CN113120973B - Preparation method of copper-doped nickel-aluminum layered double hydroxide, obtained product and application - Google Patents
Preparation method of copper-doped nickel-aluminum layered double hydroxide, obtained product and application Download PDFInfo
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- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002070 nanowire Substances 0.000 claims abstract description 38
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- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims abstract description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
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- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
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- 150000001879 copper Chemical class 0.000 claims abstract description 9
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- 238000001514 detection method Methods 0.000 claims abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 15
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000003278 mimic effect Effects 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 20
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- 239000000047 product Substances 0.000 description 21
- 229910005581 NiC2 Inorganic materials 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 description 11
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- 229940039748 oxalate Drugs 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 102000003992 Peroxidases Human genes 0.000 description 4
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- 108040007629 peroxidase activity proteins Proteins 0.000 description 4
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- 239000004366 Glucose oxidase Substances 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
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- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 108010087599 lactate dehydrogenase 1 Proteins 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 nickel chloride Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Abstract
The invention discloses a preparation method of copper-doped nickel-aluminum layered double hydroxide, an obtained product and application, wherein the preparation steps are as follows: preparing nickel oxalate nanowires; depositing alumina on the surface of the nickel oxalate nanowire by adopting an atomic layer deposition method to obtain an alumina @ nickel oxalate composite material; carrying out hydrogen reduction on the aluminum oxide @ nickel oxalate composite material to obtain the aluminum oxide @ nickel composite material; putting the aluminum oxide @ nickel composite material into a solution containing copper salt and ammonium salt, and carrying out hydrothermal reaction to obtain the copper-doped nickel-aluminum layered double hydroxide. The product obtained by the invention has a typical nanotube structure, consists of uniform ultrathin nanosheets, has a large specific surface area, shows excellent catalytic activity of peroxide mimic enzyme, overcomes the defects of difficult extraction and easy inactivation at high temperature of natural enzyme, can be used for detecting the concentrations of hydrogen peroxide and glucose, and has wide application prospects in the fields of biological medicine, environmental detection and food processing.
Description
Technical Field
The invention relates to a preparation method of copper-doped nickel-aluminum layered double hydroxide and an obtained product, and also relates to application of the product as peroxide mimic enzyme, belonging to the technical fields of nano material preparation and mimic enzyme.
Background
All life phenomena in nature are closely related to enzymes, and natural enzymes are biological macromolecules with special catalytic activity produced by living cells. Enzymes are the key parts of living organisms for maintaining their vital activities, carrying out metabolism, transmitting genetic information, and catalyzing the orderly progress of chemical reactions. Under mild reaction conditions, enzymes are widely used in a variety of fields including food processing, clinical diagnosis, biological detection, pharmaceutical manufacturing, and the like, due to their substrate specificity, catalytic efficiency, and the like.
However, most of these enzymes are proteins (few are RNA molecules with catalytic function), are easily hydrolyzed by proteases, are structurally unstable, and are easily changed under extreme conditions (too much acid, too much alkali, and high temperature) to lose catalytic activity. In addition, since the enzyme is produced from living cells, has a small content, is difficult to obtain in large quantities by purification, and has severe storage conditions, the high price greatly limits its application.
Therefore, researchers have attempted to find an artificial mimic enzyme that has both catalytic properties and compensates for the deficiencies of the enzyme. In the past decades, scientists have achieved many research results in the field of artificial mimic enzymes, and have synthesized various types of artificial mimic enzymes, and with the rapid development of scientific technology, the research on nano mimic enzymes has started to grow up as fast as spring shoots after rain, and has been widely applied in the fields of environment, biology, medicine, and the like.
Disclosure of Invention
The invention aims to provide a preparation method of copper-doped nickel-aluminum Layered Double Hydroxide (LDH) and an obtained product, the method takes nickel oxalate nanowires as templates, and combines an atomic layer deposition technology, a hydrogen reduction method and a hydrothermal method to prepare the CuNiAl LDH, the process is simple, the operation is easy, and the obtained CuNiAl LDH has a special structure, has a larger specific surface area and more active centers, and shows excellent catalytic activity of peroxide mimic enzyme.
In order to achieve the above object, the present invention uses the following embodiments:
a preparation method of copper-doped nickel-aluminum layered double hydroxide comprises the following steps:
(1) preparation of Nickel oxalate (NiC)2O4) A nanowire;
(2) depositing alumina on the surface of the nickel oxalate nanowire by adopting an atomic layer deposition method to obtain alumina @ nickel oxalate (Al)2O3@NiC2O4) A composite material;
(3) the aluminum oxide @ nickel oxalate composite material is subjected to hydrogen reduction to obtain aluminum oxide @ nickel (Al)2O3/Ni) composite material;
(4) putting the aluminum oxide @ nickel composite material into a solution containing copper salt and ammonium salt, and carrying out hydrothermal reaction to obtain the copper-doped nickel-aluminum layered double hydroxide.
Further, in the step (1), nickel salt, ethylene glycol and water are uniformly mixed, then oxalate is added and uniformly mixed under stirring, and the obtained mixed solution is subjected to hydrothermal reaction to obtain the nickel oxalate nanowire. The shape, size and dispersion uniformity of the nickel oxalate nanowire can be adjusted by factors such as the concentration of nickel salt and oxalate, the proportion of double solvents, hydrothermal reaction conditions and the like.
Further, in the step (1), the nickel salt may be a soluble nickel salt such as nickel chloride, and the oxalate may be a soluble oxalate such as sodium oxalate. The concentration of nickel salt in the reaction system is 0.0090 g/mL-0.0100 g/mL, and the concentration of oxalate in the reaction system is 0.0026 g/mL-0.0029 g/mL.
Further, in the step (1), the volume ratio of the ethylene glycol to the water is 4-6: 3.
Further, in the step (1), hydrothermal reaction is carried out in a closed reaction kettle, the reaction temperature is 200-250 ℃, and the reaction time is 9-14 hours.
Further, in the step (2), the aluminum oxide coating is uniformly deposited on the surface of the nickel oxalate nanowire through atomic layer deposition, which has a good advantage for the final formation of a layered nanotube structure of the product. And dripping the nickel oxalate nanowire dispersion liquid on a quartz plate, drying, and then putting the quartz plate into an atomic layer deposition device for depositing aluminum oxide to obtain the aluminum oxide @ nickel oxalate composite material. The nickel oxalate nanowire dispersion liquid is ethanol dispersion liquid of nickel oxalate nanowires, and is formed by uniformly dispersing the nickel oxalate nanowires into absolute ethanol, and in order to ensure the uniformity of dispersion, the nickel oxalate nanowire dispersion liquid can be dispersed in an ultrasonic mode. The concentration of the nickel oxalate nano-wires in the dispersion liquid is 0.5-1.5 mg/ml.
Further, in the step (2), the thickness of the nickel oxalate nanowire dispersion liquid drop on the quartz plate is about 3-5 mm. The thickness is not easy to be too thick, and the deposition of alumina can be influenced by too thick thickness.
Further, in the step (2), atomic layer deposition can be performed by using the method disclosed in the prior art to make nickel oxalateAnd depositing aluminum oxide on the surface of the nanowire. The method, conditions, and the like of the atomic layer deposition can be adjusted according to the thickness of the alumina. For example, atomic layer deposition may be performed using the following steps: putting the nickel oxalate nanowire into an atomic layer deposition device, controlling the temperature to be 140-160 ℃, taking trimethylaluminum and water as precursors, firstly carrying out trimethylaluminum pulse adsorption reaction, then purging redundant reactants and byproducts by using inert gas, then carrying out water pulse adsorption reaction, and then purging redundant reactants and byproducts by using inert gas. Repeating 80-100 cycles by taking the above steps as a cycle until an aluminum oxide layer with the required thickness is formed. Tests have verified that the original thickness of the alumina has a great influence on the composition of the final product. If the alumina content is low, it is difficult to provide sufficient Al in the hydrothermal process3+To construct pure phases of the LDH structure, impurities are easily generated. Therefore, it is preferable to deposit 100 cycles to obtain an aluminum oxide layer.
Further, in the step (3), the aluminum oxide @ nickel composite material is reduced in a hydrogen atmosphere at the temperature of 300-400 ℃ for 0.5-1.5 h. Preferably, the hydrogen atmosphere is a mixed gas of hydrogen and argon, and the volume fraction of hydrogen is 5%.
Further, in the step (4), the copper salt is copper nitrate, and the ammonium salt is ammonium nitrate. The concentration of the copper salt in the solution is 0.13-0.15 mol/L, the concentration of the ammonium salt in the solution is 0.18-0.23 mol/L, and the concentration of the aluminum oxide @ nickel composite material in the solution is 0.001-0.002 g/mL.
Further, in the step (4), the hydrothermal reaction is carried out in a closed reaction kettle, the reaction temperature is 100 ℃, and the reaction time is 40-50 h.
According to the invention, in the synthesis process, nickel oxalate nanowires are taken as templates, and the copper-doped nickel-aluminum layered double hydroxide (CuNiAl LDH) is obtained by a method combining atomic layer deposition, hydrogen reduction and hydrothermal technologies, and has a typical nanotube structure, wherein the nanotube structure consists of uniform ultrathin nanosheets, the nanosheets are uniformly dispersed, the structure is clear, and the thickness of each nanosheet is about 6nm, so that the benefit of the atomic layer is realizedThe deposition technique firstly adopts NiC2O4Uniform deposition of Al on nanowires2O3And the coating is helpful for maintaining the one-dimensional shape of the product. In addition, Al can be easily controlled by adjusting the number of cycles of atomic layer deposition2O3Thickness of the coating, which facilitates the formation of layered nanotube structures and morphological modulation of the LDH in subsequent stages. Therefore, the problem of LDH agglomeration is well solved by the atomic layer deposition technology, and the structural stability of LDH is improved. It has also been found in experimental studies that Al is controlled by atomic layer deposition2O3The thickness does have a significant effect on the LDH structure. As can be seen from FIG. 1, the CuNiAl LDH morphology obtained under different ALD cycle numbers is more, the LDH morphology is more close to the rule, and the structure is more stable.
Furthermore, the copper-doped nickel-aluminum layered double hydroxide has larger specific surface area, provides more active centers, shows excellent catalytic activity of the peroxide mimic enzyme and can be used as the peroxide mimic enzyme.
Further, the copper-doped nickel aluminum layered double hydroxide can be used in combination with 3,3',5,5' -Tetramethylbenzidine (TMB) to detect the hydrogen peroxide concentration. Specifically, hydrogen peroxide can make a 3,3',5,5' -Tetramethylbenzidine (TMB) solution appear blue under the catalysis of copper-doped nickel-aluminum layered double hydroxide, the blue color can be deepened along with the increase of the hydrogen peroxide concentration, and the hydrogen peroxide concentration in the system can be determined qualitatively through the change of the solution color. In addition, the change of the hydrogen peroxide concentration in the system can be quantitatively determined by detecting the change of the absorbance of the system through an ultraviolet spectrophotometry.
Further, the copper-doped nickel aluminum layered double hydroxide can be used in combination with 3,3',5,5' -Tetramethylbenzidine (TMB) to detect the concentration of glucose. Specifically, glucose can generate hydrogen peroxide under the action of glucolase, and the generated hydrogen peroxide can change the color and the absorbance of a system in the presence of copper-doped nickel-aluminum layered double hydroxides and 3,3',5,5' -tetramethylbenzidine, so that the detection of the concentration of the glucose is indirectly realized.
Compared with the prior art, the invention has the advantages that:
(1) the preparation method combines the atomic layer deposition technology, the hydrogen reduction technology and the hydrothermal technology to prepare the copper-doped nickel-aluminum layered double hydroxide (CuNiAl LDH), and has the advantages of simple and easy preparation process and low cost.
(2) The CuNiAl LDH prepared by the method has a typical nanotube structure, consists of uniform ultrathin nanosheets, solves the problem that LDH prepared by the traditional method is easy to aggregate, has a large specific surface area, and provides more active sites.
(3) The CuNiAl LDH prepared by the invention has good catalytic performance of peroxidase mimic enzyme, can be used as the peroxidase mimic enzyme, and has the strongest catalytic activity at the temperature of 55 ℃ through experiments, so that the defects that natural enzyme is difficult to extract and is easy to inactivate and denature at high temperature are overcome, the application of the enzyme at high temperature is expanded, and the CuNiAl LDH has potential application value in the fields of biological medicine, environmental detection, food processing and the like.
(4) The copper-doped nickel-aluminum layered double hydroxide can be combined with 3,3',5,5' -Tetramethylbenzidine (TMB) to realize the detection of the concentration of hydrogen peroxide and glucose.
Drawings
FIG. 1 is an SEM image of copper doped nickel aluminum layered double hydroxide (CuNiAl LDH) at different atomic layer deposition cycles; (A) 20CuNiAl LDH (B) 50CuNiAl LDH (C) 100CuNiAl LDH.
FIG. 2 is a TEM image of the copper-doped nickel-aluminum layered double hydroxide (100 CuNiAl LDH) obtained in example 1.
FIG. 3 is a BET plot of the copper-doped nickel aluminum layered double hydroxide (100 CuNiAl LDH) obtained in example 1.
FIG. 4 shows the absorption spectrum (A) and the corresponding color change (B) (a: H) for different reaction systems obtained in example 12O2-TMB; b: TMB-100CuNiAl LDH; c: H2O2-TMB-100CuNiAl LDH)
FIG. 5 is a graph of the catalytic activity of a CuNiAl LDH peroxide mimic enzyme as a function of pH.
FIG. 6 is a graph of CuNiAl LDH peroxide mimic enzyme catalytic activity versus temperature.
Fig. 7 is an SEM image of the product obtained in comparative example 2.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to be limiting.
Example 1
Copper-doped nickel-aluminum Layered Double Hydroxide (LDH) peroxide mimetic enzymes
(1) Synthesis of NiC2O4Nanowire and method of manufacturing the same
0.711 g of NiCl was weighed2•6H2O into a 100 mL beaker, 48 mL of ethylene glycol and 27 mL of ultrapure water were added, and 0.209 g of NaC was added under magnetic stirring2O4And stirred for 20 minutes until the solution is well mixed. The mixed solution was transferred to a 100 mL hydrothermal kettle and reacted at 220 ℃ for 12 hours. After the reaction is finished, naturally cooling to room temperature, centrifuging the precipitate, respectively washing with water and ethanol for three times, and naturally drying in the air to obtain blue-green NiC2O4And (3) nanowire powder.
(2) Preparation of Al2O3Ni core-shell structure
Adding 10 mg of NiC2O4Dissolving the nanowire powder in 10mL of ethanol, and carrying out ultrasonic treatment for 10 minutes to ensure that NiC is obtained2O4Uniformly dispersing in ethanol solution. Mixing NiC2O4The ethanol solution is dripped on a quartz plate with the thickness of 5mm, and Atomic Layer Deposition (ALD) is carried out after ethanol is volatilized in the air. Putting the quartz plate into an atomic layer deposition device, wherein the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. Respectively circulating for 100 circles according to the program to obtain Al with different thicknesses2O3. Has been deposited by ALDAfter completion, the sample was placed in a tube furnace and a mixture of hydrogen and argon (hydrogen volume fraction 5%) was passed through and reacted at 350 ℃ for one hour to obtain Al2O3a/Ni core-shell structure material.
(3) Preparation of CuNiAl LDH
Weighing 0.01 mol of Cu (NO)3)2•3H2O and 0.015 mol of NH4NO3Dissolved in 70 mL of ultrapure water, stirred with a glass rod until completely dissolved, and 0.1 g of a sample (Al) was added2O3Ni), mixed uniformly under magnetic stirring, transferred to a 100 mL hydrothermal kettle, and reacted at 100 ℃ for 48 hours. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product precipitate is centrifuged, washed with water and ethanol respectively for three times, and naturally dried in the air. The resulting sample was named 100CuNiAl LDH.
Fig. 1C is an SEM image of the resulting 100CuNiAl LDH, from which it can be seen that the resulting product is nanotube-shaped.
Fig. 2 is a TEM image of the obtained 100CuNiAl LDH product, and it can be seen from the figure that the nanotubes are self-assembled from nano sheets with uniform distribution.
FIG. 3 is a BET diagram of the resulting 100CuNiAl LDH product, from which it can be seen that the resulting product has a higher specific surface area.
Example 2
Copper-doped nickel-aluminum Layered Double Hydroxide (LDH) peroxide mimetic enzymes
(1) Synthesis of NiC2O4Nanowire and method of manufacturing the same
0.675 g of NiCl was weighed2•6H2O into a 100 mL beaker, 48 mL of ethylene glycol and 27 mL of ultrapure water were added, and 0.195 g of NaC was added under magnetic stirring2O4And stirred for 20 minutes until the solution is well mixed. The mixed solution was transferred to a 100 mL hydrothermal kettle and reacted at 200 ℃ for 9 hours. After the reaction is finished, naturally cooling to room temperature, centrifuging the precipitate, respectively washing with water and ethanol for three times, and naturally drying in the air to obtain blue-green NiC2O4And (3) nanowire powder.
(2) Preparation of Al2O3Ni core-shell structure
Adding 10 mg of NiC2O4Dissolving the nanowire powder in 10mL of ethanol, and carrying out ultrasonic treatment for 10 minutes to ensure that NiC is obtained2O4Uniformly dispersing in ethanol solution. Mixing NiC2O4The ethanol solution is dripped on a quartz plate with the thickness of 5mm, and Atomic Layer Deposition (ALD) is carried out after ethanol is volatilized in the air. Putting the quartz plate into an atomic layer deposition device, wherein the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. Respectively circulating for 80 circles according to the program to obtain 80 NiC2O4@Al2O3. After completion of the ALD deposition, the sample was placed in a tube furnace and reacted at 300 ℃ for one hour by passing a mixture of hydrogen and argon (hydrogen volume fraction 5%) to obtain Al2O3a/Ni core-shell structure material.
(3) Preparation of CuNiAl LDH
0.009 mol of Cu (NO) was weighed out3)2•3H2O and 0.013 mol NH4NO3Dissolved in 70 mL of ultrapure water, stirred with a glass rod until completely dissolved, and 0.1 g of a sample (Al) was added2O3Ni), mixed uniformly under magnetic stirring, transferred to a 100 mL hydrothermal kettle, and reacted at 100 ℃ for 40 hours. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product precipitate is centrifuged, washed with water and ethanol respectively for three times, and naturally dried in the air. The resulting sample was named 80CuNiAl LDH.
Example 3
The peroxide mimetic enzyme properties of the prepared CuNiAl LDHs were verified using 3,3',5,5' -Tetramethylbenzidine (TMB) solution and hydrogen peroxide solution:
(1) the reaction system comprises: 4 mM TMB (600. mu.L), 500. mu.g mL−1100CuNiAl LDH (300. mu.L) of example 1, 20 mM H2O2(600 μ L) and 20 mM phosphate buffer pH = 3.5 (1500 μ L). As a fruitA test sample (c);
(2) the reaction system comprises: 100CuNiAl LDH from example 1 (300. mu.L, 500. mu.g mL)−1) A mixed solution of TMB (600. mu.L, 4 mM) and phosphate buffer solution (2100. mu.L, 20.0 mM); as a control sample (b);
(3) the reaction system comprises: h2O2(600. mu.L, 20 mM), TMB (600. mu.L, 4 mM) and phosphate buffer solution (1800. mu.L, 20.0 mM). As a control sample (a).
(4) After reacting for 30 minutes at 55 ℃, measuring the absorbance value of the reacted solution by using a UV-vis spectrophotometer at the wavelength of 500-800 nm, and photographing to record the color state of the reacted solution (see figure 4).
As can be seen from fig. 4 (B), after the water bath reaction, the solution of group (c) showed a clear color change from colorless to blue, while the solutions of groups (a) and (B) were in colorless and transparent state with no color change, which indicates that 100CuNiAl LDH has catalytic effect on hydrogen peroxide and has activity of peroxide mimetic enzyme. As can be seen from FIG. 4 (A), the maximum absorption peak at a wavelength of 652 nm was observed, and the concentration of hydrogen peroxide was quantitatively determined from the absorbance value thereof.
Example 4
Determining the optimum pH of the catalytic reaction of the CuNiAl LDH peroxide mimic enzyme:
(1) phosphate buffers with pH values of 2.0, 3.0, 3.5, 4.0, 5.0, 6.0, 7.0, 8.0 and 9.0 and a concentration of 20 mM were prepared, respectively.
(2) 500. mu.g mL of each of the solutions was prepared using phosphate buffers of different pH−1100CuNiAl LDH solution of example 1, 20 mM H2O2Solution and 4 mM TMB solution.
(3) The reaction system comprises the following components under different pH conditions: 600 μ L of TMB solution, 300 μ L of 100CuNiAl LDH solution from example 1, 600 μ L of H2O2The solution and 1500. mu.L of phosphate buffer. The absorbance value was measured at 652 nm after 30 minutes reaction at 55 ℃. By comparing the magnitude of the absorbance values, the optimum pH is obtained (See fig. 5).
FIG. 5 shows the effect of pH on the catalytic activity of 100CuNiAl LDH peroxidase mimic. As can be seen from the figure, the mimic enzyme maintained good catalytic activity under acidic conditions, and reached the highest catalytic activity at pH 3.5.
Example 5
Determining the optimal temperature of the catalytic reaction of the CuNiAl LDH peroxide mimic enzyme:
(1) 20 mM phosphate buffer (pH = 3.5, 1500. mu.L) was added to a 5 mL vial, and 4 mM TMB solution (600. mu.L) and 20 mM H were added thereto, respectively2O2Solution (600. mu.L) and 500. mu.g mL−1The 100CuNiAl LDH solution (300 μ L) of example 1.
(2) The reaction was carried out at 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C for 30 min in this order, and the absorbance value was measured at 652 nm. By comparing the magnitude of the absorbance values, the optimal reaction temperature was obtained (see FIG. 6).
FIG. 6 shows the effect of pH on the catalytic activity of 100CuNiAl LDH peroxidase mimic. As can be reflected by the figure, the peroxide mimic enzyme keeps better catalytic activity within the range of 50-70 ℃, and reaches the highest catalytic activity at the temperature of 55 ℃. The catalytic capability of the CuNiAl LDH peroxide mimic enzyme under the high-temperature condition can make up for the defect of high-temperature inactivation and denaturation of natural enzyme.
Example 6
The detection characteristics of the prepared peroxide mimic enzyme of the CuNiAl LDH on glucose are verified:
(1) 100. mu.L of 30. mu.M glucose solution and 100. mu.L of 10. mu.g mL−1Added to 300 μ L phosphate buffer (PBS, 20 mM, pH = 5.5). The solution is evenly mixed and then reacts for 30 min in a constant temperature water bath kettle at 35 ℃.
(2) After the reaction was completed, 300. mu.L of 500. mu.g mL was added to the mixed solution−1The 100CuNiAl LDH solution of example 1, 600 μ L of 4 mM TMB and 1600 μ L of phosphate buffer (PBS, 20 mM, pH = 3) were mixed well。
(3) Placing the mixed solution into a constant temperature water bath kettle at 55 deg.C for reaction for 30 min, centrifuging, collecting supernatant, measuring absorbance at 652 nm, and recording color change.
The results show that a clear absorption peak appears at 652 nm and the solution changes color from colorless and transparent to blue. This is because glucose produces hydrogen peroxide under the action of glucose oxidase, which undergoes a color change in the presence of 100CuNiAl LDH and TMB.
Comparative example 1
(1) Synthesis of NiC2O4Nanowire: the procedure is as in example 1.
(2) Preparation of Al2O3a/Ni core-shell structure:
adding 10 mg of NiC2O4Dissolving the nanowire powder in 10mL of ethanol, and carrying out ultrasonic treatment for 10 minutes to enable NiC2O4Uniformly dispersing in ethanol solution. Mixing NiC2O4The ethanol solution is dripped on a quartz plate with the thickness of 5mm, and Atomic Layer Deposition (ALD) is carried out after ethanol is volatilized in the air. Putting a quartz plate into an atomic layer deposition device, wherein the temperature of the atomic layer deposition device is 150 ℃, and the procedure is as follows: performing pulse adsorption reaction on a trimethyl aluminum precursor with the purity of 99%; inert gas purges redundant reactants and byproducts; pulse adsorption reaction of a deionized water precursor; the inert gas purges excess reactants and byproducts. After circulating for 20 and 50 circles according to the program respectively, NiC with different thicknesses is obtained2O4@Al2O3. After completion of the ALD deposition, the sample was placed in a tube furnace and reacted at 350 ℃ for one hour by passing a mixture of hydrogen and argon (hydrogen volume fraction 5%) to yield Al2O3a/Ni core-shell structure material.
(3) Preparation of CuNiAl LDH: the procedure is as in example 2.
Fig. 1(a) and fig. 1(B) are SEM images of the obtained 20CuNiAl LDH and 50CuNiAl LDH products, and it can be seen from the images that the products agglomerate without regular structures at low ALD cycle number, which indicates that the cycle number of ALD technique plays a crucial role in product morphology and structure stability.
Comparative example 2
(1) Synthesis of NiC2O4Nanowire: the procedure is as in example 1.
(2) Preparation of Al2O3a/Ni core-shell structure: the procedure is as in example 1.
(3) Preparation of CuNiAl LDH:
weighing 0.01 mol of Cu (CH)3COO)2·H2O and 0.015 mol of NH4NO3Dissolved in 70 mL of ultrapure water, stirred with a glass rod until completely dissolved, and 0.1 g of a sample (Al) was added2O3Ni), mixed uniformly under magnetic stirring, transferred to a 100 mL hydrothermal kettle, and reacted at 100 ℃ for 48 hours. And after the reaction is finished, naturally cooling to room temperature, centrifuging the product precipitate, washing with water and ethanol respectively for three times, and naturally drying in the air to obtain the sample.
Fig. 7 is an SEM image of a product prepared using copper acetate as the copper salt, from which it can be seen that the product morphology does not have a hierarchical nanotube structure, which illustrates that the use of different copper salts also has a large impact on the final morphology of the product.
Comparative example 3
Copper-doped nickel-aluminum Layered Double Hydroxide (LDH) peroxide mimetic enzymes
(1) Synthesis of NiC2O4Nanowire: the procedure is as in example 1.
(2) Preparation of Al2O3Ni core-shell structure
Adding 10 mg of NiC2O4Dissolving the nanowire powder in 10mL of ethanol, and carrying out ultrasonic treatment for 10 minutes to ensure that NiC is obtained2O4Uniformly dispersing in ethanol solution. Mixing NiC2O4The ethanol solution was dropped onto a quartz plate with a thickness of 7 mm, and Atomic Layer Deposition (ALD) was performed after ethanol was volatilized in the air, in the same manner as in example 1.
(3) Preparation of CuNiAl LDH: the procedure is as in example 1.
Since NiC is2O4The ethanol solution is dripped on a quartz plate to an excessive thickness, resulting in precipitationAccumulated Al2O3The film was not uniform enough and some portions were actually deposited with too few cycles, so that irregularities in the agglomerated structure similar to the product of comparative example 1 might occur locally.
Claims (11)
1. A preparation method of copper-doped nickel-aluminum layered double hydroxide is characterized by comprising the following steps:
(1) preparing nickel oxalate nanowires;
(2) depositing alumina on the surface of the nickel oxalate nanowire by adopting an atomic layer deposition method to obtain an alumina @ nickel oxalate composite material;
(3) carrying out hydrogen reduction on the aluminum oxide @ nickel oxalate composite material to obtain the aluminum oxide @ nickel composite material;
(4) putting the aluminum oxide @ nickel composite material into a solution containing copper salt and ammonium salt, and performing hydrothermal reaction to obtain copper-doped nickel-aluminum layered double hydroxide;
in the step (2), the nickel oxalate nanowire dispersion liquid is dripped onto a quartz plate, the quartz plate is placed into an atomic layer deposition device for atomic layer deposition after being dried, the deposition temperature is 140-; the nickel oxalate nanowire dispersion liquid is ethanol dispersion liquid of nickel oxalate nanowires, the concentration of the nickel oxalate nanowires in the dispersion liquid is 0.5-1.5mg/ml, and the thickness of the nickel oxalate nanowire dispersion liquid on a quartz plate is 3-5 mm;
in the step (4), the copper salt is copper nitrate, and the ammonium salt is ammonium nitrate.
2. The method of claim 1, wherein: in the step (1), nickel salt, ethylene glycol and water are uniformly mixed, then oxalate is added and uniformly mixed under stirring, and the obtained mixed solution is subjected to hydrothermal reaction to obtain the nickel oxalate nanowire.
3. The method of claim 2, wherein: in the step (1), the concentration of nickel salt in a reaction system is 0.0090 g/mL-0.0100 g/mL, the concentration of oxalate in the reaction system is 0.0026 g/mL-0.0029 g/mL, and the volume ratio of glycol to water is 4-6: 3.
4. The method of claim 2, wherein: in the step (1), the hydrothermal reaction is carried out in a closed reaction kettle, the reaction temperature is 200-250 ℃, and the reaction time is 9-14 h.
5. The method of claim 1, wherein: in the step (3), the aluminum oxide @ nickel composite material is reduced in a hydrogen atmosphere at the temperature of 300-400 ℃ for 0.5-1.5 h.
6. The method according to claim 5, wherein: the hydrogen atmosphere was provided by argon gas containing an integral of hydrogen gas of 5%.
7. The method of claim 1, wherein: in the step (4), the concentration of the copper salt in the solution is 0.13-0.15 mol/L, the concentration of the ammonium salt in the solution is 0.18-0.23 mol/L, and the concentration of the aluminum oxide @ nickel composite material in the solution is 0.001-0.002 g/mL.
8. The method of claim 1, wherein: in the step (4), the hydrothermal reaction is carried out in a closed reaction kettle, the reaction temperature is 100 ℃, and the reaction time is 40-50 h.
9. The copper-doped nickel aluminum layered double hydroxide prepared by the method for preparing copper-doped nickel aluminum layered double hydroxide according to claim 1.
10. Use of the copper-doped nickel aluminium layered double hydroxide according to claim 9 as a peroxide mimetic enzyme.
11. Use of the copper doped nickel aluminium layered double hydroxide according to claim 9 in combination with 3,3',5,5' -tetramethylbenzidine for the detection of hydrogen peroxide and glucose concentration.
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