultrasonic in its 10mL ethanol, the Potassium Hydrogen Phthalate solution that filtrate pH is 5.0 is settled to 1L as actual measurement
Sample 3；Utilize the MnO that embodiment 4 prepares2/ graphene composite film modified electrode is to three kinds of actual samples after handling well
In caffeic acid content carry out mark-on and reclaim and measure, its response rate between 98.9 ~ 102.3%, relative standard deviation 2.1 ~
Between 3.6%；MnO prepared by the present invention is described2The caffeinic detection in actual sample of/graphene composite film modified electrode
There is higher accuracy and feasibility.
Claims (10)
1. a MnO2The preparation method of/graphene nanocomposite material, it is characterised in that comprise the steps of:
S11. by mesoporous carbon and KMnO4Mixing, adds deionized water stirring 8 ~ 24h, obtains suspension；
S12. in suspension, add concentrated sulphuric acid, continue stirring 0.5 ~ 3h, obtain mixture；
S13. heat the mixture to 70 ~ 90 DEG C, maintain constant temperature 0.5 ~ 3h, obtain reactant liquor；
S14. reactant liquor deionized water is diluted 3 ~ 8 times, be cooled to room temperature, produce precipitation；
S15. the filter membrane that precipitation aperture is 0.20 ~ 0.5mm of generation is collected, wash, be drying to obtain described MnO2/ graphite
Alkene nano composite material；
Mesoporous carbon described in step S11, KMnO4It is 1g:8 ~ 12g:400 ~ 600mL with the amount ratio of deionized water；Preferably,
Mesoporous carbon described in step S11, KMnO4It is 1g:10 ~ 12g:400 ~ 500mL with the amount ratio of deionized water；Most preferably,
Mesoporous carbon described in step S11, KMnO4It is 1g:12g:450mL with the amount ratio of deionized water；
Concentrated sulphuric acid described in step S12 is the H that mass fraction is more than or equal to 70%2SO4Aqueous solution；The volume of described concentrated sulphuric acid is used
Amount is 0.5% ~ 3% of the suspension vol described in step S11；Preferably, the concentrated sulphuric acid described in step S12 is mass fraction
H more than or equal to 90%2SO4Aqueous solution；Preferably, the volumetric usage of described concentrated sulphuric acid is the suspension liquid described in step S11
Long-pending 0.5% ~ 2%；Most preferably, the volumetric usage of described concentrated sulphuric acid be the suspension vol described in step S11 0.5% ~
1%。
Preparation method the most according to claim 1, it is characterised in that the mixing time in step S11 is 10 ~ 12h；Step
Mixing time described in S12 is 0.5 ~ 1.5h；Step S13 heats the mixture to 75 ~ 85 DEG C, maintain constant temperature 0.5 ~
1.5h。
Preparation method the most according to claim 1, it is characterised in that in step S14, reactant liquor deionized water is diluted 3
~ 5 times.
Preparation method the most according to claim 1, it is characterised in that in step S14 by the precipitation aperture of generation be
The filter membrane of 0.20 ~ 0.25mm is collected.
Preparation method the most according to claim 1, it is characterised in that the filter membrane described in step S14 is politef
Film.
6. the MnO that the preparation method described in any one of claim 1 ~ 5 prepares2/ graphene nanocomposite material.
7. a MnO2The preparation method of/graphene composite film modified electrode, it is characterised in that comprise the steps of:
Pretreatment glass-carbon electrode；
By the MnO described in claim 102/ graphene nanocomposite material solvent dissolves, and fully dispersed dispersion liquid；
Dispersant liquid drop is added in the glassy carbon electrode surface handled well, the most i.e. obtains MnO2/ graphene composite film modified electrode.
Preparation method the most according to claim 7, it is characterised in that pretreatment glass-carbon electrode method particularly includes: take glass
Carbon electrode, at Al2O33 ~ 10min, then fine grinding 3 ~ 10min on polishing powder is first roughly ground on powder, clean, stand-by；Described
MnO2/ graphene nanocomposite material DMF disperses, MnO2/ graphene nanocomposite material is 1 ~ 3mg with the amount ratio of DMF:
1mL；Described dispersion uses ultrasonic disperse.
9. the MnO that the preparation method described in claim 7 or 8 prepares2/ graphene composite film modified electrode.
10. the MnO described in claim 92/ graphene composite film modified electrode caffeic acid in detection beverage, food or medicine contains
The application of amount.
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