CN112129823B - Preparation method of Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection - Google Patents
Preparation method of Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection Download PDFInfo
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Abstract
The invention discloses a Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection and a preparation method thereof. The composite metal wire comprises a Ni metal wire, a NiO nano layer formed by oxidizing the surface layer of the Ni metal wire, a ZnO nano flower cluster uniformly coated on the surface of the NiO and a CS film uniformly distributed on the ZnO nano flower cluster. The preparation method of the composite metal wire comprises the following steps: preparing a NiO nano layer by using a thermal oxidation method and using a Ni metal wire as a substrate through thermal oxidation in a tubular furnace; growing ZnO nanoflower clusters on the NiO nano-layer by adopting a hydrothermal method and taking Ni @ NiO as a substrate; a physical impregnation method is adopted, the Ni @ NiO @ ZnO composite metal wire is used as a substrate, and a CS film is wrapped on the surface of ZnO. The method has the advantages of simple process, mild reaction conditions, low preparation cost and good stability. The prepared composite metal wire combines the advantages of a p-n junction interface and a selective adsorption film, plays a synergistic effect, has excellent sensing performance and can be applied to the online detection of copper ions in water.
Description
Technical Field
The invention relates to a Ni @ NiO @ ZnO @ CS composite metal wire, a preparation method thereof and application of the composite metal wire in detection of copper ions in water, and belongs to the technical field of novel composite materials.
Background
Copper ion (Cu)2+) Is an essential element in organisms and plays an important role in body functions. However, excess Cu2+Intake ofWill cause Wilson, Alzheimer's and Menkes diseases. With Cu2+Pollution in rivers or oceans, Cu2+The potential toxic effects on humans remains a global challenge. Thus, an effective trace amount of Cu was developed2+The detection method has important significance for clinical research, food industry and environmental monitoring.
Various methods for detecting Cu have been established2+Including inductively coupled plasma atomic emission spectroscopy (ICP-AES), Flameless Atomic Absorption Spectroscopy (FAAS), and Atomic Absorption Spectroscopy (AAS). Although the above techniques have good sensitivity and selectivity, they require relatively expensive instruments, complicated procedures and long time.
Electrochemical analysis methods are of great interest because of their advantages of simple operation, fast response speed, high sensitivity, and the like. Currently detecting Cu2+The electrochemical method of (a) is Adsorption Stripping Voltammetry (ASV), but it is an indirect complex process involving enrichment and dissolution. Therefore, the development of a method for directly detecting Cu in water on line is urgently needed2+Sensing materials and techniques.
Disclosure of Invention
In view of the above problems, it is an object of the present invention to provide a Ni @ NiO @ ZnO @ CS composite wire for on-line detection of copper ions in water, which has excellent sensitivity and selectivity.
The invention also aims to provide the preparation method of the Ni @ NiO @ ZnO @ CS composite metal wire, which has the advantages of simple process, mild reaction conditions and low preparation cost.
The principle of the invention is as follows:
with the development of nanotechnology, metal oxide nanostructures become a promising electrochemical sensing material due to their easy availability, excellent electrical properties and chemical stability. Wherein NiO is a wide bandgap p-type semiconductor material (E)g=3.55eV), has been extensively studied in catalysts and sensors due to their good catalytic and sensing properties. ZnO is a wide bandgap n-type semiconductor (E)g=3.37eV), which is recognized as an excellent sensing material due to its high photosensitivity, excellent electron transport characteristics. Because NiOAnd ZnO both have wider band gaps, so that a p-n junction interface potential barrier can be formed, the interface potential barrier is a factor highly sensitive to charged molecules under low application voltage, when the charged molecules contact the interface potential barrier, induced charges can cause the height of the potential barrier to change, and further cause conductivity change, and the detection method can be used for generating a high-sensitivity detection signal. However, the above combinations lack selective recognition capability for the target ion. While Chitosan (CS) is a polymer material having adhesion, no toxicity and good film-forming ability, and has Cu in solution due to its large amount of hydroxyl and amino reactive functional groups2+Has selective adsorption capacity. CS in Ni2+， Pb2+， Co2+， Ba2+， Zn2+For Cu under the condition of coexistence of various metal ions2+Shows a high affinity, however, the sensitivity is low, so that the CS action alone cannot reach Cu2+And (5) detecting the ideal effect. In order to solve the important problem of detection sensitivity and selectivity, a p-type semiconductor NiO is combined with ZnO to form a p-n junction barrier, and then a polymer CS is modified on the surface of the p-n junction barrier, so that the synergistic effect of the p-n junction barrier and a selective film is exerted, and the sensitivity and the selectivity are improved.
The composite metal wire is prepared by a thermal oxidation method, a hydrothermal method and a physical impregnation method. Firstly growing a NiO nano layer on the Ni wire through thermal oxidation, and sequentially attaching a ZnO nano flower cluster and a CS film to the surface of the NiO nano layer through a hydrothermal method and a physical impregnation method to form the Ni @ NiO @ ZnO @ CS composite metal wire. According to the invention, NiO and ZnO form a p-n junction barrier, and then are combined with the selectively adsorbed polymer CS to synthesize the multi-component nano composite material, so that the synergistic effect is exerted, and the detection sensitivity is improved while the high selectivity is realized.
The reaction process of the present invention is shown in the following equation.
2Ni + O2 = 2NiO (1)
Zn2+ + 2NH3·H2O = Zn(OH)2↓+ 2NH4 + (2)
Zn(OH)2↓= ZnO + H2O (3)
The specific technical scheme of the invention is as follows:
the Ni @ NiO @ ZnO @ CS composite metal wire for detecting copper ions in water comprises a Ni metal wire, a NiO nano layer formed by oxidizing the surface layer of the Ni metal wire, ZnO nano flower clusters uniformly coated on the surface of the NiO nano layer, and a CS film uniformly distributed on the ZnO nano flower clusters.
The thickness of the CS film layer is 70-100 nanometers.
The ZnO nano flower cluster consists of regular hexagonal nano rods, the length of the ZnO nano flower cluster is 10 micrometers, and the diameter of the ZnO nano flower cluster is 0.1-1.5 micrometers.
The NiO nano-layer crystal grains have a regular crystal grain arrangement, the crystal grain size is 1.5 microns, and the thickness is 1 micron.
The preparation method of the Ni @ NiO @ ZnO @ CS composite metal wire is characterized by comprising the following steps of:
the method comprises the following steps: the nickel wire was polished, ultrasonically cleaned, then blow-dried with nitrogen, and immediately transferred to a tube furnace. Raising the furnace temperature to 850 ℃ within 300min, keeping the temperature of the nickel wire at the temperature for 4h, and taking out a sample after the furnace temperature is gradually cooled to obtain a Ni @ NiO metal wire;
step two: dissolving a proper amount of zinc nitrate and a small amount of ammonia water in deionized water to form a zinc nitrate solution, then putting the zinc nitrate solution and the prepared Ni @ NiO metal wire into a hydrothermal kettle, preparing a ZnO nano flower cluster on the Ni @ NiO metal wire by a hydrothermal method, taking out, washing and drying to finally obtain a Ni @ NiO @ ZnO composite metal wire;
step three: preparing a CS modified Ni @ NiO @ ZnO composite metal wire by adopting a physical impregnation method: adding a proper amount of CS into an acetic acid aqueous solution, and stirring vigorously for 1h to obtain a CS solution; and then immersing the Ni @ NiO @ ZnO composite metal wire into the CS solution for 30s, taking out, and drying at room temperature to finally obtain the Ni @ NiO @ ZnO @ CS composite metal wire.
Further, in the step (i), the ultrasonic cleaning is ultrasonic cleaning with acetone, ethanol and deionized water, respectively.
Further, in the above step, the washing is washing with ethanol and deionized water, respectively.
Further, in the above step ②, the drying means drying in an oven at 60 ℃ for 6 hours.
The Ni @ NiO @ ZnO @ CS composite metal wire is applied to detection of copper ions in water.
The method synthesizes the Ni @ NiO metal wire by a thermal oxidation method, enables ZnO nano flower clusters to be uniformly coated on the surface of NiO by a hydrothermal method, and finally enables CS to be uniformly distributed on the surface of the Ni @ NiO @ ZnO by a physical impregnation method. The preparation method is simple, the reaction condition is mild, and the preparation cost is low. In the prepared composite metal wire, NiO and ZnO form a p-n junction barrier, and high-sensitivity electrochemical response can be generated on charged molecules; the CS film is mainly used for selectively adsorbing copper ions. The structure has the advantages that the p-n junction potential barrier is fully utilized to generate high-sensitivity response and the high-selectivity property of the CS film, the advantages of all components are integrated, the synergistic effect is exerted, the structure can be effectively applied to the field of electrochemical sensing, and the selectivity is improved while the detection sensitivity is improved. The Ni @ NiO @ ZnO @ CS composite metal wire is used as a working electrode, and copper ions in water are used as a detection target, so that the excellent sensing performance is shown.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the present invention.
FIG. 2 is a scanning electron micrograph and a three-dimensional schematic of the material prepared in example 1 of the present invention.
Wherein, a-b, Ni @ NiO metal wire scanning electron microscope images; c-d, a scanning electron microscope image of the Ni @ NiO @ ZnO composite metal wire; e. a scanning electron microscope image of the Ni @ NiO @ ZnO @ CS composite metal wire; f. a three-dimensional schematic diagram of the Ni @ NiO @ ZnO @ CS composite metal wire.
FIG. 3 is an XRD representation of the Ni @ NiO @ ZnO @ CS composite wire prepared in example 1 of the present invention.
FIG. 4 is a FT-IR characterization of the Ni @ NiO @ ZnO @ CS composite wire made in example 1 of the present invention.
FIG. 5 is a linear plot of the current intensity as a function of copper ion concentration for the Ni @ NiO @ ZnO @ CS composite wire prepared in example 1 of the present invention.
FIG. 6 is a graph showing the difference in current intensity between the Ni @ NiO @ ZnO @ CS composite wire prepared in example 1 of the present invention and a common interfering substance.
Detailed Description
The invention is further explained by the specific embodiment in the following with the attached drawings.
Example 1:
the specific preparation process of the invention is shown in figure 1.
(1) Cutting a nickel wire with the diameter of 0.8mm into small sections of 2cm, polishing the nickel wire for 5min by using 1200-mesh abrasive paper, ultrasonically cleaning the polished nickel wire for 10 min by using acetone, ethanol and water respectively, and drying the nickel wire by using nitrogen. And then putting the dried nickel wire into a tubular furnace, calcining in the air, setting the furnace temperature to 850 ℃ within 300min, keeping the temperature of the nickel wire at the temperature for 4h, and taking out a sample after the furnace temperature is gradually cooled, so that the Ni wire with the blackish green surface can be seen, and the Ni NiO @ metal wire is obtained.
From the scanning electron microscope shown in fig. 2b, it can be seen that the NiO nanolayer grown on the basis of the Ni filament has a relatively uniform grain arrangement, a grain size of about 1.5 microns and a thickness of about 1 micron.
(2) Weighing 0.416g of zinc nitrate hexahydrate, dissolving in 38mL of deionized water, carrying out ultrasonic treatment for 10 minutes, slowly dropwise adding 2mL of ammonia water into the zinc nitrate aqueous solution, continuously stirring, after completely dissolving, putting the mixed solution and the Ni @ NiO composite material into a hydrothermal kettle, keeping the temperature at 95 ℃ for 6 hours, taking out a sample, washing with ethanol and deionized water, and drying in an oven at 60 ℃ for 6 hours.
From fig. 2c-d, the surface of NiO was covered with ZnO nanoflower clusters, and from fig. 2d, it can be seen that the nanoflower clusters consist of regular hexagonal nanorods, approximately 10 microns in length and approximately 0.1-1.5 microns in diameter. Fig. 3 is an XRD spectrum of the Ni @ NiO @ ZnO composite wire, in which characteristic peaks of Ni (200) and NiO (111), NiO (200), NiO (220), NiO (311), NiO (222), and characteristic peaks of ZnO (100), ZnO (002), ZnO (101), ZnO (102), ZnO (110), ZnO (112) are clearly seen, and no impurity peak is present.
(3) 0.5g of CS powder was weighed out by physical immersion method and dissolved in 99.5mL of deionized water and 0.5mL of glacial acetic acid aqueous solution, and stirred vigorously for 1h to obtain CS solution. And then immersing the Ni @ NiO @ ZnO composite metal wire into the CS solution for 30s, taking out, and drying at room temperature to finally obtain the Ni @ NiO @ ZnO @ CS composite metal wire.
As can be seen from a scanning electron microscope shown in FIG. 2e, CS is uniformly covered on the surface of Ni @ NiO @ ZnO, and the thickness of the CS film layer is about 70-100 nanometers. FIG. 4 is a FT-IR spectrum of a Ni @ NiO @ ZnO @ CS composite wire, which can be seen at 466 cm−1The peak at (a) belongs to the bond between zinc and oxygen; 570 cm−1And 673 cm−1The peak at (a) belongs to the bond between nickel and oxygen; 893 cm−1、1033 cm−1、1081 cm−1、1055 cm−1、1255 cm−1、1422 cm−1、1599 cm−1、2877 cm−1And 3301 cm−1The peak at (A) belongs to the bond of CS.
The electrochemical test is carried out on an electrochemical workstation, and a traditional three-electrode system is adopted, wherein a Pt electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the prepared Ni @ NiO @ ZnO @ CS composite metal wire is used as a working electrode, and a phosphate buffer solution with the pH value of 7.0 is used as a reaction environment. As can be seen from FIG. 5, the Ni @ NiO @ ZnO @ CS composite wire pair Cu2+The detection range of (A) is 0-6000 nM, and the lowest detection limit is 0.81 nM. As can be seen from FIG. 6, at a concentration of 500 nM for each component, the Ni @ NiO @ ZnO @ CS composite wire pair Cu2+Has the highest response to other than Cu2+The responses of other interfering substances are lower, which shows that the composite metal wire has anti-interference capability to common interfering substances.
Example 2:
(1) cutting a nickel wire with the diameter of 0.8mm into small sections of 3cm, polishing the nickel wire for 5min by using 1200-mesh abrasive paper, ultrasonically cleaning the polished nickel wire for 10 min by using acetone, ethanol and water respectively, and drying the nickel wire by using nitrogen. And then putting the dried nickel wire into a tubular furnace, calcining in the air, setting the furnace temperature to 850 ℃ within 300min, keeping the temperature of the nickel wire at the temperature for 4h, and taking out a sample after the furnace temperature is gradually cooled, so that the Ni wire with the blackish green surface can be seen, and the Ni NiO @ metal wire is obtained. Experiments show that the synthesis of the material is not influenced by changing the length of the Ni wire within a certain range.
(2) Weighing 0.416g of zinc nitrate hexahydrate, dissolving in 38mL of deionized water, carrying out ultrasonic treatment for 10 minutes, slowly dropwise adding 2mL of ammonia water into the zinc nitrate aqueous solution, continuously stirring, after completely dissolving, putting the mixed solution and the Ni @ NiO composite material into a hydrothermal kettle, keeping the temperature at 95 ℃ for 3 hours, taking out a sample, washing with ethanol and deionized water, and drying in an oven at 60 ℃ for 6 hours. Experiments show that the length of the ZnO nano floral grouping can be changed within the range of 5-10 microns by changing the hydrothermal time within a certain range, and the quantity of the ZnO nano floral grouping loaded on the NiO nano layer is reduced.
(3) 0.5g of CS powder was weighed out by physical immersion method and dissolved in 99.5mL of deionized water and 0.5mL of glacial acetic acid aqueous solution, and stirred vigorously for 1h to obtain CS solution. And then immersing the Ni @ NiO @ ZnO composite metal wire into a CS solution for 1min, taking out, and drying at room temperature to finally obtain the Ni @ NiO @ ZnO @ CS composite metal wire. Experiments have shown that appropriate immersion times can increase the thickness of the CS film.
Example 3:
(1) cutting a nickel wire with the diameter of 0.8mm into small sections of 2cm, polishing the nickel wire for 5min by using 1200-mesh abrasive paper, ultrasonically cleaning the polished nickel wire for 10 min by using acetone, ethanol and water respectively, and drying the nickel wire by using nitrogen. And then putting the dried nickel wire into a tubular furnace, calcining in the air, setting the furnace temperature to 800 ℃ within 300min, keeping the temperature of the nickel wire at the temperature for 4h, and taking out a sample after the furnace temperature is gradually cooled, so that the Ni wire with the blackish green surface can be seen, and the Ni NiO @ metal wire is obtained. Experiments have shown that varying the heating temperature within a certain range results in a variation of the grain size of the NiO nanolayer within the range of 1-1.5 microns.
(2) Weighing 0.832g of zinc nitrate hexahydrate, dissolving in 38mL of deionized water, carrying out ultrasonic treatment for 10 minutes, slowly dropwise adding 2mL of ammonia water into the zinc nitrate aqueous solution, continuously stirring, after completely dissolving, putting the mixed solution and the Ni @ NiO composite material into a hydrothermal kettle, keeping the temperature at 95 ℃ for 6 hours, taking out a sample, washing with ethanol and deionized water, and drying in an oven at 60 ℃ for 6 hours. Experiments show that the proper increase of the concentration of the zinc nitrate has no obvious influence on the length and the diameter of the generated ZnO nano flower cluster, but the quantity of the ZnO nano flower cluster loaded on the NiO nano layer is increased.
(3) Using a physical immersion method, 1g of CS powder was weighed into a solution containing 99.5mL of deionized water and 0.5mL of glacial acetic acid in water and stirred vigorously for 1h to obtain a CS solution. And then immersing the Ni @ NiO @ ZnO composite metal wire into a CS solution, taking out, and drying at room temperature to finally obtain the Ni @ NiO @ ZnO @ CS composite metal wire. Experiments show that the proper increase of the concentration of the CS aqueous solution can increase the film thickness of the CS.
Those skilled in the art will appreciate that modifications, additions and substitutions are possible, without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (4)
1. The preparation method of the Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection is characterized in that the Ni @ NiO @ ZnO @ CS composite metal wire for copper ion detection comprises a Ni metal wire, a NiO nano layer formed by oxidizing the surface layer of the Ni metal wire, ZnO nano flower clusters uniformly coated on the surface layer of the NiO nano flower clusters and a CS film uniformly distributed on the ZnO nano flower clusters; the thickness of the CS film layer is 70-100 nanometers; the ZnO nano flower cluster consists of regular hexagonal nano rods, the length of the ZnO nano flower cluster is 10 micrometers, and the diameter of the ZnO nano flower cluster is 0.1-1.5 micrometers; the NiO nano layer has regular crystal grain arrangement, the crystal grain size is 1.5 microns, and the thickness is 1 micron;
the preparation method of the Ni @ NiO @ ZnO @ CS composite metal wire comprises the following steps of:
the method comprises the following steps: polishing a nickel wire, ultrasonically cleaning, blow-drying by using nitrogen, and immediately transferring to a tubular furnace; raising the furnace temperature to 850 ℃ within 300min, keeping the temperature of the nickel wire at the temperature for 4h, and then naturally cooling to obtain Ni @ NiO metal wire;
step two: dissolving a proper amount of zinc nitrate and a small amount of ammonia water in deionized water to form a zinc nitrate solution, then putting the zinc nitrate solution and the prepared Ni @ NiO metal wire into a hydrothermal kettle, preparing a ZnO nano flower cluster on the Ni @ NiO metal wire by a hydrothermal method, taking out, washing and drying to finally obtain a Ni @ NiO @ ZnO composite metal wire;
step three: preparing a CS modified Ni @ NiO @ ZnO composite metal wire by adopting a physical impregnation method: adding a proper amount of CS into an acetic acid aqueous solution, and stirring vigorously for 1h to obtain a CS solution; and then immersing the Ni @ NiO @ ZnO composite metal wire into the CS solution for 30s, taking out, and drying at room temperature to finally obtain the Ni @ NiO @ ZnO @ CS composite metal wire.
2. The preparation method according to claim 1, wherein in step (r), the ultrasonic cleaning is ultrasonic cleaning with acetone, ethanol, and deionized water, respectively.
3. The method according to claim 1, wherein the rinsing in step (II) is performed by respectively rinsing with ethanol and deionized water.
4. The method according to claim 1, wherein the drying in step (ii) is performed in an oven at 60 ℃ for 6 hours.
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