CN109752433A - Nickel phosphate/Co-MOFs composite material and preparation method and application thereof - Google Patents
Nickel phosphate/Co-MOFs composite material and preparation method and application thereof Download PDFInfo
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- CN109752433A CN109752433A CN201910161825.4A CN201910161825A CN109752433A CN 109752433 A CN109752433 A CN 109752433A CN 201910161825 A CN201910161825 A CN 201910161825A CN 109752433 A CN109752433 A CN 109752433A
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- 229910000159 nickel phosphate Inorganic materials 0.000 title claims abstract description 65
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 239000012921 cobalt-based metal-organic framework Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 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 claims abstract description 35
- 239000008103 glucose Substances 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 230000001376 precipitating effect Effects 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- GANMEEJISNNTGT-UHFFFAOYSA-N ethanol;2-methyl-1h-imidazole Chemical compound CCO.CC1=NC=CN1 GANMEEJISNNTGT-UHFFFAOYSA-N 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 210000002966 serum Anatomy 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 239000010411 electrocatalyst Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 3
- 229930091371 Fructose Natural products 0.000 description 3
- 239000005715 Fructose Substances 0.000 description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 3
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 3
- 241000219095 Vitis Species 0.000 description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 description 3
- 235000014787 Vitis vinifera Nutrition 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 206010012601 diabetes mellitus Diseases 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 229960002737 fructose Drugs 0.000 description 3
- 239000008101 lactose Substances 0.000 description 3
- 229960001375 lactose Drugs 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229940116269 uric acid Drugs 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- PQLQPCFUTCUMDL-UHFFFAOYSA-N CN(C=O)C.CC=1NC=CN1 Chemical compound CN(C=O)C.CC=1NC=CN1 PQLQPCFUTCUMDL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- -1 P elements Chemical compound 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- XNMUCIILODALDI-UHFFFAOYSA-N nickel phosphoric acid Chemical compound [Ni].P(O)(O)(O)=O XNMUCIILODALDI-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Landscapes
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a nickel phosphate/Co-MOFs composite material and a preparation method and application thereof, belonging to the technical field of electrocatalyst materials. Dissolving nickel salt and phosphate in water, adding N, N-dimethylformamide, uniformly mixing, performing hydrothermal reaction in a reaction kettle, filtering after the hydrothermal reaction is finished, taking precipitate, washing and drying the precipitate to obtain nano nickel phosphate; and then dispersing nano nickel phosphate into a solvent, adding cobalt salt, stirring for 1-5h, then adding a 2-methylimidazole solution to obtain a reaction solution, stirring the reaction solution for 0.5-5h, standing for 1-24h, centrifuging, and taking a precipitate to obtain the nickel phosphate/Co-MOFs composite material. The electrode modified by the composite material has high sensitivity and low detection limit on glucose sensing, and can be used for detecting glucose in human serum. The composite material has simple preparation process, no need of additives such as reducing agent, structure directing agent and the like, low requirement on equipment, low cost and suitability for industrial production.
Description
Technical field
The invention belongs to electrocatalyst materials technical fields, and in particular to a kind of nickel phosphate/Co-MOFs composite material and its
Preparation method and application.
Background technique
In normal human blood glucose content be 3.8-6.9mmol/L, blood-sugar content be above standard value illustrate human body occur
Lesion, wherein the diabetes due to caused by hypoinsulinism are exactly a kind of disease that can not be cured.Diabetes threaten at present
Up to more than the 600000000 people's health in the whole world, diabetic needs blood sugar concentration in daily real-time monitoring body, therefore develops portable, low
The glucose sensor of cost has great importance.
Currently, high performance liquid chromatography, colorimetric method, chemoluminescence method, fluorescence method, surface-enhanced Raman method, mass spectrography and
Electrochemical process is all the technology for detecting glucose.Wherein, electrochemical method is with easy to operate, equipment cost is low, easy of integration, portable
The advantages that become current most potential glucose detection means, the core component of electrochemical sensor is to pass in this method
The elctro-catalyst of sensor, generally noble metal nano particles used in the glucose sensor of present business.Noble metal price is high
Expensive and easy inactivation prevents it to be widely applied.
Transition metal element has the high electrochemical activity of similar noble metal, while storing and enriching, and price is low, is that one kind is replaced
Important elctro-catalyst for noble metal as glucose sensor.In order to solve the reunion during nickel phosphate electro-catalysis and compare table
The low problem of area, the present invention design a kind of phosphoric acid nickel composite catalyst of aperture MOF support, the electrocatalytic oxidation for glucose
Change.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of nickel phosphate/Co-MOFs composite material preparation sides
Method；The second purpose is a kind of nickel phosphate/Co-MOFs composite material；The third purpose is to provide a kind of electrochemical sensor；Mesh
Four be to provide application of the electrochemical sensor in glucose detection.
In order to achieve the above objectives, the invention provides the following technical scheme:
1, a kind of nickel phosphate/Co-MOFs composite material preparation method, described method includes following steps:
(1) after nickel salt and phosphate being dissolved in water, n,N-Dimethylformamide is added, in carrying out water in reaction kettle after mixing
Thermal response filters to take precipitating after the hydro-thermal reaction, the precipitating is carried out nanometer nickel phosphate is made after washing is dry；
(2) it disperses nanometer nickel phosphate obtained in step (1) in solvent, is then added cobalt salt, stir after 1-5h again
2-methylimidazole solution is added, obtains reaction solution, stands 1-24h, centrifuging and taking precipitating, system after the reaction solution is stirred 0.5-5h
Obtain nickel phosphate/Co-MOFs composite material.
Preferably, in step (1), nickel element in the nickel salt, P elements, water and n,N-Dimethylformamide in phosphate
Molar ratio be 40:20:5-35:1-9；The condition of the hydro-thermal reaction is to react 3-10h at 100-180 DEG C.
Preferably, in step (1), the nickel salt is one of nickel nitrate, nickel chloride or nickel sulfate；The phosphate is
One of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
Preferably, in step (1), the drying is specially the dry 10h at 60 DEG C.
Preferably, in step (2), nanometer nickel phosphate, cobalt salt and 2- methyl miaow obtained in step (1) in the reaction solution
The mass ratio of azoles is 100:14-742:16-821.
Preferably, in step (2), the solvent is one of methanol, n,N-Dimethylformamide or ethyl alcohol；The 2-
Methyl imidazole solution is 2-methylimidazole methanol solution, 2-methylimidazole N,N-dimethylformamide solution or 2-methylimidazole second
One of alcoholic solution.
Preferably, in step (2), the cobalt salt is one of cobalt nitrate, cobalt chloride or cobaltous sulfate.
2, nickel phosphate/Co-MOFs composite material of method preparation.
3, a kind of electrochemical sensor, including electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell and
Electrolyte, the working electrode surface are coated with the nickel phosphate/Co-MOFs composite material.
Preferably, the working electrode is prepared as follows:
It disperses nickel phosphate/Co-MOFs composite material in n,N dimethylformamide with the matched proportion density of 1-5mg/mL,
Electrode modification solution is obtained, the electrode modification solution is coated on the electrode after being polished, being cleaned, is dried.
Preferably, the electrode is one of glass-carbon electrode, graphite electrode or gold electrode.
4, application of a kind of electrochemical sensor in glucose detection.
The beneficial effects of the present invention are: the present invention provides a kind of nickel phosphate/Co-MOFs composite material and its preparation sides
Method and application enable nanometer nickel phosphate to be equably supported in this method by the exchange interaction of cobalt ions and nickel ion
On Co-MOFs, and Co-MOFs can effectively prevent the reunion of nanometer nickel phosphate, and then increase the specific surface area of nanometer nickel phosphate,
So that the performance of the electrocatalytic oxidation glucose of nanometer nickel phosphate improves 21 times.With the electrode of composite material modification to grape
The sensing sensitivity of sugar is up to 2783 μ A/mMcm2, limit is detected down to 0.7 μm of ol/L, can be used for glucose in human serum
Detection.The composite material preparation process is simple, not high to equipment requirement woth no need to additives such as reducing agent, structure directing agents,
It is at low cost, it is suitble to industrialized production.
Other advantages, target and feature of the invention will be illustrated in the following description to a certain extent, and
And to a certain extent, based on will be apparent to those skilled in the art to investigating hereafter, Huo Zheke
To be instructed from the practice of the present invention.Target of the invention and other advantages can be realized by following specification and
It obtains.
Detailed description of the invention
To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is made below in conjunction with attached drawing excellent
The detailed description of choosing, in which:
Fig. 1 is the SEM figure of the nanometer nickel phosphate prepared in embodiment 1；
Fig. 2 is the SEM of the Co-MOFs formed during preparing nickel phosphate/Co-MOFs composite material in embodiment 1
Figure；
Fig. 3 is that nickel phosphate/Co-MOFs composite material SEM figure is prepared in embodiment 1；
Fig. 4 is current-responsive test result figure of the glucose molecule on different materials modified electrode in embodiment 4；
Fig. 5 is the i-t curve graph of different glucose solution in embodiment 5；
Fig. 6 is for current value on i-t curve in Fig. 5 as glucose concentration increases and linearly increasing linearity curve
Figure；
Fig. 7 is the anti-interference test of the nickel phosphate/Co-MOFs composite material modification working electrode prepared in embodiment 1
Result figure.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
Prepare nickel phosphate/Co-MOFs composite material
(1) after nickel nitrate and ammonium dihydrogen phosphate being dissolved in deionized water, n,N-Dimethylformamide is added, in anti-after mixing
The interior hydro-thermal reaction 5h at 100 DEG C of kettle is answered, filters to take precipitating after hydro-thermal reaction, precipitating is washed dry at 60 DEG C
Nanometer nickel phosphate is made in 10h, wherein nickel element in nickel nitrate, P elements, water and n,N-Dimethylformamide in ammonium dihydrogen phosphate
Molar ratio be 40:20:6:9；
(2) it disperses nanometer nickel phosphate obtained in step (1) in methanol, is then added cobalt nitrate, stir after 2h again
2-methylimidazole methanol solution is added, obtains reaction solution, is stood for 24 hours after reaction solution is stirred 2h, phosphoric acid is made in centrifuging and taking precipitating
Nickel/Co-MOFs composite material, wherein nanometer nickel phosphate obtained in step (1) in reaction solution, cobalt nitrate and 2-methylimidazole
Mass ratio is 100:145:324.
Embodiment 2
Prepare nickel phosphate/Co-MOFs composite material
(1) after nickel sulfate and sodium dihydrogen phosphate being dissolved in deionized water, n,N-Dimethylformamide is added, in anti-after mixing
The interior hydro-thermal reaction 10h at 150 DEG C of kettle is answered, precipitating is filtered to take after hydro-thermal reaction, precipitating is washed and is done at 60 DEG C
Nanometer nickel phosphate is made in dry 10h, and wherein nickel element in nickel salt, P elements in phosphate, water and n,N-Dimethylformamide are rubbed
You are than being 40:20:35:1；
(2) it disperses nanometer nickel phosphate obtained in step (1) in ethyl alcohol, is then added cobaltous sulfate, stir after 1h again
2-methylimidazole ethanol solution is added, obtains reaction solution, stands 10h after reaction solution is stirred 0.5h, phosphorus is made in centrifuging and taking precipitating
Sour nickel/Co-MOFs composite material, wherein nanometer nickel phosphate obtained in step (1) in reaction solution, cobalt salt and 2-methylimidazole
Mass ratio is 100:14:821.
Embodiment 3
Prepare nickel phosphate/Co-MOFs composite material
(1) after nickel chloride and diammonium hydrogen phosphate being dissolved in deionized water, n,N-Dimethylformamide is added, in anti-after mixing
The interior hydro-thermal reaction 3h at 180 DEG C of kettle is answered, filters to take precipitating after hydro-thermal reaction, precipitating is washed dry at 60 DEG C
Nanometer nickel phosphate is made in 10h, wherein nickel element in nickel salt, in phosphate P elements, water and n,N-Dimethylformamide mole
Than for 40:20:18:5；
(2) it disperses nanometer nickel phosphate obtained in step (1) in n,N-Dimethylformamide, chlorination is then added
Cobalt adds 2-methylimidazole n,N-Dimethylformamide solution after stirring 5h, obtains reaction solution, will be quiet after reaction solution stirring 5h
Set 18h, nickel phosphate/Co-MOFs composite material is made in centrifuging and taking precipitating, wherein nanometer phosphorus obtained in step (1) in reaction solution
The mass ratio of sour nickel, cobalt salt and 2-methylimidazole is 100:742:16.
Fig. 1 is the SEM figure of the nanometer nickel phosphate prepared in embodiment 1, as shown in Figure 1, nanometer nickel phosphate agglomeration ratio
It is more serious.
Fig. 2 is the SEM of the Co-MOFs formed during preparing nickel phosphate/Co-MOFs composite material in embodiment 1
Figure, as shown in Figure 2, the pattern of Co-MOFs are regular granatohedron.
Fig. 3 is that nickel phosphate/Co-MOFs composite material SEM figure is prepared in embodiment 1, from the figure 3, it may be seen that nickel phosphate success
Co-MOFs has been gone up in ground load, load it is relatively uniform, compared to Figure 1 it is found that the agglomeration of nanometer nickel phosphate obtained it is bright
It is aobvious to improve.
Embodiment 4
Test current-responsive of the glucose molecule on nickel phosphate/Co-MOFs composite material modified electrode
(1) nickel phosphate, Co-MOFs, nickel phosphate/Co-MOFs composite material are dispersed respectively with the matched proportion density of 3mg/mL
In n,N dimethylformamide, 3 kinds of electrode modification solution are obtained, takes each 5 μ L of electrode modification solution to be respectively coated and is thrown through polishing
Light, dehydrated alcohol and deionized water alternately clean after glass-carbon electrode on, dry, obtain 3 kinds of working electrodes (each working electrode according to
Secondary label is3(PO4)2/GCE、Co-MOFs/GCE、Ni3(PO4)2/ Co-MOFs/GCE), then respectively with this 3 kinds work electricity
Pole and saturated calomel electrode (reference electrode), platinum filament (to electrode), electrolyte (NaOH solution that concentration is 0.1M), electrochemistry work
It stands and constructs 3 kinds of electrochemical sensors together, and simultaneously after sanding and polishing, dehydrated alcohol and deionized water are alternately cleaned
Glass-carbon electrode is working electrode (working electrode is labeled as GCE), and equally with saturated calomel electrode (reference electrode), platinum filament is (right
Electrode), the electrolyte NaOH solution of 0.1M (concentration be), electrochemical workstation electrochemical sensor together, as blank control.
(2) concentration is added in 4 electrochemical sensors constructed respectively into step (1) in electrolyte is 0.1M glucose
Standard solution makes the concentration of glucose in electrolyte be 1mmol/L, and control magneton mixing speed is 500r/min, while each
A forward scan voltage is loaded in electrochemical sensor on working electrode, scanning range is 0V to 0.8V, sweep amplitude 50mV/
S records oxidation current-voltage change situation by electrochemical workstation in each electrochemical sensor, has obtained CV curve graph, such as schemes
Shown in 4, as shown in Figure 4, on the nickel phosphate that glucose molecule is prepared in embodiment 1/Co-MOFs composite material modified electrode
Current-responsive is maximum, and the oxidation peak near 0.26V and 0.52V is respectively belonging to the oxidation peak and grape oxidation of nickel phosphate
Peak.
Embodiment 5
Nickel phosphate/Co-MOFs composite material modification the working electrode prepared in embodiment 1 will be configured in embodiment 4
Electrochemical sensor as test device, the glucose standards solution of compound concentration 0.001M, 0.01M, 0.1M, 8mL's
0.1M NaOH solution is as electrolyte.Using chronoamperometry, setting initial voltage is 0.4-0.6V, and runing time is set as
Successively pressing 8 μ L concentration every 30s after 1200s, operation beginning 200s is 0.001M glucose standards solution, 4 μ L, 4 μ L, 8 μ L, 16
μ L, 16 μ L, 16 μ L, 16 μ L additional amount be added concentration be 0.01M glucose standards solution, and then successively press 8 μ L, 16 μ
L, 16 μ L, 16 μ L, 16 μ L, 40 μ L, 40 μ L additional amount be added concentration be 0.1M glucose standards solution, during which control magneton
Mixing speed is 500r/min, and records the corresponding oxidation current of each concentration of glucose, obtains i-t curve graph, as a result such as Fig. 5
Shown, as shown in Figure 5, current value is linearly increasing with glucose concentration increase on i-t curve.With current value to grape
The mapping of sugared concentration, the figure as shown in fig. 6, and according to Fig. 6 linear equation, it will be appreciated from fig. 6 that glucose current is to its concentration
The linear relation of responsing linear range 0.001-4.0mM, fitting are: y (μ A)=196.6x (μm ol/L)+19.2, phase relation
Number R2=0.993, detection sensitivity is 196.6 μ A/ μM, which is 3mm based on nickel phosphate/Co-MOFs modification diameter
Glass-carbon electrode obtains, therefore unit area sensitivity can be converted into 2783 μ A/mMcm2, sensor of the invention is to glucose
Detection limit (be based on 3 times of noises) be 0.7 × 10-6mol/L。
Embodiment 6
The anti-interference test of the nickel phosphate prepared in embodiment 1 /Co-MOFs composite material modification working electrode
Nickel phosphate/Co-MOFs composite material modification the working electrode prepared in embodiment 1 will be configured in embodiment 4
Electrochemical sensor as test device, using chronoamperometry, initial voltage is set as 0.5V, and 80 μ L are added after running 100s
Concentration be 0.1mol/L glucose standard, control magneton mixing speed be 500r/min, continue to run, successively every 20s
It is added that fructose soln, 8 μ L concentration that 8 μ L concentration are 0.1mol/L are 0.1mol/L lactose solution, 8 μ L concentration are 0.1mol/L sugarcane
Sugar juice, 8 μ L concentration are 0.1mol/L ascorbic acid solution, 8 μ L concentration are 0.1mol/L dopamine solution, 8 μ L concentration are
0.1mol/L uric acid solution, and the corresponding oxidation current of different solutions is recorded, as a result as shown in fig. 7, as shown in Figure 7, concentration is equal
Cause current value that can ignore for the fructose of 0.1mM, lactose, sucrose, ascorbic acid, dopamine and uric acid, well below concentration
For the current value of the glucose of 1.0mM, therefore fructose, lactose, sucrose, ascorbic acid, dopamine and uric acid are configured with invention
The influence of the electrochemical sensor detection glucose of nickel phosphate/Co-MOFs composite material modification working electrode is little, illustrates this
Electrochemical sensor has good interference free performance.
Embodiment 7
Detect the glucose in human serum
Two human body serum samples (number is respectively 1 and 2) are provided by Zigong City No.4 People's hospital, and concentration passes through entirely certainly
Dynamic biological analyser measurement will be configured with the nickel phosphate/Co-MOFs composite material modification prepared in embodiment 1 in embodiment 4
The electrochemical sensor of working electrode is detected as follows as test device, 2 human body serum samples: pipetting 8 μ
It is in 0.1mol/LNaOH electrolyte that L serum, which is put into 8mL concentration, and control magneton mixing speed is 500r/min, using timing electricity
Stream method detects the reliability of the electrochemical sensor, runs 100s, and 16 μ L concentration of addition are 0.1mol/L glucose standard, meter
Calculate the rate of recovery of standard glucose.Each concentration does parallel test three times, calculates the rate of recovery of each concentration, the knot of mark-on reclaims
Fruit is as shown in table 1.
Table 1
As shown in Table 1, the rate of recovery illustrates to repair in the present invention configured with nickel phosphate/Co-MOFs composite material in 92-109%
The electrochemical sensor of the working electrode of decorations has practical application value.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to compared with
Good embodiment describes the invention in detail, those skilled in the art should understand that, it can be to skill of the invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of the technical program, should all be covered in the present invention
Scope of the claims in.
Claims (10)
1. a kind of nickel phosphate/Co-MOFs composite material preparation method, which is characterized in that described method includes following steps:
(1) after nickel salt and phosphate being dissolved in water, n,N-Dimethylformamide is added, it is anti-in carrying out hydro-thermal in reaction kettle after mixing
It answers, precipitating is filtered to take after the hydro-thermal reaction, the precipitating is carried out nanometer nickel phosphate is made after washing is dry；
(2) it disperses nanometer nickel phosphate obtained in step (1) in solvent, cobalt salt is then added, added after stirring 1-5h
2-methylimidazole solution obtains reaction solution, stands 1-24h after the reaction solution is stirred 0.5-5h, phosphorus is made in centrifuging and taking precipitating
Sour nickel/Co-MOFs composite material.
2. the method as described in claim 1, which is characterized in that in step (1), nickel element in the nickel salt, phosphorus in phosphate
The molar ratio of element, water and N,N-dimethylformamide is 40:20:5-35:1-9；The condition of the hydro-thermal reaction is in 100-
180 DEG C, react 3-10h.
3. method according to claim 2, which is characterized in that in step (1), the nickel salt is nickel nitrate, nickel chloride or sulphur
One of sour nickel；The phosphate is one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate or sodium dihydrogen phosphate
Kind.
4. the method as described in claim 1, which is characterized in that obtained in step (1) in the reaction solution in step (2)
The mass ratio of nanometer nickel phosphate, cobalt salt and 2-methylimidazole is 100:14-742:16-821.
5. the method as described in claim 1, which is characterized in that in step (2), the solvent is methanol, N, N- dimethyl methyl
One of amide or ethyl alcohol；The 2-methylimidazole solution is 2-methylimidazole methanol solution, 2-methylimidazole N, N- diformazan
One of base formamide solution or 2-methylimidazole ethanol solution.
6. the method as described in claim 1, which is characterized in that in step (2), the cobalt salt is cobalt nitrate, cobalt chloride or sulphur
One of sour cobalt.
7. nickel phosphate/Co-MOFs composite material of method preparation described in any one of claims 1-6.
8. a kind of electrochemical sensor, including electrochemical workstation, working electrode, to electrode, reference electrode, electrolytic cell and electrolysis
Liquid, which is characterized in that the working electrode surface is coated with nickel phosphate as claimed in claim 7/Co-MOFs composite material.
9. a kind of electrochemical sensor as claimed in claim 8, which is characterized in that the working electrode is made as follows
It is standby:
It disperses nickel phosphate/Co-MOFs composite material in n,N dimethylformamide with the matched proportion density of 1-5mg/mL, obtains
The electrode modification solution is coated on the electrode after being polished, being cleaned, dries by electrode modification solution.
10. a kind of application of the electrochemical sensor according to any one of claims 8 in glucose detection.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552789A (en) * | 2020-12-07 | 2021-03-26 | 内江师范学院 | Self-healing coating based on metal organic framework material and preparation method thereof |
| CN112683974A (en) * | 2019-10-17 | 2021-04-20 | 天津大学 | Enzyme-free glucose electrochemical sensor based on flexible Ni-P paper electrode and preparation method and application thereof |
| CN113075269A (en) * | 2021-03-26 | 2021-07-06 | 常州大学 | Electrochemical luminescence aptamer sensor for specifically detecting chloramphenicol and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058173A (en) * | 2013-02-04 | 2013-04-24 | 苏州纳格光电科技有限公司 | Preparation method of nano metal oxide functionalized carbon nanotubes and gas sensor |
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN108435256A (en) * | 2018-04-26 | 2018-08-24 | 四川理工学院 | A kind of preparation method of metal (II) functional graphene oxide catalyst |
| CN109354698A (en) * | 2018-11-05 | 2019-02-19 | 青岛科技大学 | Bimetal nano phosphate, preparation method and application based on metal-organic framework object |
-
2019
- 2019-03-04 CN CN201910161825.4A patent/CN109752433B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058173A (en) * | 2013-02-04 | 2013-04-24 | 苏州纳格光电科技有限公司 | Preparation method of nano metal oxide functionalized carbon nanotubes and gas sensor |
| CN106941151A (en) * | 2016-01-05 | 2017-07-11 | 中国石油大学(北京) | A kind of graphene composite graphite negative electrode material and its preparation method and application |
| CN108435256A (en) * | 2018-04-26 | 2018-08-24 | 四川理工学院 | A kind of preparation method of metal (II) functional graphene oxide catalyst |
| CN109354698A (en) * | 2018-11-05 | 2019-02-19 | 青岛科技大学 | Bimetal nano phosphate, preparation method and application based on metal-organic framework object |
Non-Patent Citations (2)
| Title |
|---|
| DENGRONG SUN 等: "Mixed-Metal Strategy on Metal-Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74", 《INORGANIC CHEMISTRY》 * |
| ZHENYU XIAO 等: "Construction of Hollow Cobalt-Nickel Phosphate Nanocages through a Controllable Etching Strategy for High Supercapacitor Performances", 《ACS APPLIED ENERGY MATERIALS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112683974A (en) * | 2019-10-17 | 2021-04-20 | 天津大学 | Enzyme-free glucose electrochemical sensor based on flexible Ni-P paper electrode and preparation method and application thereof |
| CN112552789A (en) * | 2020-12-07 | 2021-03-26 | 内江师范学院 | Self-healing coating based on metal organic framework material and preparation method thereof |
| CN112552789B (en) * | 2020-12-07 | 2021-11-23 | 内江师范学院 | Self-healing coating based on metal organic framework material and preparation method thereof |
| CN113075269A (en) * | 2021-03-26 | 2021-07-06 | 常州大学 | Electrochemical luminescence aptamer sensor for specifically detecting chloramphenicol and preparation method and application thereof |
| CN113075269B (en) * | 2021-03-26 | 2023-01-17 | 常州大学 | Electrochemical luminescence aptamer sensor for specifically detecting chloramphenicol and preparation method and application thereof |
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