CN112748162B - Ni/ZnO/Cu composite material electrode, preparation method and application thereof, and detection method of chemical oxygen demand of water body - Google Patents
Ni/ZnO/Cu composite material electrode, preparation method and application thereof, and detection method of chemical oxygen demand of water body Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000001514 detection method Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000126 substance Substances 0.000 title claims description 27
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- 238000010438 heat treatment Methods 0.000 claims description 6
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- 239000004471 Glycine Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
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- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
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- 238000004134 energy conservation Methods 0.000 abstract 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
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- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1806—Biological oxygen demand [BOD] or chemical oxygen demand [COD]
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Abstract
The invention relates to a Ni/ZnO/Cu composite material electrode and a preparation method and application thereof. A Ni/ZnO/Cu composite material electrode comprises a nickel sheet as a substrate, ZnO nano columns growing on the surface of the nickel sheet and copper electrodeposited on the surfaces of the ZnO nano columns. The method comprises the steps of firstly growing a ZnO nano column on a nickel sheet serving as a substrate by a solution method, and then electrodepositing copper on the ZnO nano column. The method has the characteristics of simple preparation process, simple operation, energy conservation, environmental protection and the like, and the prepared Ni/ZnO/Cu composite material electrode has excellent electrocatalytic activity, has higher sensitivity and lower detection limit on the detection of water body COD, has accurate numerical value, and has good environmental protection and economic benefits.
Description
Technical Field
The invention relates to a Ni/ZnO/Cu composite material electrode, a preparation method and application thereof, and a detection method of water chemical oxygen demand, and belongs to the field of electrode materials.
Background
In environmental chemistry, Chemical Oxygen Demand (COD) is an indicator of the amount of oxygen that can be consumed by a reaction in a solution. COD is mainly used for evaluating organic pollution in water and is one of the most important parameters in water monitoring. It has been accepted by many countries as a national standard for organic pollution evaluation. The traditional COD measuring method is to oxidize and degrade organic matters in water by using dichromate, permanganate and other strong oxidants. This method continues until now, but in the course of use, the sample volume to be used is relatively large, and corrosive (concentrated sulfuric acid) and toxic (HgSO) are used 4 And chromium (VI)). In addition, the method has the disadvantages of overlong operation flow, complex operation in the experimental process, poor operability, high requirement on the operation capability of experimenters, and low reproducibility and large errors of test results. Therefore, efforts have been made to overcome these disadvantages and develop a convenient and rapid method for COD analysis and determination.
In recent years, rapid and environment-friendly COD measurement methods have been receiving more and more attention. These new methods include spectroscopy and electrochemical oxidation detection techniques, among others. Although spectroscopy greatly reduces the detection time compared to conventional methods, it is difficult to make a convenient detector because spectroscopy still uses toxic reagents and requires a light source. The electrochemical technology has the characteristics of high sensitivity, high efficiency, low cost, convenient operation and the like, and has great potential in COD measurement.
The electrochemical detection technology of COD is based on electro-catalysis (EC), and the organic matter is quickly oxidized by an electro-catalysis active electrode. Electrodes with higher electrocatalytic activity have so far been mainly composed of transition metals and their oxides (M/MO) or carbon materials, for example: PbO 2 、AgO/CuO、Rh 2 O 3 a/Ti, Cu/CuO, and Boron Doped Diamond (BDD) electrode, and the like. Compared with a carbon doped electrode, the M/MO electrode is relatively simple and has high oxidation capacity. Li and the like research on fluorine-doped nano PbO 2 The electrode sensor is used for measuring COD, experiments prove that the correlation exists between response current and COD, the modified electrode has strong stability and good conductivity, more catalytic active sites are arranged on the surface of the electrode, the kinetic constant of hydroxyl generated by anode decomposition is obviously improved, the anodic oxidation reaction rate of organic matters is improved, the response time of each sample is only dozens of seconds, the linear range is 100-1200 mg/L, and the sensitivity is 2.3 multiplied by 10 -7 mA /(mg L -1 ). The manual Gutierrez-Capitan and the like find that a composite electrode prepared by doping AgO/CuO nano particles in a carbon nano tube-polystyrene composite material has good current response signals for various organic matters, and is further used for measuring COD, the detection limit in the electrode is 28 mg/L, the detection range is 106-1292 mg/L, and the sensitivity is 1.16 multiplied by 10 -6 mA /(mg L -1 )。
Copper-based sensors are more environmentally friendly than lead-based sensors, and are more cost-advantageous than silver-based sensors. In addition, the copper-based material has strong oxidizing ability, can oxidize some refractory organic matters, is considered to be a very promising working electrode material for measuring COD of a water sample, and receives more and more attention in recent years.
At present, the COD electrochemical sensor electrode mainly comprises a copper-based electrode, and Silva et al use the copper bar electrode as a sensor, and find that the electrode has better capability of generating an electrocatalytic active substance CuO (OH) and has wider COD linear range (53)0-2801.4 mg/L), but higher detection limit (20.3 mg/L) and lower sensitivity (4.717X 10) -4 mA /mgL -1 ). If it is desired to increase the sensitivity of the sensor by increasing the specific surface area, it has been found that the specific surface area of the copper or copper oxide nanoparticles prepared on the copper substrate, such as the nano-copper/copper disk, the nano-copper/Glassy Carbon Electrode (GCE) and the nano-copper/copper cable, is increased, and the sensor has higher detection sensitivity, lower detection limit and higher electrocatalytic activity. However, the nano material is easy to agglomerate during preparation, and accurate and uniform loading is difficult to realize.
Disclosure of Invention
The invention is completed based on the discovery that when a nano-scale three-dimensional structure is formed on a substrate firstly, the specific surface area of the substrate is improved, and then nano-copper is electrodeposited on the substrate, the agglomeration phenomenon of nano-materials in the preparation process can be effectively inhibited, and the preparation of a copper-based electrode with high dispersion and large specific surface area is facilitated.
Therefore, the invention aims to provide a Ni/ZnO/Cu composite material electrode with high sensitivity and low detection limit. The sensitivity of the Ni/ZnO/Cu composite material electrode is 2.403 multiplied by 10 -2 mA /(mg L -1 ) The detection limit is 0.6036 mg/L.
It is another object of the present invention to provide a method for preparing the above composite electrode. The method prepares the ZnO nano-column on the nickel plate by a solution method, improves the specific surface area of the electrodeposited Cu by utilizing the three-dimensional structure of the ZnO nano-column, and induces the formation of the self-assembled flower-shaped copper of the nano-belt. Compared with a sensor directly depositing copper on a nickel plate, the sensor has better deposition effect, improves the sensitivity of the sensor and obtains lower detection limit.
It is a further object of the present invention to provide an application of the above-described composite electrode.
The invention also aims to provide a method for detecting the chemical oxygen demand of the water body.
The invention provides a Ni/ZnO/Cu composite material electrode which comprises a nickel sheet serving as a substrate, ZnO nano columns growing on the surface of the nickel sheet and copper electrodeposited on the surfaces of the ZnO nano columns.
Preferably, the ZnO nano column has a length of 3-10 μm and a cross-sectional area of 1-10 μm 2 。
Preferably, the copper nanoflower is loaded on the lateral surface of the nano-column ZnO; the copper nanoflower is composed of copper nanobelts, the width of each copper nanobelt is 20-30 nm, and the length of each copper nanobelt is 3-4 microns.
The invention provides a preparation method of a Ni/ZnO/Cu composite material electrode, which comprises the following steps:
s1, placing the nickel sheet in a container containing a growth solution to form a growth system; the growth solution is a mixture of urotropine and zinc acetate;
s2, heating the growth system in a water bath at 60-90 ℃, and replacing the growth solution once every 1-4 hours;
s3, placing the nickel sheet processed in the step S2 in a mixed solution composed of copper sulfate pentahydrate and hexadecyl trimethyl ammonium bromide, and electrodepositing the nano copper film.
Preferably, in step S1, the concentration ratio of urotropine to zinc acetate in the growth solution is 1 (0.8-1.2).
Preferably, in step S3, the concentration of copper sulfate pentahydrate in the mixed solution is 0.5mol/L, and the concentration of cetyltrimethylammonium bromide is 2 mmol/L.
The invention provides an application of a Ni/ZnO/Cu composite material electrode in water body chemical oxygen demand detection.
The invention also provides a detection method of the water body chemical oxygen demand; the Ni/ZnO/Cu composite material electrode is used as a working electrode, a standard three-electrode system is adopted for detection, a calibration curve between the chemical oxygen demand and the current is constructed, and the chemical oxygen demand of the water body is obtained by detecting the current value of the water body.
Preferably, when a platinum sheet is used as an auxiliary electrode and silver/silver chloride and saturated KCl are used as reference electrodes, the operating voltage range of the test is as follows: 0.5-0.8V.
Preferably, in the above-described embodiment, the organic substance used in constructing the calibration curve between chemical oxygen demand and electric current is one selected from fructose, glycine, glucose, maltose, ascorbic acid and sucrose.
The invention has the following beneficial effects:
1. the Ni/ZnO/Cu composite material electrode prepared by the invention has excellent electrocatalytic activity and higher sensitivity for detecting COD (chemical oxygen demand) of water body, and the sensitivity is 2.403 multiplied by 10 -2 mA /(mg L -1 )。
2. When the sensor is applied to COD detection, under the optimized alkali concentration and scanning rate, the linear range of the sensor is 2.3603-577.8 mg/L, and the detection limit is 0.6036 mg/L; the sensitivity is higher and the detection limit is lower;
3. the data obtained in the real water sample COD detection by the method disclosed by the invention is very consistent with the measurement result of the dichromate method of HJ 828-.
Drawings
FIG. 1 is an XRD pattern of a Ni/ZnO/Cu composite electrode of example one;
FIG. 2 is an SEM image of a Ni/ZnO/Cu composite electrode of one example;
FIG. 3 is SEM images of Ni/ZnO/Cu composite electrodes of example I at different magnification;
FIG. 4 is SEM images of Ni/ZnO/Cu composite electrodes of example one at different magnification.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to these examples.
Example one
A preparation method of a Ni/ZnO/Cu composite material electrode comprises the following steps:
s1, placing the nickel sheet in a growth solution consisting of 50mmol/L urotropine and 50mmol/L zinc acetate;
s2, heating the system in the step S1 in a water bath at 90 ℃, and replacing the growth solution every 3 hours;
s3, placing the nickel sheet obtained in the step S2 in a mixed solution of 0.5mol/L copper sulfate pentahydrate and 2 mmol/L cetyl trimethyl ammonium bromide, and electrodepositing the nano copper film for 100S under the voltage of-0.5V;
and S4, rinsing the nickel sheet obtained in the step S3 for 2 times by using distilled water to remove adsorbed substances, and thus obtaining the Ni/ZnO/Cu composite material electrode.
FIG. 1 is an XRD pattern of the Ni/ZnO/Cu composite electrode in the first example; the structural characteristics of the composite material can be seen from fig. 1, namely, the composite material comprises a nickel sheet as a substrate, ZnO nano-pillars grown on the surface of the nickel sheet, and copper electrodeposited on the surface of the ZnO nano-pillars.
FIGS. 2-4 are SEM images of Ni/ZnO/Cu composite electrodes in the first embodiment; as can be seen from figures 2-4, the morphology characteristics of the composite material under different multiples of an electron microscope are that the length of the ZnO nano-column is 3-10 mu m, and the sectional area is 1-10 mu m 2 (ii) a Copper nanoflowers are loaded on the lateral surfaces of the nano columns ZnO; the copper nanoflower is composed of copper nanobelts, the width of each copper nanobelt is 20-30 nm, and the length of each copper nanobelt is 3-4 microns.
Example two
A preparation method of a Ni/ZnO/Cu composite material electrode comprises the following steps:
s1, placing the nickel sheet in a growth solution consisting of 50mmol/L urotropine and 50mmol/L zinc acetate;
s2, heating the system in the step S1 in a water bath at 90 ℃, and replacing the growth solution every 3 hours;
s3, placing the nickel sheet obtained in the step S3 in a mixed solution of 0.5mol/L copper sulfate pentahydrate and 2 mmol/L cetyl trimethyl ammonium bromide, and electrodepositing the nano copper film for 100S under the voltage of-0.6V;
and S4, rinsing the nickel sheet obtained in the step S3 for 2 times by using distilled water to remove adsorbed substances, and obtaining the Ni/ZnO/Cu composite material electrode.
EXAMPLE III
A preparation method of a Ni/ZnO/Cu composite material electrode comprises the following steps:
s1, placing the nickel sheet in a growth solution consisting of 50mmol/L urotropine and 50mmol/L zinc acetate;
s2, heating the system in the step S1 in a water bath at 90 ℃, and replacing the growth solution every 3 hours;
s3, placing the product obtained in the step S2 in a mixed solution of 0.5mol/L copper sulfate pentahydrate and 2 mmol/L cetyl trimethyl ammonium bromide, and electrodepositing the nano copper film for 80S under the voltage of-0.7V;
and S4, rinsing the product obtained in the step S3 for 2 times by using distilled water to remove adsorbed substances, and obtaining the Ni/ZnO/Cu composite material electrode.
Example four
A preparation method of a Ni/ZnO/Cu composite material electrode comprises the following steps:
s1, placing the nickel sheet in a growth solution consisting of 50mmol/L urotropine and 50mmol/L zinc acetate;
s2, heating the system in the step S1 in a water bath at 90 ℃, and replacing the growth solution every 3 hours;
s3, placing the nickel sheet obtained in the step S2 in a mixed solution of 0.5mol/L copper sulfate pentahydrate and 2 mmol/L cetyl trimethyl ammonium bromide, and electrodepositing the nano copper film for 90S under the voltage of-0.7V;
and S4, rinsing the nickel sheet obtained in the step (3) with distilled water for 2 times to remove adsorbed substances, and thus obtaining the Ni/ZnO/Cu composite material electrode.
Application example 1
The Ni/ZnO/Cu composite material electrode is used as a working electrode, a platinum sheet is used as an auxiliary electrode, silver/silver chloride and saturated KCl are used as reference electrodes, and the working voltage is 0.7V during testing. A calibration curve between chemical oxygen demand and current was constructed using glucose, and a linear relationship was obtained as I (mA) = 0.02403[ COD)](mg/L) +0.39021, R2= 0.99516. A45 ml sample of real water and 180 mg of sodium hydroxide were mixed in a beaker and homogenized with a magnetic stirrer to homogenize the electrolyte. Obtaining a current I-t curve through an electrochemical workstation, and comparing the current I-t curve with a reference current I-t curve obtained by using a pure sodium hydroxide solution to obtain I 1 =0.786705 mA，I 2 The chemical oxygen demand of real water samples obtained by the method of (= 0.94651 mA) is 16.5 mg/L and 23.15 mg/L respectively.
The results are compared with the chemical oxygen demand values obtained by the HJ 828-.
Table 1 shows the chemical oxygen demand values of the two samples measured by the two methods, and it can be seen from Table 1 that the relative difference between the two methods is in the range of-6.67% to-5.89%. The good consistency of the two methods shows that the Ni/ZnO/Cu composite material electrode has great practical application potential in water body COD measurement.
Claims (6)
1. A Ni/ZnO/Cu composite material electrode is characterized in that: the composite material electrode comprises a nickel sheet as a substrate, ZnO nano columns growing on the surface of the nickel sheet and copper electrodeposited on the surfaces of the ZnO nano columns;
the ZnO nano column has a length of 3-10 μm and a cross-sectional area of 1-10 μm 2 (ii) a Copper nanoflowers are loaded on the lateral surfaces of the nano columns ZnO; the copper nanoflower is composed of copper nanobelts, the width of each copper nanobelt is 20-30 nm, and the length of each copper nanobelt is 3-4 microns;
the preparation method of the composite material electrode comprises the following steps:
s1, placing the nickel sheet in a container containing a growth solution to form a growth system; the growth solution is a mixture of urotropine and zinc acetate;
s2, heating the growth system in a water bath at 60-90 ℃, and replacing the growth solution once every 1-4 hours;
s3, placing the nickel sheet processed in the step S2 in a mixed solution composed of copper sulfate pentahydrate and hexadecyl trimethyl ammonium bromide, and electrodepositing the nano copper film.
2. The Ni/ZnO/Cu composite electrode of claim 1, wherein: in step S1, the concentration ratio of urotropine to zinc acetate in the growth solution is 1 (0.8-1.2).
3. The Ni/ZnO/Cu composite electrode of claim 1, wherein: in step S3, the concentration of copper sulfate pentahydrate in the mixed solution is 0.5mol/L, and the concentration of cetyl trimethyl ammonium bromide is 2 mmol/L.
4. The method for detecting the chemical oxygen demand of the water body is characterized by comprising the following steps: the Ni/ZnO/Cu composite material electrode of any one of claims 1-3 is used as a working electrode, a standard three-electrode system is adopted for detection, a calibration curve between chemical oxygen demand and current is constructed, and the chemical oxygen demand of the water body is obtained by detecting the current value of the water body.
5. The method for detecting the chemical oxygen demand of the water body according to claim 4, wherein: when a platinum sheet is used as an auxiliary electrode and silver/silver chloride and saturated KCl are used as reference electrodes, the operating voltage range of the test is: 0.5-0.8V.
6. The method for detecting the chemical oxygen demand of the water body according to claim 4, wherein: when a calibration curve between chemical oxygen demand and current is constructed, the organic substance used is one selected from fructose, glycine, glucose, maltose, ascorbic acid or sucrose.
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