CN114235920B - NiCo LDH/NiCoS@C composite material and preparation method and application thereof - Google Patents
NiCo LDH/NiCoS@C composite material and preparation method and application thereof Download PDFInfo
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- CN114235920B CN114235920B CN202111560798.1A CN202111560798A CN114235920B CN 114235920 B CN114235920 B CN 114235920B CN 202111560798 A CN202111560798 A CN 202111560798A CN 114235920 B CN114235920 B CN 114235920B
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- 229910003266 NiCo Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 60
- 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 32
- 239000008103 glucose Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 27
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000035945 sensitivity Effects 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002135 nanosheet Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 9
- 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 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 210000002966 serum Anatomy 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- XTFPYEOBVLWDDP-UHFFFAOYSA-N CCO.CC(N)=S Chemical compound CCO.CC(N)=S XTFPYEOBVLWDDP-UHFFFAOYSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
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- 238000011056 performance test Methods 0.000 description 4
- 229930091371 Fructose Natural products 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
- 239000005715 Fructose Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910000474 mercury oxide Inorganic materials 0.000 description 3
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 206010012601 diabetes mellitus Diseases 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
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- 239000002064 nanoplatelet Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- 238000009825 accumulation Methods 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention belongs to a Co MOF-based low-sulfur doped NiCo LDH/NiCoS@C nanocomposite, and particularly relates to an application of simple steps and short time consumption, and can be used for Oxygen Evolution Reaction (OER), enzyme-free glucose and hydrogen peroxide sensors. When the invention is used as a catalyst for OER, only 207mV overpotential is required to reach a current density of 10mA cm ‑2, and the Tafil slope is as low as 48mV dec ‑1. When NiCo LDH/NiCoS@C was used as an enzyme-free glucose sensor, the linear range of the material response to glucose was 1. Mu.M-3 mM and 3-9mM, with sensitivities as high as 2167. Mu. AmM ‑1cm‑2 and 1417. Mu. AmM ‑ 1cm‑2, and detection limits as low as 208nM. When the material is used as a catalytic material of an enzyme-free hydrogen peroxide sensor, the detection range is 10 mu M-12mM, the sensitivity is as high as 285 mu AmM ‑1cm‑2, and the detection limit is as low as 1.66 mu M. The invention has low cost, high electrocatalytic activity, simple operation and strong anti-interference capability, can rapidly detect glucose and hydrogen peroxide in human serum, and has excellent oxygen evolution performance.
Description
Technical Field
The invention belongs to the technical field of new energy materials and bioelectrochemical sensing, and particularly relates to a NiCo LDH/NiCoS@C composite material and a preparation method and application thereof.
Background
With the rapid growth of population and the continuous demand of people for good life, the development and innovation of modern science and technology are particularly important. From the energy technology perspective, the pollution caused by the combustion and emission of fossil energy sources causes great harm to the environment and human bodies. Especially in recent years, the strategic planning and powerful fund support of China on new energy technology promote the low-carbon economic development mode to gradually replace the traditional high-pollution development mode, and the development of new energy is gradually becoming a research focus. The hydrogen energy has the advantages of rich sources, high energy density, easily obtained raw materials and the like, so that the electrochemical decomposition of water for hydrogen production becomes one of the effective methods. However, the low rate of Oxygen Evolution Reaction (OER) as a key factor in the water electrolysis process limits the rate of water splitting. Therefore, the research on the efficient OER catalyst has great significance and value.
Diabetes has been one of the killers that endanger human health and life since the 21 st century. The regular monitoring of blood sugar is a great help for preventing diabetes, especially for patients, the blood sugar content is monitored timely, and the medicine is reasonably used, so that complications can be reduced, and the life and health can be saved. Hydrogen peroxide is widely used in industry, clinic, medicine, and is one of the most important molecules in biological systems. Hydrogen peroxide is a metabolic by-product or intermediate in cell growth. The overproduction and accumulation of hydrogen peroxide in cells may lead to various diseases such as Alzheimer's disease, cardiovascular diseases and cancers. The accurate detection and real-time monitoring of the concentration level of hydrogen peroxide is of great importance. However, the conventional detection enzymes are expensive, have low stability, and require a strict living environment. Therefore, it is necessary to design a low-cost, high-stability sensor that can accurately and rapidly detect blood glucose and hydrogen peroxide content.
Metal Organic Frameworks (MOFs) are crystalline porous materials composed of coordination bonds between metal ions or clusters and organic ligands, with diverse framework and pore structures. These unique advantages give MOFs good catalytic capabilities and thus MOFs are a promising electrochemical sensing platform. However, the organic ligands that typically make up the MOF are inert and the MOF formed is bulky and thick, which is detrimental to the conductivity of the material.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a NiCo LDH/NiCoS@C composite material, a preparation method and application thereof, wherein the thickness of a nano sheet layer of the material is only 20-30nm, and the NiCo LDH/NiCoS@C composite material further has the advantages of high electrocatalytic activity, high sensitivity, wide linear range, excellent selectivity and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The invention provides a NiCo LDH/NiCoS@C composite material, wherein a NiCo LDH/NiCoS nano sheet array is uniformly distributed on the surface of a carbon substrate, niCo LDH/NiCoS nano sheets are perpendicular to the surface of carbon cloth fibers, the thickness of the NiCo LDH/NiCoS nano sheets is 20-30 nm, and the thickness of folds on the surfaces of the nano sheets is about 3-6nm. The formation of the ultrathin structure is beneficial to the rapid transmission of electrons/ions, and effectively reduces the resistance and the reaction energy barrier, thereby promoting the improvement of the electrocatalytic performance.
The invention also provides a preparation method of the NiCo LDH/NiCoS@C composite material, which comprises the following steps:
(1) Preparation of Co MoF@C: respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole in deionized water, uniformly stirring to prepare a cobalt nitrate hexahydrate aqueous solution and a 2-methylimidazole aqueous solution, rapidly pouring the 2-methylimidazole aqueous solution into the cobalt nitrate hexahydrate aqueous solution, immersing a carbon substrate in the mixed solution, standing at room temperature for 3-4 hours for reaction, and washing and drying to obtain Co MOF@C;
(2) Preparation of NiCo ldh@c: weighing nickel nitrate hexahydrate, dissolving the nickel nitrate hexahydrate in absolute ethyl alcohol, fully stirring, immersing Co MOF@C into a nickel nitrate hexahydrate ethanol solution, reacting for 1-3 hours at room temperature, washing and drying to obtain NiCo LDH@C;
(3) Dissolving thioacetamide in absolute ethyl alcohol to prepare thioacetamide ethanol solution, transferring the thioacetamide ethanol solution and NiCo LDH@C obtained in the step (2) into an autoclave, and heating for 2-6h at 100-150 ℃; after natural cooling to room temperature, the NiCo LDH/NiCoS@C is obtained by washing with deionized water and drying.
Further, the mass concentration of the cobalt nitrate hexahydrate aqueous solution in the step (1) is 0.005-0.05g/mL, and the mass concentration of the 2-methylimidazole aqueous solution is 0.02-0.2g/mL. Preferably, the mass concentration of the cobalt nitrate hexahydrate aqueous solution is 0.01-0.02g/mL, and the mass concentration of the 2-methylimidazole aqueous solution is 0.03-0.05g/mL.
Further, the mass concentration of the nickel nitrate ethanol hexahydrate solution in the step (2) is 0.003-0.03g/mL. Preferably, the mass concentration of the nickel nitrate hexahydrate ethanol solution is 0.004-0.005g/mL.
Further, the mass concentration of the thioacetamide ethanol solution in the step (3) is 0.10-1mg/mL. Preferably, the mass concentration of the thioacetamide ethanol solution is 0.1-0.2mg/mL.
Further, the carbon substrate is a textile carbon substrate with high flexibility and high conductivity, such as carbon cloth or carbon felt or carbon paper or carbon fiber.
The invention also provides application of the NiCo LDH/NiCoS@C composite material serving as an OER catalyst in a water electrolysis hydrogen production reaction.
The invention also provides application of the NiCo LDH/NiCoS@C composite material as an enzyme-free glucose sensor.
The invention also provides application of the NiCo LDH/NiCoS@C composite material as an enzyme-free hydrogen peroxide sensor.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, a carbon substrate is used as a substrate, co MOF is grown at room temperature, MOF is used as a sacrificial template, niCo LDH is grown by etching, niCo LDH/NiCoS@C is generated through hydrothermal reaction, and the advantages of high electrocatalytic activity, high sensitivity, wide linear range, excellent selectivity and the like are shown in oxygen evolution reaction, enzyme-free glucose and hydrogen peroxide sensors. When the material is used as a catalyst for OER, only 207mV overpotential is needed under the current density of 10mAcm 2; in addition, when the material is used as a catalytic material of an enzyme-free glucose sensor, the sensitivity is as high as 2167 mu AmM -1cm-2 and 1417 mu AmM -1cm-2 and the detection limit is as low as 208nM for glucose with the detection range of 1 mu M-3mM and 3-9 mM; when the material is used as a catalytic material of an enzyme-free hydrogen peroxide sensor, the detection range is 10 mu M-12mM, the sensitivity is as high as 285 mu AmM -1cm-2, and the detection limit is as low as 1.66 mu M. The sensor has good anti-interference performance on sodium chloride, ascorbic acid, fructose and the like.
2. The thickness of the nano sheet layer is only 20-30nm, the thickness of folds on the surface of the nano sheet is about 3-6nm, the transmission rate of electrons and ions is greatly enhanced, and the defect of poor conductivity of MOF is overcome. The nano material grows on the carbon base in a self-supporting way, and the electrode material can exert the optimal electrocatalytic performance based on a conductive network rich in the carbon base, excellent pseudocapacitance characteristic of transition metal sulfide and a unique MOF structure.
3. The transition metal sulfur compound of the present invention has excellent conductivity, redox activity and cycle stability. The transition metal sulfur compound electrochemical reaction occurs on the surface or interface of the electrode material, and the ultrathin structure of the material has larger specific surface area, so that more active sites can be provided for OER reaction.
Drawings
Fig. 1: SEM image of NiCo LDH/NiCoS@C was prepared in example 1.
Fig. 2: TEM images of NiCo LDH/NiCoS@C were prepared in example 1.
Fig. 3: SEM images of NiCo LDH 1h@C、NiCo LDH3h@C、NiCo LDH1h/NiCoS@C and NiCo LDH 3h/NiCoS@C were prepared in example 1.
Fig. 4: example 1 LSV plots of NiCo LDH 1h@C、NiCo LDH3h@C、NiCo LDH1h/NiCoS@C and NiCo LDH 3h/NiCoS@C in 1M KOH solution were prepared.
Fig. 5: example 1 an LSV plot of NiCo LDH/NiCoS@C with a control in 1M KOH solution was prepared.
Fig. 6: a Taphill slope plot of NiCo LDH/NiCoS@C versus the control was prepared in example 1.
Fig. 7: an impedance plot of NiCo LDH/NiCoS@C and a control sample was prepared in example 1.
Fig. 8: example 1 a CV plot of NiCo LDH/NiCoS@C versus glucose at different concentrations was prepared.
Fig. 9: example 1 an amperometric current test chart of an enzyme-free glucose sensor of NiCo LDH/nicos@c was prepared.
Fig. 10: example 1 an anti-interference performance test chart of an enzyme-free glucose sensor of NiCo LDH/NiCoS@C was prepared.
Fig. 11: example 1a CV plot of NiCo LDH/nicos@c with hydrogen peroxide of different concentrations was prepared.
Fig. 12: example 1 an amperometric test chart of an enzyme-free hydrogen peroxide sensor of NiCo LDH/nicos@c was prepared.
Fig. 13: example 1 an anti-interference performance test chart of an enzyme-free hydrogen peroxide sensor of NiCo LDH/NiCoS@C was prepared.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, so that those skilled in the art can better understand the technical solutions of the present invention.
Example 1: a preparation method of a NiCo LDH/NiCoS@C composite material comprises the following steps: .
(1) Taking 0.65g of cobalt nitrate hexahydrate and 1.2g of 2-methylimidazole to be respectively dissolved in 40mL of deionized water, stirring for 10min, rapidly pouring the 2-methylimidazole aqueous solution into the cobalt nitrate hexahydrate aqueous solution under vigorous stirring, placing a carbon substrate (carbon cloth) with the length of 1X 2cm 2 into the fully and uniformly dissolved mixed solution, standing for 3h at room temperature, and washing and drying with deionized water to obtain a sample Co MOF@C.
(2) 0.2G of nickel nitrate hexahydrate is taken and dissolved in 30mL of absolute ethyl alcohol, co MOF@C is immersed into ethanol solution of nickel nitrate hexahydrate after being stirred uniformly, and after standing for 2 hours at room temperature, niCo LDH@C is obtained by washing and drying with deionized water.
(3) 20Mg of thioacetamide is taken and dissolved in 40mL of absolute ethyl alcohol, after being stirred uniformly, the thioacetamide ethanol solution and NiCo LDH@C are transferred into a 100mL polytetrafluoroethylene lining stainless steel autoclave, and the mixture is heated for 4 hours at 100 ℃. After natural cooling to room temperature, the NiCo LDH/NiCoS@C is obtained by washing with deionized water and drying. FIGS. 1-2 are SEM and TEM images of NiCo LDH/NiCoS@C, respectively. The SEM image can observe that the NiCo LDH/NiCoS nano-sheet array grows on the surface of the carbon cloth fiber uniformly, and the appearance of the nano-sheet is kept complete. The doping of the S element promotes the thickness reduction of the nanoplatelets to 28nm. In TEM images, ultrathin NiCo LDH/NiCoS nanoplatelets grow vertically, and the upper wrinkles are observed to be about 3-6nm thick. The formation of the ultrathin structure is beneficial to the rapid transmission of electrons/ions, and effectively reduces the resistance and the reaction energy barrier, thereby promoting the improvement of the electrocatalytic performance.
Example 2: the Co MOF@C obtained in example 1 was obtained by changing the standing time of example 1 at room temperature in step (1) to 5 hours, and the Co MOF grown on the carbon substrate was grown to be dense and thick and large in sheet structure under the same conditions as those in example 1 and 5 hours.
Example 3: the etching time (room temperature standing time) in the step (2) of the example 1 was changed to 3 hours, and the NiCo LDH 3h @ C was obtained under the same conditions as in the example 1. By comparing SEM images (fig. 3 (a)), the Co MOF surface was complete and a distinct platelet was observed; however, the Co MOF was etched so thin that cracking of the NiCo LDH 3h/NiCoS@C surface after the further vulcanization process occurred (FIG. 3 (b)), and it was evident that there was an overetch phenomenon. The etching time (room temperature standing time) in step (2) of example 1 was changed to 1h, and the other conditions were the same as in example 1. The resulting NiCo LDH 1h @ C sample had no apparent platelets on the surface (fig. 3 (C)), and the NiCo LDH 3h/nicos @ C did not form an ultrathin structure after further vulcanization (fig. 3 (d)). By LSV testing (fig. 4), the difference in etch time has an effect on the material properties. As the etching time is prolonged, i.e., the doping amount of Ni 2+ is increased, the overpotential of the material at the current density of 10mAcm -2 becomes smaller. However, the etching time is too long, which leads to an increase in overpotential.
Example 4: the NiCo LDH/NiCoS@C composite material prepared in example 1 was used as a catalyst for OER reaction, and the main test procedure was as follows:
(1) Electrochemical test is carried out by selecting a three-electrode system, and in a 1M KOH solution, niCo LDH/NiCoS@C is used as a working electrode, a platinum sheet is used as a counter electrode, and a mercury/mercury oxide electrode is used as a reference electrode.
(2) Prior to testing, the catalyst was subjected to cyclic voltammetric scanning (CV) for 40 cycles to better activate the catalyst. When Linear Sweep Voltammetry (LSV) is performed, the voltage window is-0.3-0.7V, the sweep speed is 5mV s -1, and the LSV test is performed with 90% iR compensation. The overpotential required for each catalyst at a current density of 10mAcm -2 was calculated by testing the LSV of the different catalysts. The lower the overpotential, the better its performance in electrocatalytic OER reactions. FIG. 5 is an overpotential image of NiCo LDH/NiCoS@C and a control at a current density of 10mAcm -2. From fig. 5, it can be derived that by etching Ni 2+ and doping S element, the electronic structure of NiCo LDH/nicos@c is effectively tuned, and the heterostructure can expose more active sites, so that NiCo LDH/nicos@c has the best catalytic activity.
(3) The tafel slope is a slope value calculated by linear transformation of the equation η=a+ blgI in combination with the LSV curve. The lower the tafel slope value, the faster the oxygen evolution reaction rate. FIG. 6 is a Taphill slope image of NiCo LDH/NiCoS@C and a control. From FIG. 6, it can be derived that the Tafil slope of NiCo LDH/NiCoS@C is minimal (48 mV dec -1) compared to the control, demonstrating that it possesses minimal reaction kinetics.
(4) The amplitude potential of the impedance test EIS is 0.05V, the frequency range is 0.01-100kHz, and the measured potential is consistent with the open circuit voltage. FIG. 7 is an impedance image of NiCo LDH/NiCoS@C and a control sample. From FIG. 7, it can be derived that the resistance of NiCo LDH/NiCoS@C is minimal, demonstrating that the structure of NiCo LDH/NiCoS@C is conducive to rapid electron/ion transfer.
Example 5: the NiCo LDH/NiCoS@C composite material prepared in example 1 is used as a catalytic material of an enzyme-free glucose sensor, and the main test steps are as follows:
(1) Respectively taking NiCo LDH/NiCoS@C as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode, and selecting 0.5M NaOH solution as electrolyte, and carrying out electrochemical test under a three-electrode system.
(2) In cyclic voltammetry, the voltage window was chosen to be-0.1-0.7V and the sweep rate was 20mV s -1, 0-10mM glucose was added to the 0.5M NaOH solution, respectively. As the glucose concentration increases, the current density of the anodic peak increases and the potential also shifts toward a higher potential, indicating that the oxidation process of glucose is surface controlled. FIG. 8 is an image of the CV curve of NiCo LDH/NiCoS@C versus glucose at various concentrations.
(3) In amperometric current test, the voltage was 0.5V and the test time was 3000s, glucose was added every 100 s. It can be seen that each glucose addition caused a step-like current response of the electrode to glucose and reached stability within 2 s. As the glucose concentration increases, the current response increases with it. As a result of calculation, the detection range of glucose was 1. Mu.M-3 mM and 3-9mM, the sensitivity was as high as 2167. Mu. AmM -1cm-2 and 1417. Mu. AmM -1cm-2, and the detection limit was as low as 208nM (signal to noise ratio was 3). FIG. 9 is an amperometric current test image of NiCo LDH/NiCoS@C as an enzyme-free glucose sensor.
(4) When the anti-interference performance is tested, the voltage is 0.5V, the test time is 1400s, and the current response is obvious only when glucose is added, and when other 9 kinds of interferents such as sodium chloride, ascorbic acid and fructose are added, the current response is weak or basically no. FIG. 10 is an image of the anti-interference performance test of NiCo LDH/NiCoS@C as an enzyme-free glucose sensor.
Example 6: the NiCo LDH/NiCoS@C composite material prepared in example 1 is used as a catalytic material of an enzyme-free hydrogen peroxide sensor, and the main test steps are as follows:
(1) Respectively taking NiCo LDH/NiCoS@C as a working electrode, a platinum sheet as a counter electrode, a mercury/mercury oxide electrode as a reference electrode, and selecting 0.5M NaOH solution as electrolyte, and carrying out electrochemical test under a three-electrode system.
(2) In cyclic voltammetry, the voltage window was chosen to be-0.1-0.8V and the sweep rate was 10-80mV s -1, 3mM hydrogen peroxide was added to the 0.5M NaOH solution, respectively. As the sweep rate increases, the current density of the cathodic peak increases, indicating that the hydrogen peroxide reduction process is diffusion controlled. FIG. 11 is an image of the CV curve of NiCo LDH/NiCoS@C versus 3mM hydrogen peroxide at different sweep rates.
(3) The amperometric current was measured at a voltage of-0.35V for a period of 3000s with hydrogen peroxide added every 100 s. It can be seen that each hydrogen peroxide addition caused a step-wise current response of the electrode to hydrogen peroxide and reached stability within 5 s. As the hydrogen peroxide concentration increases, the current response increases with it. The detection range of the hydrogen peroxide is 10 mu M-12mM, the sensitivity is as high as 285 mu AmM -1cm-2, and the detection limit is as low as 1.66 mu M (signal to noise ratio is 3). FIG. 12 is an amperometric test image of NiCo LDH/NiCoS@C as an enzyme-free hydrogen peroxide sensor.
(4) When the anti-interference performance is tested, the voltage is-0.35V, the test time is 1400s, and the current response is obvious only when hydrogen peroxide is added, and when other interferents are added, the current response is weak or basically no. FIG. 13 is an image of the anti-interference performance test of NiCo LDH/NiCoS@C as an enzyme-free hydrogen peroxide sensor.
In summary, a NiCo LDH/NiCoS@C composite material for an oxygen evolution reaction, an enzyme-free glucose and hydrogen peroxide sensor was prepared, which required only 207mV overpotential at a current density of 10mAcm 2 when used as a catalyst for OER; in addition, when the material is used as a catalytic material of an enzyme-free glucose sensor, the sensitivity is as high as 2167 mu AmM -1cm-2 and 1417 mu AmM -1cm-2 and the detection limit is as low as 208nM for glucose with the detection range of 1 mu M-3mM and 3-9 mM; when the material is used as a catalytic material of an enzyme-free hydrogen peroxide sensor, the detection range is 10 mu M-12mM, the sensitivity is as high as 285 mu AmM -1cm-2, and the detection limit is as low as 1.66 mu M. The sensor has good anti-interference performance on sodium chloride, ascorbic acid, fructose and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A NiCo LDH/nicos@c composite material for an oxygen evolution reaction, an enzyme-free glucose sensor or a hydrogen peroxide sensor, which material, when used as a catalyst for OER, requires an overpotential of only 207mV at a current density of 10mAcm 2; when the material is used as a catalytic material of an enzyme-free glucose sensor, the sensitivity of the material to glucose with the glucose detection range of 1 mu M-3mM and 3-9mM reaches 2167 mu AmM -1cm-2 and 1417 mu AmM -1cm-2, and the detection limit is as low as 208nM; when the material is used as a catalytic material of an enzyme-free hydrogen peroxide sensor, the detection range is 10 mu M-12mM, the sensitivity reaches 285 mu AmM -1cm-2, and the detection limit is as low as 1.66 mu M;
the preparation method of the material comprises the following steps: comprising the following steps:
(1) Taking 0.65g of cobalt nitrate hexahydrate and 1.2g of 2-methylimidazole to be respectively dissolved in 40mL of deionized water, stirring for 10min, rapidly pouring the 2-methylimidazole aqueous solution into the cobalt nitrate hexahydrate aqueous solution under vigorous stirring, placing 1X 2cm 2 of carbon cloth into a fully and uniformly dissolved mixed solution, standing for 3h at room temperature, and washing and drying with deionized water to obtain a sample Co MOF@C;
(2) Dissolving 0.2g of nickel nitrate hexahydrate in 30mL of absolute ethyl alcohol, immersing Co MOF@C into an ethanol solution of nickel nitrate hexahydrate after stirring uniformly, standing for 2 hours at room temperature, and washing and drying with deionized water to obtain NiCo LDH@C;
(3) Dissolving 20mg of thioacetamide in 40mL of absolute ethyl alcohol, transferring an ethanol solution of the thioacetamide and NiCo LDH@C into a 100mL polytetrafluoroethylene lining stainless steel autoclave after stirring uniformly, heating for 4 hours at 100 ℃, naturally cooling to room temperature, washing with deionized water, and drying to obtain NiCo LDH/NiCoS@C;
the NiCo LDH/NiCoS@C is characterized in that a NiCo LDH/NiCoS nano sheet array is uniformly distributed on the surface of a carbon substrate, the NiCo LDH/NiCoS nano sheet is perpendicular to the surface of a carbon cloth fiber, the doping of S element promotes the thickness of the nano sheet to be reduced to 28nm, and the thickness of folds on the surface of the nano sheet is 3-6nm.
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