CN114965627B - Reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode and preparation method and application thereof - Google Patents
Reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000004254 Ammonium phosphate Substances 0.000 title claims abstract description 56
- 229910000148 ammonium phosphate Inorganic materials 0.000 title claims abstract description 56
- 235000019289 ammonium phosphates Nutrition 0.000 title claims abstract description 56
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 description 64
- 239000008103 glucose Substances 0.000 claims description 64
- 239000000843 powder Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 230000035945 sensitivity Effects 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 229920000557 Nafion® Polymers 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
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- 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
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
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- 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 2
- 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 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
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- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- PJDBVVBEOBZFDJ-UHFFFAOYSA-L azanium nickel(2+) phosphate Chemical compound [NH4+].[Ni+2].[O-]P([O-])([O-])=O PJDBVVBEOBZFDJ-UHFFFAOYSA-L 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- 229960001375 lactose Drugs 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 229910002703 Al K Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000005715 Fructose Substances 0.000 description 1
- 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 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention belongs to the technical field of electrochemical sensors, in particular to a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode and a preparation method and application thereof.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensors, and relates to a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, a glucose sensor, a preparation method and application.
Background
Glucose is a monosaccharide which is most widely distributed in nature and extremely important, and the energy released by oxidation reaction enables most of animal and plant life activities to have main energy sources, so that quantitative detection of glucose has important significance in the fields of medicine, biology, food science and the like. Since Clark and Lyons invented the first enzyme-based electrochemical glucose sensor in 1962, the development of the glucose sensor has been over 60 years, but the industrialization market of the electrochemical glucose sensor is still occupied by the enzyme-based sensor of the first generation and the second generation today, but the enzyme sensor is free from the inherent instability defect of the enzyme, and in addition, the application of the enzyme is limited by other conditions such as pH, temperature, humidity, dependence on oxygen and the like, and the expensive price of the enzyme, so that the sensor always faces the problem of construction cost; the above reasons have forced the further development of enzyme-based electrochemical glucose sensors, which have been the dominant electrochemical glucose sensor industry for twenty years, to be greatly limited, and the current research of non-enzyme glucose sensors has received great attention based on the above factors.
The nickel-based electrode material has potential application value in a non-enzymatic glucose sensor due to rich element storage, excellent electrochemical performance and low cost; however, after the conventional nickel-based electrode material is applied to the detection of the glucose sensor, the application of the conventional nickel-based electrode material is often limited due to the technical defects of narrow linear range, low sensitivity and poor anti-interference capability, so that a new nickel-based material is needed to be searched for improving the electrocatalytic activity of the non-enzymatic glucose sensor.
NH in recent years 4 NiPO 4 Due to its excellent energy storage properties, there is an increasing interest in the field of supercapacitors, and in addition, nickel ammonium phosphate materials have been reported to have the potential to enhance the fire resistance of polymers and thus to be a potential, yet NH, material that is worthy of intensive research 4 NiPO 4 The application value in non-enzymatic glucose sensors is not clear, so NH is used 4 NiPO 4 As an active material, it is very interesting to develop a simple and reliable non-enzymatic glucose sensor.
Disclosure of Invention
Aiming at the technical defects, the invention provides a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, a glucose sensor, a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode comprises the following steps:
(1) Preparing reduced graphene oxide/nickel ammonium phosphate powder;
s1, dissolving a nickel source in deionized water to prepare a nickel source solution;
ammonium dihydrogen phosphate and urea are dissolved in deionized water together to obtain a mixed solution; the urea is used as a template agent, a source, a nitrogen source and a reducing agent of graphene oxide;
s2, adding a nickel source solution into the mixed solution, uniformly mixing to obtain a reaction solution, adding graphene oxide powder into the reaction solution, and performing ultrasonic dispersion, hydrothermal reaction, suction filtration and grinding until the graphene oxide powder is uniformly dispersed to obtain reduced graphene oxide/nickel ammonium phosphate powder;
(2) Preparation of a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode:
the reduced graphene oxide/nickel ammonium phosphate powder, ethanol and Nafion are uniformly mixed and then dripped on a glassy carbon electrode to obtain the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, and researches show that the nickel ammonium phosphate material growing on foam nickel is easy to fall off, so that a Nafion binder is added, and a smooth reduced graphene oxide/nickel ammonium phosphate/Nafion modified layer is formed on GCE by drying in ethanol atmosphere.
Preferably, the nickel source in the step S1 is selected from nickel nitrate, nickel acetate or nickel sulfate, the nickel source is prepared by using foam nickel as a raw material, and the nickel source is selected from divalent nickel salts which are soluble in water, but nickel chloride cannot be selected because the nickel chloride has a toxic effect on the electrode.
Preferably, the ratio of the amounts of the substances of the nickel source, the monoammonium phosphate and the urea in the step S2 is 1:3-4:50; the ratio of the amounts of the nickel source and the ammonium dihydrogen phosphate is 1:3-4, so that the nickel source is completely consumed, and the generation of heavy metal wastewater is reduced; the volume ratio of the graphene oxide to the reaction liquid is 0.045-0.05mg: when the volume ratio of the graphene oxide to the reaction liquid is 1mL and is higher than the ratio, the graphene oxide cannot be dispersed in the reaction liquid.
Preferably, in the step S2, the hydrothermal reaction conditions are as follows: heating at 100-140 ℃ for 10-14h, and performing a hydrothermal process to realize reduction of graphene oxide and formation of phosphorus nickel ammonium rod-like crystals.
The invention also protects the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode prepared by the preparation method.
The invention also provides a glucose sensor prepared by using the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, wherein the glucose sensor comprises a reference electrode, a counter electrode, electrolyte and the prepared reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, and the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, the reference electrode and the counter electrode are jointly arranged in the electrolyte.
The invention also protects the application of the glucose sensor in glucose hypersensitivity detection.
Preferably, the specific steps of glucose detection are as follows:
a saturated Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, a three-electrode system is formed by the platinum sheet electrode and a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode serving as a working electrode, the three-electrode system is connected to photoelectrochemical detection equipment, a sodium hydroxide solution with the concentration of 0.1mol/L is used as electrolyte, and a working curve is drawn according to current-potential by adopting a cyclic voltammetry method.
Preferably, the sensitivity of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode to the concentration of glucose is 328 mu AmM -1 cm -2 The limit of detection of the glucose concentration was 1. Mu.M, and the linear range was 1-5000. Mu.M.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts low-temperature high-pressure hydrothermal reaction, takes urea as a reducing agent of GO, a nitrogen source and an ammonium source, takes monoammonium phosphate as a nitrogen source and a phosphorus source simultaneously, takes nickel nitrate as a nickel source, and synthesizes rod-shaped NH 4 NiPO 4 @ rGO composite powder.
2、NH 4 NiPO 4 The sensitivity of the @ rGO/GCE electrode to glucose concentration at a test voltage of 0.55V was 328. Mu. AmM -1 cm -2 The sensitivity in the linear range is high. NH (NH) 4 NiPO 4 The detection limit of the @ rGO/GCE composite material on the concentration of glucose is 1 mu M, and the linear range is 1-5000 mu M.
3. The reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode prepared by the invention can effectively resist the interference of various interfering substances in human body fluid such as lactose, galactose, lactic acid, dopamine, sucrose, ascorbic acid and the like, has negligible response current to the selected common interfering substances, has good specificity to glucose, and is suitable for detecting the glucose concentration of engineering actual samples.
Drawings
FIG. 1 is a NH produced in example 1 of the present invention 4 NiPO 4 SEM and TEM spectra of @ rGO powder; wherein, (a) - (c) are SEM images respectively, and (d) - (f) are TEM images respectively;
FIG. 2 is a NH produced in example 1 of the present invention 4 NiPO 4 EDS spectrum of @ rGO;
FIG. 3 is a NH group produced in example 1 of the present invention 4 NiPO 4 EDS Mapping selection region map (a-b) of@rGO and EDS Mapping C-K (C), N-K (d), ni-K (e), O-K (f), ni-L (g) and P-K (h) distribution map;
FIG. 4 is a NH group obtained in example 1 of the present invention 4 NiPO 4 XRD pattern of @ rGO;
FIG. 5 is a NH group produced in example 1 of the present invention 4 NiPO 4 XPS full spectrum of @ rGO;
FIG. 6 is a NH group produced in example 1 of the present invention 4 NiPO 4 P2P fine spectrogram of @ rGO;
FIG. 7 is a NH group obtained in example 1 of the present invention 4 NiPO 4 C1s fine spectrogram @ rGO;
FIG. 8 is a NH group produced in example 1 of the present invention 4 NiPO 4 N1s fine spectrogram @ rGO;
FIG. 9 is a NH group produced in example 1 of the present invention 4 NiPO 4 Ni2p fine spectrogram of @ rGO;
FIG. 10 is a sample of NH produced in example 1 of the present invention 4 NiPO 4 IT test patterns of the@rGO/GCE electrode at different potentials;
FIG. 11 shows (a) NH produced in example 1 of the present invention 4 NiPO 4 An IT curve for glucose at 0.55V test potential for the @ rGO/GCE electrode; (b) NH (NH) 4 NiPO 4 A plot of the current response scatter plot of the @ rGO/GCE electrode against glucose concentration at a test potential of 0.55V;
FIG. 12 is a NH group produced in example 1 of the present invention 4 NiPO 4 Specific recognition IT graph of the @ rGO/GCE electrode on glucose.
Detailed Description
The following detailed description of specific embodiments of the invention is, but it should be understood that the invention is not limited to specific embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified.
Example 1
The preparation method of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode comprises the following steps:
(1) Preparation of reduced graphene oxide/nickel ammonium phosphate powder:
s1, preparing 100mL of nickel nitrate solution with the concentration of 0.01mol of foam nickel, 95mL of deionized water and 5mL of concentrated nitric acid (68%) into 0.1mol/L, and taking 10mL of nickel nitrate solution for the following reaction;
0.004mol of monoammonium phosphate and 3g of urea are dissolved in 50mL of ultrapure water to obtain a mixed solution;
s2, mixing a nickel nitrate solution with the mixed solution, adding graphene oxide powder in a proportion of 0.05mg/mL, performing ultrasonic treatment in a constant-temperature water bath at 60 ℃ for 25min to fully disperse the graphene oxide, pouring a polytetrafluoroethylene lining when the mixture is cooled to room temperature, sealing a hydrothermal reactor, heating at 120 ℃ for 12h, naturally cooling to room temperature, and performing suction filtration and grinding to obtain reduced graphene oxide/nickel ammonium phosphate powder;
(2) Preparation of a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode:
mixing 10mg of reduced graphene oxide/nickel ammonium phosphate powder, 350 mu L of ethanol and 95 mu L of Nafion (5%) in an ultrasonic machine uniformly to obtain a dripping liquid;
and (3) respectively dripping 3 mu L of the dripping liquid onto the glassy carbon electrode with the diameter of 3mm for three times, and naturally drying in an ethanol atmosphere to obtain the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode.
Example 2
The preparation method of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode comprises the following steps:
(1) Preparation of reduced graphene oxide/nickel ammonium phosphate powder:
s1, preparing 10mL of nickel nitrate solution with the concentration of 0.1 mol/L;
0.003mol of monoammonium phosphate and 3g of urea are dissolved in 50mL of ultrapure water to obtain a mixed solution;
s2, mixing a nickel nitrate solution with the mixed solution, adding graphene oxide powder in a proportion of 0.05mg/mL, performing ultrasonic treatment in a constant-temperature water bath at 60 ℃ for 25min to fully disperse the reduced graphene oxide, pouring a polytetrafluoroethylene lining when the mixture is cooled to room temperature, sealing a hydrothermal reactor, heating at 100 ℃ for 14h, naturally cooling to room temperature, and performing suction filtration and grinding to obtain reduced graphene oxide/nickel ammonium phosphate powder;
(2) Preparation of a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode:
mixing 10mg of reduced graphene oxide/nickel ammonium phosphate powder, 350 mu L of ethanol and 95 mu L of Nafion (5%) in an ultrasonic machine uniformly to obtain a dripping liquid;
and (3) respectively dripping 3 mu L of the dripping liquid onto the glassy carbon electrode with the diameter of 3mm for three times, and naturally drying in an ethanol atmosphere to obtain the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode.
Example 3
The preparation method of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode comprises the following steps: (1)
Preparation of reduced graphene oxide/nickel ammonium phosphate powder:
s1, preparing 10mL of nickel nitrate solution with the concentration of 0.1 mol/L;
0.0035mol of monoammonium phosphate and 3g of urea are dissolved in 50mL of ultrapure water to obtain a mixed solution;
s2, mixing a nickel nitrate solution with the mixed solution, adding reduced graphene oxide powder in a proportion of 0.045mg/mL, performing ultrasonic treatment in a constant-temperature water bath at 60 ℃ for 25min to fully disperse the graphene oxide, pouring a polytetrafluoroethylene lining when the mixture is cooled to room temperature, sealing a hydrothermal reactor, heating at 140 ℃ for 10h, naturally cooling to room temperature, and performing suction filtration and grinding to obtain reduced graphene oxide/nickel ammonium phosphate powder;
(2) Preparation of a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode:
mixing 10mg of reduced graphene oxide/nickel ammonium phosphate powder, 350 mu L of ethanol and 95 mu L of Nafion (5%) in an ultrasonic machine uniformly to obtain a dripping liquid;
and (3) respectively dripping 3 mu L of the dripping liquid onto the glassy carbon electrode with the diameter of 3mm for three times, and naturally drying in an ethanol atmosphere to obtain the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode.
According to the invention, the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode with wide detection linear range, high sensitivity and good anti-interference capability is prepared in each of the embodiments 1-3, the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode prepared in the embodiment 1 is used as an example for research, and the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode prepared in the embodiment 1 is used as a working electrode to construct an electrochemical sensor, and specific research methods and research results are as follows:
electrochemical performance studies reduced graphene oxide/nickel ammonium phosphate/GCE composite electrodes were tested using Chronoamperometry (CA). All electrochemical tests were performed on the CHI660E electrochemical workstation and the electrochemical sensor of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode was prepared as follows:
a saturated Ag/AgCl electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode is used as a working electrode to form a three-electrode system, the three-electrode system is connected to photoelectrochemical detection equipment, 50mL of 0.1mol/L sodium hydroxide aqueous solution is used as electrolyte, and a cyclic voltammetry is adopted to draw a working curve according to current-potential.
The research method comprises the following steps:
the X-ray diffraction pattern adopts a D8-advance (Bruker) X-ray diffractometer to obtain CuK α For radiation source, NH is in the range of 10-80 DEG 4 NiPO 4 The @ rGO/GCE composite electrode was analyzed. The microstructure and morphology of the resulting product were analyzed using EVO MA10 (ZEISS) Scanning Electron Microscope (SEM) and JEM2100F (JEOL) Transmission Electron Microscope (TEM). The chemical composition and elemental chemical state of the sample are determined by EscaLab 250Xi (Thermo Fisher Scientific) X-ray photoelectron Spectrometry (XPS) measurement, wherein the X-ray source is Al K α . In addition, energy dispersive X-ray analysis was performed using an X-Max 80 (Oxford) Energy Dispersive Spectrometer (EDS).
Electrode performance test:
NH 4 NiPO 4 electrochemical performance of the @ rGO/GCE electrode foam nickel composite electrodes were tested using Cyclic Voltammetry (CV) and Chronoamperometry (CA). All electrochemical tests were performed on the CHI660E (Shanghai cinnabar) electrochemical workstation. Three electrode structure: NH (NH) 4 NiPO 4 The @ rGO/GCE composite electrode is a working electrode, a 0.1mm multiplied by 10mm platinum sheet electrode is a counter electrode, and an Ag/AgCl (saturated KCl) electrode is a reference electrode. Electrochemical testing was done in 0.1m naoh aqueous solution.
Study results:
FIGS. 1 (a) - (c) are bar-shaped NH 4 NiPO 4 SEM image of @ rGO powder; from the figure it is seen that the powder is microscopically composed of rod-shaped NH 4 NiPO 4 @ rGO.
FIGS. 1 (d) - (f) are bar-like NH 4 NiPO 4 TEM image of @ rGO powder; because the material itself contains C element, micro-grid sample preparation is adopted to prevent inaccurate EDS and Mapping information, as shown in fig. 1 (f), the bar-shaped NH is calculated 4 NiPO 4 Lattice spacing of @ rGO is 0.87nm and can correspond to NH 4 NiPO 4 ·H 2 The (010) crystal plane of O.
FIG. 2 is a bar-shaped NH 4 NiPO 4 EDS spectrum of @ rGO powder; the relative content of the elements of the powder sample P, ni, N, O, C is seen in fig. 2, where the Cu peak line was introduced due to the use of micro-grid copper mesh for TEM fabrication.
FIGS. 3 (a) - (b) are bar-shaped NH 4 NiPO 4 EDS Mapping selection area diagram of@rGO powder, wherein a rod-shaped crystal is selected from TEM for displaying element distribution; FIGS. 3 (c) - (h) are bar-like NH 4 NiPO 4 EDS Mapping of the @ rGO powder, C, ni, O, P, N was detected in rod crystals, indicating NH 4 NiPO 4 The @ rGO composite material is successfully synthesized.
The results in FIG. 4 show that the powder sampleDiffraction peak and NH of each crystal face 4 NiPO 4 ·H 2 O (JSPDS No. 50-0425) was substantially coincident with the presence of preferential epitaxial growth at the (010) crystal plane, which coincides with the lattice spacing shown in FIG. 1 (f), further demonstrating NH 4 NiPO 4 ·H 2 And (3) preparing O crystals.
As shown in fig. 5, P 2p 、C 1s 、N 1s 、O 1s 、Ni 2p The existence of the overlap of the auger peak and the main element photoelectron peak is known from the standard manual. And P, C, N, O, ni relative element contents are respectively: 9.53At%, 25.91At%, 7.16At%, 45.35At%, 12.05At%. Wherein, the ratio of N, O, P, ni relative element content is close to 1:5:1:1, which accords with NH 4 NiPO 4 ·H 2 Ratio of the contents of the four elements.
As shown in FIG. 6, P of the phosphate appeared at 132.8eV and 133.8eV, respectively 2p3/2 Characteristic peak and P2P 1/2 Characteristic peaks, indicating the presence of phosphate components in the powder sample, are present in an absolute advantage.
As shown in fig. 7, graphene C appears at 284.1eV 1s Sp of (2) 2 Characteristic peaks, which indicate that the aromatic region c=c remains partially retained during oxidation of graphene to GO; this further demonstrates the incorporation of graphene components into the composite powder samples. Furthermore, C was observed at 284.8eV 1s Sp of (2) 3 Characteristic peaks, this fraction may have a number of components: the graphene lattice is destroyed by the oxidation process to form a fatty six-membered ring region C-C and C-C, C-H contaminated with carbon. Additionally, graphene C was observed at 288.8eV 1s This may be due to the failure to completely reduce GO in the hydrothermal reaction vessel.
As shown in FIG. 8, N occupying the main component was found at 401.1eV 1s Characteristic peaks of ammonium salt, namely characteristic peaks of pyridine nitrogen and picolinic nitrogen are respectively observed at 400.3eV and 399.1eV, which are possibly the result of doping N element into rGO under the combined action of urea and a low-temperature high-pressure environment in a hydrothermal reaction kettle.
As shown in FIG. 9, in856.1eV and 873.8eV respectively show Ni 2p3/2 With Ni 2p1/2 The spin energy difference is 17.7eV; ni is respectively corresponding to 861.3eV and 879.7eV 2p3/2 With Ni 2p1/2 Is a satellite peak of (2).
FIG. 10 is NH 4 NiPO 4 IT test patterns of different potentials of the@rGO/GCE electrode; wherein a total of five control groups of 0.4V to 0.6V are provided, and the potential difference between the adjacent two control groups is 0.05V. The stepwise current response was achieved by increasing the glucose concentration in the electrolyte system by 1mM every 50s, with a response current increase. As can be seen from the graph, the current response is smaller when the IT test potential is 0.4V, 0.45V, 0.5V, indicating NH at the corresponding test potential 4 NiPO 4 The sensitivity of the @ rGO/GCE electrode to glucose is not high; at 0.6V, the current response is large, but the noise is serious; therefore, the sensitivity and accuracy are integrated, 0.55V is selected as NH 4 NiPO 4 Optimal test potential for glucose sensing performance of the @ rGO/GCE electrode.
In FIG. 11 (a) is NH 4 NiPO 4 Current response IT plot of @ rGO/GCE electrode at 0.55V versus glucose concentration; the change of the glucose concentration in the electrolyte system was performed by 4 high concentration glucose solutions (1M, 0.1M, 10mM, 1mM, respectively); one drop of glucose solution (50. Mu.L) was added dropwise every 50s, so that 1 drop of the above 4 kinds of high-concentration glucose solutions were added every drop, and the glucose concentrations in the electrolyte system were raised by 1000. Mu.M, 100. Mu.M, 10. Mu.M, 1. Mu.M, respectively. From the graph, it can be seen that when the glucose concentration in the electrolyte system increases by 1. Mu.M, there is a significant current response in the electrode, which indicates NH 4 NiPO 4 The @ rGO/GCE electrode has a good detection limit.
Analysis of FIG. 11 (a) yields NH 4 NiPO 4 The current response scatter diagram of the electrode on the glucose concentration is obtained through scattered point fitting (figure 11 b) NH of the current response scatter diagram of the electrode on the glucose concentration 4 NiPO 4 @rGO/GCE electrode. The linear equation after fitting is i=0.328C glu +218.581(R 2 = 0.99184), and its corresponding linear range is 1-5000 μm; this means NH 4 NiPO 4 @rGO/The sensitivity of the GCE electrode to glucose concentration at a test voltage of 0.55V was 328. Mu. AmM -1 cm -2 While its limit of detection of glucose concentration under the test methods described herein is 1 μm.
The application also uses NH 4 NiPO 4 Performance comparison of nickel-based enzyme-free glucose sensors is disclosed for the @ rGO/GCE electrode with other prior art, as shown in table 1:
table 1 NH 4 NiPO 4 Performance comparison of @ rGO/GCE electrode with other Nickel-based enzyme-free glucose sensors
a FL: flower-like; b HPA: hollow and porous; c MOF: metal organic framework
The results in Table 1 show that the linear range of high sensitivity is not as wide as the electrode, and that the linear range of high sensitivity is not as high as the electrode.
FIG. 12 is NH 4 NiPO 4 An IT plot of the @ rGO/GCE electrode at 0.55V for glucose and various other substances that readily produce a response current with the glucose sensor; wherein, every 50s, glucose, sucrose, lactose, fructose, ascorbic acid, uric acid, dopamine and glucose are sequentially increased by 0.1mM in concentration in the electrolyte system. The response current of these interferents is negligible compared to the current signal of the electrode to glucose concentration, which means NH 4 NiPO 4 The @ rGO/GCE electrode glucose sensor has better specificity on glucose and is suitable for detecting the glucose concentration of engineering actual samples.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof. The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of protection is not limited thereto. Equivalent substitutions and modifications are intended to be within the scope of the present invention, as will be apparent to those skilled in the art based upon the present disclosure.
Claims (7)
1. The preparation method of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode is characterized by comprising the following steps of:
(1) Preparing reduced graphene oxide/nickel ammonium phosphate powder;
s1, dissolving a nickel source in deionized water to prepare a nickel source solution;
ammonium dihydrogen phosphate and urea are dissolved in deionized water together to obtain a mixed solution;
s2, adding a nickel source solution into the mixed solution, uniformly mixing to obtain a reaction solution, adding graphene oxide powder into the reaction solution, and performing ultrasonic dispersion, hydrothermal reaction, suction filtration and grinding until the graphene oxide powder is uniformly dispersed to obtain reduced graphene oxide/nickel ammonium phosphate powder;
(2) Preparation of a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode:
uniformly mixing reduced graphene oxide/nickel ammonium phosphate powder, ethanol and Nafion, and then dripping the mixture on a glassy carbon electrode to obtain a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode;
the nickel source in the step S1 is selected from nickel nitrate, nickel acetate or nickel sulfate, and the nickel source is prepared by taking foam nickel as a raw material;
the ratio of the amounts of the substances of the nickel source, the monoammonium phosphate and the urea in the step S2 is 1:3-4:50; the volume ratio of the graphene oxide to the reaction liquid is 0.045-0.05mg:1mL.
2. The method for preparing the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode according to claim 1, wherein in the step S2, the hydrothermal reaction conditions are as follows: heating at 100-140 deg.C for 10-14 hr.
3. A reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode prepared by the method of any one of claims 1-2.
4. A glucose sensor prepared by the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode according to claim 3, wherein the glucose sensor comprises a reference electrode, a counter electrode, an electrolyte and the prepared reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, and the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode, the reference electrode and the counter electrode are placed in the electrolyte together.
5. Use of the glucose sensor of claim 4 in glucose hypersensitivity detection.
6. The use of a glucose sensor according to claim 5 for glucose hypersensitivity detection, characterized in that the specific steps of glucose detection are:
a saturated Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, a three-electrode system is formed by the platinum sheet electrode and a reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode serving as a working electrode, the three-electrode system is connected to photoelectrochemical detection equipment, a sodium hydroxide solution with the concentration of 0.1mol/L is used as electrolyte, and a working curve is drawn according to current-potential by adopting a cyclic voltammetry method.
7. The use of a glucose sensor according to claim 5 for glucose hypersensitivity detection, wherein the sensitivity of the reduced graphene oxide/nickel ammonium phosphate/GCE composite electrode to glucose concentration is 328 μΑ mM -1 cm -2 The limit of detection of the glucose concentration was 1. Mu.M, and the linear range was 1-5000. Mu.M.
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| CN106248754A (en) * | 2016-08-09 | 2016-12-21 | 上海应用技术学院 | A kind of chemical modification GCE electrode based on functionalization rGO and its preparation method and application |
| CN108007998A (en) * | 2017-11-10 | 2018-05-08 | 东北电力大学 | Nickel oxide non-enzymatic glucose electrochemical sensor |
| CN109507271A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | It is a kind of for the GO/NiCO LDHs catalysis material of glucose detection and the preparation method of electrochemical sensor |
| CN110183850A (en) * | 2019-05-31 | 2019-08-30 | 西北工业大学 | Copper oxide/poly-dopamine/redox graphene CuO/PDA/rGO preparation method |
| CN113707466A (en) * | 2021-08-30 | 2021-11-26 | 新余学院 | Graphene oxide/ammonium nickel phosphate composite electrode material and preparation method and application thereof |
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| CN106248754A (en) * | 2016-08-09 | 2016-12-21 | 上海应用技术学院 | A kind of chemical modification GCE electrode based on functionalization rGO and its preparation method and application |
| CN108007998A (en) * | 2017-11-10 | 2018-05-08 | 东北电力大学 | Nickel oxide non-enzymatic glucose electrochemical sensor |
| CN109507271A (en) * | 2018-11-16 | 2019-03-22 | 天津工业大学 | It is a kind of for the GO/NiCO LDHs catalysis material of glucose detection and the preparation method of electrochemical sensor |
| CN110183850A (en) * | 2019-05-31 | 2019-08-30 | 西北工业大学 | Copper oxide/poly-dopamine/redox graphene CuO/PDA/rGO preparation method |
| CN113707466A (en) * | 2021-08-30 | 2021-11-26 | 新余学院 | Graphene oxide/ammonium nickel phosphate composite electrode material and preparation method and application thereof |
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