CN110514700B - Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method - Google Patents
Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method Download PDFInfo
- Publication number
- CN110514700B CN110514700B CN201910926480.7A CN201910926480A CN110514700B CN 110514700 B CN110514700 B CN 110514700B CN 201910926480 A CN201910926480 A CN 201910926480A CN 110514700 B CN110514700 B CN 110514700B
- Authority
- CN
- China
- Prior art keywords
- cuo
- sensitive material
- nanowire
- heterostructure
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method thereof, and CuO/Co sensor3O4The heterostructure nanowire is in a core-shell structure, wherein CuO is used as a core, and Co is wrapped by an outer layer of the heterostructure nanowire3O4The nanosheets serve as the shell. In the preparation process of the sensitive material, the preparation method adopts the nanowire precursor synthesized by the hydrothermal method through high-temperature annealing treatment in the air atmosphere to prepare CuO/Co3O4A nanowire. The whole synthesis process is simple and efficient, and is suitable for large-scale production. The multi-stage core-shell structure provides more active sites for gas reaction. And the existence of the p-p type heterojunction further promotes the response of the composite material to ethylene glycol. The gas sensor has excellent sensitivity, ultra-fast response speed, excellent selectivity, reliable long-term stability and lower theoretical detection limit, and is suitable for detecting glycol gas with high sensitivity.
Description
Technical Field
The invention relates to the field of gas sensors, in particular to a copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, an ethylene glycol sensor and a preparation method, and aims to realize rapid, sensitive and repeatable detection of ethylene glycol gas.
Background
In industrial production, ethylene glycol is used as an important raw material and widely applied to organic solvents, anti-freezing agents and synthetic terylene. However, ethylene glycol contains hydroxyl groups, and when it is operated at 80 ℃ to 90 ℃ for a long period of time, ethylene glycol is oxidized first to glycolic acid and then to oxalic acid. Oxalic acid and its byproducts can affect the central nervous system of the human body first, resulting in dyspnea, pulmonary edema and the like, and if the treatment is not carried out in a proper way, excessive glycol intake can result in death. Therefore, the manufacture of high-performance ethylene glycol gas sensors is of great and urgent importance for environmental monitoring and human health protection.
Among various gas sensors, the semiconductor metal oxide-based resistance type gas sensor has the advantages of low preparation cost, low detection lower limit, high response and recovery speed and the like, and is a favorable candidate device for realizing the real-time detection of the ethylene glycol gas.
Among them, CuO and Co3O4As a typical p-type oxide semiconductor sensitive material, the material has high catalytic activity, can work at a lower temperature, and has attracted great attention in the field of toxic gas monitoring. However, many are based on simple CuO and Co3O4The sensitivity of the gas sensor is low and the selectivity is not good. Therefore, it is necessary to mix CuO and Co3O4And a heterojunction is constructed by compounding, and the sensing performance of the composite material is further improved by the synergistic effect of the two components.
Disclosure of Invention
The invention aims to provide a copper oxide and cobaltosic oxide heterogeneous medium aiming at the problems of low sensitivity and poor selectivity of the gas sensor in the prior artStructural nanowire composite sensitive material, ethylene glycol sensor and preparation method, and core-shell structure CuO/Co obtained by using structural nanowire composite sensitive material3O4The nano wire has a multi-stage structure, so that the sensitive material has a larger specific surface area, more adsorption sites are provided for gas molecules, and the prepared gas sensor is beneficial to realizing high-sensitivity and rapid detection of the glycol gas.
In order to achieve the purpose, the invention has the following technical scheme:
CuO/Co3O4Heterostructure nanowire composite sensitive material with CuO/Co3O4The heterostructure nanowire is in a core-shell structure, wherein CuO is used as a core, and Co is wrapped by an outer layer of the heterostructure nanowire3O4Nanosheet as shell, single nanowire with length greater than 10 μm and diameter of 600-800 nm, and Co3O4The thickness of the nano-sheet is less than 6 nm.
CuO/Co of the invention3O4The preparation method of the heterostructure nanowire composite sensitive material comprises the following steps:
(1) preparation of CuO/Co3O4A nanowire precursor;
firstly, mixing ethanol and deionized water, adding Cu nanowires into the solution, performing ultrasonic treatment to uniformly disperse the Cu nanowires, respectively adding cobalt nitrate hexahydrate, ammonium fluoride and urea into the solution, and continuously stirring uniformly to obtain a mixed solution;
secondly, carrying out hydrothermal reaction on the solution obtained in the step one at the temperature of 80-100 ℃ for 6-8 h, naturally cooling to room temperature, centrifugally cleaning the obtained brownish black precipitate, and drying to obtain CuO/Co3O4A nanowire precursor;
(2) preparation of CuO/Co3O4A nanowire composite sensitive material;
the prepared CuO/Co3O4Annealing the nanowire precursor to obtain CuO/Co3O4A nanowire.
Preferably, in an embodiment of the preparation method of the present invention, in the step (1), the volume ratio of ethanol to deionized water is 1: 1; the diameter of the Cu nanowire is less than 250nm, and the length of the Cu nanowire is greater than 10 μm.
Preferably, in an embodiment of the preparation method of the present invention, the concentration of the cobalt nitrate hexahydrate in the mixed solution after adding the ammonium fluoride is 0.005M to 0.02M, the concentration of the ammonium fluoride in the mixed solution after adding the ammonium fluoride is 0.0025M to 0.02M, and the concentration of the urea in the mixed solution after adding the urea is 0.0125M to 0.05M.
Preferably, in one embodiment of the preparation method of the present invention, the solvent for centrifugal cleaning is selected from one of deionized water, ethanol, or a mixed solvent of deionized water and ethanol; the centrifugation speed is 5000-8000 rpm, the centrifugation time is 5-10 min, the drying temperature is 50-80 ℃, and the drying time is 5-12 h.
Preferably, in an embodiment of the preparation method of the present invention, the annealing treatment is performed in a muffle furnace, the calcination temperature is 350 ℃ to 550 ℃, the calcination time is 2h to 3h, and the temperature rise rate is 2 ℃/min to 10 ℃/min.
The invention also provides an ethylene glycol sensor which comprises Al with two annular gold electrodes separated from each other on the outer surface2O3Ceramic tube, Al2O3The ceramic tube is internally provided with a nickel-cadmium alloy coil, a ring-shaped gold electrode and Al2O3The copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material is uniformly coated on the outer surface of the ceramic tube.
The invention also provides a preparation method of the ethylene glycol sensor, which comprises the following steps:
combining CuO/Co3O4Mixing heterostructure nanowire composite sensitive material powder and absolute ethyl alcohol according to the mass ratio of 1:10, uniformly dispersing the heterostructure nanowire composite sensitive material powder and the absolute ethyl alcohol, and then taking the dispersed liquid to drop on Al with two mutually-separated annular gold electrodes on the outer surface2O3Until the ethanol is evaporated, a sensitive material film which completely covers the annular gold electrode is formed on the surface of the ceramic tube;
② passing the nickel-cadmium alloy coil through Al2O3The interior of the ceramic tube is used as a heating wire; finally, the above-mentioned devices are combinedAnd welding and packaging according to the universal indirectly heated gas sensitive element to obtain the ethylene glycol sensor.
Preferably, in the method for preparing the ethylene glycol sensor, in the step (i), CuO/Co is used3O4The heterostructure nanowire composite sensitive material powder and absolute ethyl alcohol are dispersed uniformly through ultrasonic vibration, 6-10 mu L of the dispersion liquid drop is taken by a liquid transfer gun, and Al with two mutually discrete annular gold electrodes is self-contained on the outer surface2O3Surface of ceramic tube, Al2O3The ceramic tube horizontally rotates at a constant speed until the ethanol is evaporated to form a sensitive material film which completely covers the annular gold electrode.
Compared with the prior art, the composite sensitive material has the following beneficial effects: having CuO/Co of3O4The heterostructure nanowire is of a core-shell structure, the specific surface area of the sensitive material can be effectively improved, and Co wrapped by the outer layer3O4The thickness of the nano-sheet is less than 6nm, so that the active sites of the sensitive material reacting with the gas to be detected are increased to a great extent.
Compared with the prior art, the preparation method of the composite sensitive material has the following beneficial effects: the core-shell structure nanowire sensitive material is prepared by combining a hydrothermal method and high-temperature annealing treatment, and the synthesis method is simple. CuO, Co3O4The two typical P-type materials have the advantages of high catalytic activity and low gas detection temperature. The p-p heterojunction is constructed by combining the two p-type semiconductors, so that the sensitivity of the sensitive material to the glycol is greatly improved due to the synergistic effect of the two materials, the response speed is high, the stable test characteristic is realized, and the method has a wide application prospect in the aspect of detecting the content of the glycol in the environment.
Compared with the prior art, the ethylene glycol sensor provided by the invention selects commercially available Al2O3The ceramic tube type electrode has simple device process and small volume, and is suitable for mass production. The gas sensor has excellent sensitivity, ultra-fast response speed, excellent selectivity, reliable long-term stability and low theoretical detection limit, and is suitable for high content of ethylene glycol gasAnd (5) detecting the sensitivity.
Drawings
FIG. 1a is a schematic representation of example 2 in which CuO/Co is used3O4Scanning electron micrographs of nanowires;
FIGS. 1b and 1c are the CuO/Co values of example 23O4Transmission electron microscopy of nanowires;
FIG. 2 is a schematic representation of the CuO/Co ratio of example 23O4An X-ray diffraction pattern of the nanowire heterostructure composite;
FIG. 3 is a schematic structural diagram of an indirectly heated glycol sensor;
FIG. 4 is a graph of the response of the sensor to 100ppm ethylene glycol at different operating temperatures based on example 1, example 2 and example 3;
FIG. 5 is a graph showing the recovery of the response of the sensor according to example 2 to different concentrations of ethylene glycol at 130 ℃;
FIG. 6 is a graph of gas selectivity performance for ethanol, formaldehyde, methanol, ammonia, acetone, n-propanol, ethylene glycol at 130 deg.C and 100ppm concentration based on the sensor of example 2;
FIG. 7 is a graph showing the long-term stability of the sensor based on example 2 for detecting 100ppm concentration of ethylene glycol gas at an operating temperature of 130 ℃.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and specific embodiments. These descriptions are provided only to help explain the present invention and are not intended to limit the scope of the claims of the present invention.
The invention provides a CuO/Co3O4Heterostructure nanowires, CuO/Co3O4The heterostructure nanowire is in a core-shell structure, wherein CuO is a 'core', and Co wrapped by an outer layer3O4The nanosheets are "shells". CuO/Co3O4The heterostructure nanowires have a length greater than 10 μm and a diameter of about 600nm, Co3O4The thickness of the nano-sheet is less than 6 nm. The method comprises the steps of firstly synthesizing the Cu nanowire, and then coating Co on the surface of the Cu nanowire by a hydrothermal method3O4Nanosheet, to obtainTo CuO/Co3O4A nanowire precursor; then annealing at high temperature in air atmosphere to make the above-mentioned CuO/Co3O4Oxidizing the nanowire precursor to finally obtain CuO/Co3O4A nanowire.
The invention is based on CuO/Co3O4Glycol sensor of heterostructure nanowire made of Al with external surface provided with two annular gold electrodes separated from each other2O3Ceramic tube, uniformly coated on annular gold electrode and Al2O3Sensitive material film on outer surface of ceramic tube, Al2O3The nickel-cadmium alloy coil in the ceramic tube is prepared by the following steps:
(1)CuO/Co3O4preparing a nanowire precursor:
mixing 20mL of ethanol with 20mL of deionized water, adding 20mg of Cu nanowires into the solution, and performing ultrasonic treatment to uniformly disperse the Cu nanowires. Then, 0.4mmol of cobalt nitrate hexahydrate, 0.2mmol to 0.4mmol of ammonium fluoride and 1mmol of urea were added to the above solution, respectively. Stirring for 20min to mix the above solutions.
② reacting the reaction solution for 8h at 90 ℃.
After the reaction is finished, centrifugally cleaning the gray-black precipitate by using one of deionized water and ethanol or a mixed solution of the deionized water and the ethanol, and then drying the gray-black precipitate in an oven for 5 to 12 hours at the drying temperature of 50 to 80 ℃ to obtain CuO/Co3O4And (3) a nanowire precursor.
(2)CuO/Co3O4Preparing a nanowire composite sensitive material:
mixing CuO/Co3O4And placing the nanowire precursor in a muffle furnace for annealing treatment. The annealing temperature is 350-550 ℃, the annealing time is 2-3 h, and the heating rate is 2-10 ℃/min. Then naturally cooling to room temperature to obtain CuO/Co3O4A nanowire.
(3) Manufacturing the ethylene glycol gas sensor:
combining CuO/Co3O4Mixing the nano-wire composite powder with absolute ethyl alcohol according to the mass ratio of 1:10, and performing ultra-high treatmentDispersing uniformly by sound, then taking 6-10 mu L of the dispersed liquid drops by a liquid-transfering gun, and self-arranging Al with two annular gold electrodes on the outer surface of the commercially available Al2O3And (3) horizontally rotating the ceramic tube at a constant speed on the surface of the ceramic tube until the ethanol is evaporated to form a sensitive material film which completely covers the annular gold electrode.
② passing the nickel-cadmium alloy coil through Al2O3The ceramic tube is internally used as a heating wire, and finally the device is welded and packaged according to a general indirectly heated gas sensitive element, so that CuO/Co is obtained3O4Nanowire composite ethylene glycol sensors.
Example 1:
CuO/Co3O4the preparation method of the heterostructure nanowire comprises the following steps:
(1) and mixing 20mL of ethanol with 20mL of deionized water, adding 20mg of Cu nanowires into the solution, and performing ultrasonic treatment to uniformly disperse the Cu nanowires. Then, 0.4mmol of cobalt nitrate hexahydrate, 0.2mmol of ammonium fluoride and 1mmol of urea were added to the above solution, respectively. Stirring for 20min to mix the above solutions. The reaction solution was reacted at 90 ℃ for 8h while maintaining magnetic stirring. After the reaction is finished, the obtained gray-black precipitate is alternately centrifugally cleaned for 6 times by deionized water and ethanol, and dried for 12 hours at the temperature of 60 ℃ to obtain CuO/Co3O4And (3) a nanowire precursor.
(2) The sample was annealed in a muffle furnace. The annealing conditions are as follows: raising the temperature from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and then naturally cooling to room temperature to obtain CuO/Co3O4A heterostructure nanowire.
Example 2:
CuO/Co3O4the preparation method of the heterostructure nanowire comprises the following steps:
(1) and mixing 20mL of ethanol with 20mL of deionized water, adding 20mg of Cu nanowires into the solution, and performing ultrasonic treatment to uniformly disperse the Cu nanowires. Then, 0.4mmol of cobalt nitrate hexahydrate, 0.3mmol of ammonium fluoride and 1mmol of urea were added to the above solution, respectively. Stirring for 20min to mix the above solutions. Will be reversedThe solution was allowed to react at 90 ℃ for 8h while maintaining magnetic stirring. After the reaction is finished, the obtained gray-black precipitate is alternately centrifugally cleaned by deionized water and ethanol, and is dried for 12 hours at the temperature of 60 ℃ to obtain CuO/Co3O4And (3) a nanowire precursor.
(2) The sample was annealed in a muffle furnace. The annealing conditions are as follows: raising the temperature from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and then naturally cooling to room temperature to obtain CuO/Co3O4A heterostructure nanowire.
Example 3:
CuO/Co3O4the preparation method of the heterostructure nanowire comprises the following steps:
(1) and mixing 20mL of ethanol with 20mL of deionized water, adding 20mg of Cu nanowires into the solution, and performing ultrasonic treatment to uniformly disperse the Cu nanowires. Then, 0.4mmol of cobalt nitrate hexahydrate, 0.4mmol of ammonium fluoride and 1mmol of urea were added to the above solution, respectively. Stirring for 20min to mix the above solutions. The reaction solution was reacted at 90 ℃ for 8h while maintaining magnetic stirring. After the reaction is finished, the obtained gray-black precipitate is alternately centrifugally cleaned by deionized water and ethanol, and is dried for 12 hours at the temperature of 60 ℃ to obtain CuO/Co3O4And (3) a nanowire precursor.
(2) The sample was annealed in a muffle furnace. The annealing conditions are as follows: raising the temperature from room temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, and then naturally cooling to room temperature to obtain CuO/Co3O4A heterostructure nanowire.
Example 4:
the specific method for preparing the ethylene glycol gas sensor comprises the following steps:
(1) the nano materials obtained in examples 1-3 were mixed with absolute ethyl alcohol at a mass ratio of 1:10, and dispersed uniformly by ultrasonic, and then 6. mu.L of the dispersed solution was applied to a commercially available Al alloy with two gold ring electrodes on the outer surface by using a pipette2O3And (3) horizontally rotating the ceramic tube at a constant speed on the surface of the ceramic tube until the ethanol is evaporated to form a sensitive material film which completely covers the annular gold electrode.
(2) Passing a nickel-cadmium alloy coil through Al2O3And (3) taking the inside of the ceramic tube as a heating wire, and finally welding and packaging the device according to the universal indirectly heated gas sensitive element to obtain the ethylene glycol sensor.
From FIG. 1a, it can be seen that CuO/Co3O4The nanowires are longer than 10 μm, and CuO/Co can be seen in FIG. 1b3O4The diameter of the nanowires is about 600nm, and the composition CuO/Co can be seen in FIG. 1c3O4Co of nanowires3O4The thickness of the nano-sheet is less than 6 μm.
As shown in FIG. 2, all diffraction peaks in the X-ray diffraction pattern can correspond to CuO and Co3O4The standard peak of (A) proves the CuO/Co prepared after annealing treatment3O4The nanowires have good crystallinity.
As shown in FIG. 3, the glycol sensor prepared by the invention is made of Al2O3The device comprises a ceramic tube, an annular gold electrode, a platinum wire welded on the annular gold electrode, a semiconductor sensitive material, a nickel-cadmium alloy coil and a wiring terminal base.
As shown in FIG. 4, the optimum working temperature was 110 ℃ for example 1, 130 ℃ for example 2, and 120 ℃ for example 3. The sensitivity of the gas sensor is defined as its resistance R in ethylene glycol vaporgWith resistance in air RaExample 1, example 2 and example 3 have sensitivities to 100ppm ethylene glycol at the optimum temperature of 2.81, 6.27 and 2.53, respectively. Starting from the high sensitivity, example 2 was chosen as the optimal sample.
As shown in fig. 5, when the sensor in example 2 was operated at the optimum operating temperature (130 ℃), the devices had excellent response-recovery performance in the concentration range of 5-200ppm, and the sensitivity increased with the increase in the concentration of ethylene glycol.
As shown in FIG. 6, when the sensor in example 2 is operated at the optimum operating temperature (130 ℃), its response sensitivity to ethylene glycol is much higher than that to other gases, indicating that the core-shell structure CuO/Co of example 2 of the present invention3O4The glycol gas sensor prepared by the nano-wire has excellent gas selectivity to glycol gas.
As shown in FIG. 7, example 2 is a core-shell structure of CuO/Co3O4The glycol gas sensor prepared by the nano wire still has a response value of more than 6 to glycol at the concentration of 100ppm at the working temperature of 130 ℃ within 30 days, which shows that the core-shell structure CuO/Co in the embodiment 2 of the invention3O4The gas sensor prepared by the nano wire has good long-term stability for detecting glycol gas, can be suitable for monitoring glycol in actual environment, and has wide application prospect.
Claims (7)
1. The preparation method of the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material is characterized in that the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material has CuO/Co3O4Heterostructure nanowires, said CuO/Co3O4The heterostructure nanowire is in a core-shell structure, wherein CuO is used as a core, and Co is wrapped by an outer layer of the heterostructure nanowire3O4Nanosheet as shell, single nanowire with length greater than 10 μm and diameter of 600-800 nm, and Co3O4The thickness of the nano sheet is less than 6 nm; the method comprises the following steps:
(1) preparation of CuO/Co3O4A nanowire precursor;
firstly, mixing ethanol and deionized water, adding Cu nanowires into the solution, performing ultrasonic treatment to uniformly disperse the Cu nanowires, respectively adding cobalt nitrate hexahydrate, ammonium fluoride and urea into the solution, and continuously stirring uniformly to obtain a mixed solution; the volume ratio of the ethanol to the deionized water is 1: 1; the diameter of the Cu nanowire is less than 250nm, and the length of the Cu nanowire is more than 10 mu m;
secondly, carrying out hydrothermal reaction on the solution obtained in the step one at the temperature of 80-100 ℃ for 6-8 h, naturally cooling to room temperature, centrifugally cleaning the obtained brownish black precipitate, and drying to obtain CuO/Co3O4A nanowire precursor;
(2) preparation of CuO/Co3O4A nanowire composite sensitive material;
the prepared CuO/Co3O4Annealing the nanowire precursor to obtain CuO/Co3O4A nanowire.
2. The method for preparing the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material according to claim 1, is characterized in that: the concentration of the added cobalt nitrate hexahydrate in the mixed solution is 0.005-0.02M, the concentration of the added ammonium fluoride in the mixed solution is 0.0025-0.02M, and the concentration of the added urea in the mixed solution is 0.0125-0.05M.
3. The method for preparing the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material according to claim 1, is characterized in that: the solvent for centrifugal cleaning is one of deionized water and ethanol or a mixed solvent of the deionized water and the ethanol; the centrifugation speed is 5000-8000 rpm, the centrifugation time is 5-10 min, the drying temperature is 50-80 ℃, and the drying time is 5-12 h.
4. The method for preparing the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material according to claim 1, is characterized in that: the annealing treatment is carried out in a muffle furnace, the calcining temperature is 350-550 ℃, the calcining time is 2-3 h, and the heating rate is 2-10 ℃/min.
5. An ethylene glycol sensor, characterized by: comprising Al with an outer surface provided with two mutually discrete annular gold electrodes2O3Ceramic tube, Al2O3The ceramic tube is internally provided with a nickel-cadmium alloy coil, a ring-shaped gold electrode and Al2O3The outer surface of the ceramic tube is uniformly coated with copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive materials; the copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material is prepared by any of claims 1 to 4The copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material is prepared by the preparation method.
6. A method for manufacturing the glycol sensor according to claim 5, comprising the steps of:
combining CuO/Co3O4Mixing heterostructure nanowire composite sensitive material powder and absolute ethyl alcohol according to the mass ratio of 1:10, uniformly dispersing the heterostructure nanowire composite sensitive material powder and the absolute ethyl alcohol, and then taking the dispersed liquid to drop on Al with two mutually-separated annular gold electrodes on the outer surface2O3Until the ethanol is evaporated, a sensitive material film which completely covers the annular gold electrode is formed on the surface of the ceramic tube;
② passing the nickel-cadmium alloy coil through Al2O3The interior of the ceramic tube is used as a heating wire; and finally, welding and packaging the device according to the universal indirectly heated gas sensitive element to obtain the ethylene glycol sensor.
7. The method of claim 6, wherein: in the step (i), CuO/Co is added3O4The heterostructure nanowire composite sensitive material powder and absolute ethyl alcohol are dispersed uniformly through ultrasonic vibration, 6-10 mu L of the dispersion liquid drop is taken by a liquid transfer gun, and Al with two mutually discrete annular gold electrodes is self-contained on the outer surface2O3Surface of ceramic tube, Al2O3The ceramic tube horizontally rotates at a constant speed until the ethanol is evaporated to form a sensitive material film which completely covers the annular gold electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910926480.7A CN110514700B (en) | 2019-09-27 | 2019-09-27 | Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910926480.7A CN110514700B (en) | 2019-09-27 | 2019-09-27 | Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110514700A CN110514700A (en) | 2019-11-29 |
| CN110514700B true CN110514700B (en) | 2021-09-07 |
Family
ID=68633923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910926480.7A Active CN110514700B (en) | 2019-09-27 | 2019-09-27 | Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110514700B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113358710B (en) * | 2021-06-03 | 2022-06-28 | 吉林大学 | Olivine structure gas sensitive material for detecting formaldehyde and preparation method thereof |
| CN113387397B (en) * | 2021-06-15 | 2022-05-20 | 河北工业大学 | Based on O2Two-dimensional Co plasma treated3O4Preparation method of nanosheet material and ethanol gas sensor |
| CN113948690B (en) * | 2021-10-12 | 2023-07-18 | 西安交通大学 | Hollow ball-type CuO/Co 3 O 4 Composite material and preparation method and application thereof |
| CN113960122A (en) * | 2021-10-29 | 2022-01-21 | 上海理工大学 | Three-dimensional SnO2/Co3O4Core-shell nano composite material and humidity-resistant acetone gas-sensitive element prepared from same |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948139A (en) * | 2010-09-21 | 2011-01-19 | 上海大学 | Method for preparing novel mesoporous silica nano balls |
| KR101161525B1 (en) * | 2010-11-30 | 2012-07-02 | 고려대학교 산학협력단 | N-type oxide semiconductor nanowire gas sensors coated with discrete nano-islands of p-type oxide semiconductors and fabrication method thereof |
| CN102730622A (en) * | 2011-04-01 | 2012-10-17 | 中国科学院电子学研究所 | Integrated chip of micro thermal conductive detector and manufacturing method for same |
| WO2013028691A1 (en) * | 2011-08-25 | 2013-02-28 | Georgia Tech Research Corporation | Gas sensors and methods of preparation thereof |
| CN105084426A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | In-situ grown three-dimensional multi-structural cobaltosic oxide/carbon composite micro-nanomaterial and controllable preparation method thereof |
| CN105158297A (en) * | 2015-09-24 | 2015-12-16 | 雷鸣 | MEMS metal-oxide semiconductor gas sensor and manufacturing method thereof |
| CN106093135A (en) * | 2016-06-02 | 2016-11-09 | 中国石油大学(华东) | A kind of Power Transformer Faults intelligent diagnostics device based on Graphene gas sensor array |
| CN106124573A (en) * | 2016-06-20 | 2016-11-16 | 吉林大学 | A kind of acetone gas sensor based on NiO/ZnO heterojunction structure hollow ball sensitive material and preparation method thereof |
| CN106145179A (en) * | 2015-04-08 | 2016-11-23 | 天津大学 | The cupric oxide nano-rod of a kind of supported cobaltosic oxide and synthetic method thereof |
| WO2017022992A1 (en) * | 2015-07-31 | 2017-02-09 | 한양대학교 에리카산학협력단 | Multi-layer ceramic/metal gas sensor and manufacturing method therefor |
| CN106504902A (en) * | 2016-09-21 | 2017-03-15 | 浙江大学 | A kind of CuO@MnO2Core shell structure porous nano wire material and preparation method thereof |
| CN107817279A (en) * | 2017-09-28 | 2018-03-20 | 东北大学 | A kind of NO based on electrode surface growth in situ NiO nano thin-films2Sensor |
| CN108538926A (en) * | 2017-12-29 | 2018-09-14 | 西安电子科技大学 | InGaAs bases MOS capacitor in flexible substrate and production method |
| CN108682868A (en) * | 2018-03-21 | 2018-10-19 | 上海理工大学 | A kind of preparation method and application of carbon nanotube loaded transition metal oxide material |
| CN108993491A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | The activation persulfate catalyst and preparation that are prepared with modified carbon nano-tube and application |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10208384B2 (en) * | 2011-08-11 | 2019-02-19 | Toyota Motor Engineering & Manufacturing North America, Inc. | Efficient water oxidation catalysts and methods of oxygen and hydrogen production by photoelectrolysis |
| CN104925846A (en) * | 2014-03-17 | 2015-09-23 | 北京化工大学 | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery |
| CN107855539A (en) * | 2017-11-16 | 2018-03-30 | 武汉工程大学 | A kind of method for preparing superfine metal and metal oxide |
| CN108671939A (en) * | 2018-05-03 | 2018-10-19 | 北京化工大学 | A kind of flower-shaped cobaltosic oxide nano micro-ball load bimetallic catalyst and its method for preparing DMF reactions for HMF hydrogenolysis |
| CN108671923B (en) * | 2018-05-10 | 2021-06-29 | 宁波大学 | Copper oxide/cobalt oxide core-shell structure catalyst for water electrolysis and preparation method thereof |
| CN109663595A (en) * | 2018-12-11 | 2019-04-23 | 中科廊坊过程工程研究院 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
-
2019
- 2019-09-27 CN CN201910926480.7A patent/CN110514700B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948139A (en) * | 2010-09-21 | 2011-01-19 | 上海大学 | Method for preparing novel mesoporous silica nano balls |
| KR101161525B1 (en) * | 2010-11-30 | 2012-07-02 | 고려대학교 산학협력단 | N-type oxide semiconductor nanowire gas sensors coated with discrete nano-islands of p-type oxide semiconductors and fabrication method thereof |
| CN102730622A (en) * | 2011-04-01 | 2012-10-17 | 中国科学院电子学研究所 | Integrated chip of micro thermal conductive detector and manufacturing method for same |
| WO2013028691A1 (en) * | 2011-08-25 | 2013-02-28 | Georgia Tech Research Corporation | Gas sensors and methods of preparation thereof |
| CN105084426A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | In-situ grown three-dimensional multi-structural cobaltosic oxide/carbon composite micro-nanomaterial and controllable preparation method thereof |
| CN106145179A (en) * | 2015-04-08 | 2016-11-23 | 天津大学 | The cupric oxide nano-rod of a kind of supported cobaltosic oxide and synthetic method thereof |
| CN107235504A (en) * | 2015-04-08 | 2017-10-10 | 天津大学 | The synthetic method of the cupric oxide nano-rod of supported cobaltosic oxide |
| WO2017022992A1 (en) * | 2015-07-31 | 2017-02-09 | 한양대학교 에리카산학협력단 | Multi-layer ceramic/metal gas sensor and manufacturing method therefor |
| CN105158297A (en) * | 2015-09-24 | 2015-12-16 | 雷鸣 | MEMS metal-oxide semiconductor gas sensor and manufacturing method thereof |
| CN106093135A (en) * | 2016-06-02 | 2016-11-09 | 中国石油大学(华东) | A kind of Power Transformer Faults intelligent diagnostics device based on Graphene gas sensor array |
| CN106124573A (en) * | 2016-06-20 | 2016-11-16 | 吉林大学 | A kind of acetone gas sensor based on NiO/ZnO heterojunction structure hollow ball sensitive material and preparation method thereof |
| CN106504902A (en) * | 2016-09-21 | 2017-03-15 | 浙江大学 | A kind of CuO@MnO2Core shell structure porous nano wire material and preparation method thereof |
| CN107817279A (en) * | 2017-09-28 | 2018-03-20 | 东北大学 | A kind of NO based on electrode surface growth in situ NiO nano thin-films2Sensor |
| CN108538926A (en) * | 2017-12-29 | 2018-09-14 | 西安电子科技大学 | InGaAs bases MOS capacitor in flexible substrate and production method |
| CN108682868A (en) * | 2018-03-21 | 2018-10-19 | 上海理工大学 | A kind of preparation method and application of carbon nanotube loaded transition metal oxide material |
| CN108993491A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | The activation persulfate catalyst and preparation that are prepared with modified carbon nano-tube and application |
Non-Patent Citations (4)
| Title |
|---|
| Binary CuO/Co3O4 nanofibers for ultrafast and amplified electrochemical sensing of fructose;Yang Wang 等;《Electrochimica Acta》;20110909;第56卷(第27期);第10191-10196页 * |
| Co3O4基纳米复合材料的可控制备及NOx气敏性能研究;刘思宇;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20180915;第B020-23页 * |
| Remarkable improvement of gas-sensing abilities in p-type oxide nanowires by local modification of the hole-accumulation layer;Sun-Woo Chio 等;《ACS Applied Materials & Interfaces》;20141216;第7卷(第1期);第647-652页 * |
| 金属氧化物异质结气体传感器气敏增强机理;唐伟 等;《物理化学学报》;20160222;第32卷(第5期);第1087-1104页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110514700A (en) | 2019-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110514700B (en) | Copper oxide and cobaltosic oxide heterostructure nanowire composite sensitive material, ethylene glycol sensor and preparation method | |
| Bai et al. | Novel α-Fe2O3/BiVO4 heterojunctions for enhancing NO2 sensing properties | |
| CN109001263B (en) | Method for synthesizing ZnO-loaded ferric oxide nano heterostructure gas sensitive element based on MOF template | |
| CN108254416A (en) | Meso-hole structure In is supported based on Au2O3The NO of nano sensitive material2Sensor, preparation method and applications | |
| CN102539487A (en) | Air-sensitive material compounded by titanium dioxide nanometer lines and stannic oxide nanometer particles and preparation method thereof | |
| CN110455891B (en) | Based on CoWO4-Co3O4Dimethyl benzene gas sensor of heterojunction nano structure sensitive material and preparation method thereof | |
| CN110243881B (en) | Based on rGO-SnO2NO of nanocomposite2Gas sensor and preparation method thereof | |
| CN102012386A (en) | Preparation method of nitric oxide gas sensor element based on pseudodirected tungsten trioxide nano tape | |
| CN105675664A (en) | Acetone sensor on basis of compounds with rGO/alpha-Fe2O3 heterogeneous structures and method for preparing acetone sensor | |
| CN111830089A (en) | Based on two shell shape Cu2N-propanol gas sensor of O-grade structure micron sphere sensitive material and preparation method thereof | |
| CN109626425B (en) | Nano linear Na1.1V3O7.9Material, method for the production thereof and use thereof | |
| CN105424759A (en) | Preparation method of zinc oxide nanotube array gas sensitive sensor | |
| CN110530937B (en) | Preparation method of glycol sensor based on CuO-NiO nanotube heterostructure | |
| CN110596196A (en) | Semiconductor heterojunction gas sensitive material and preparation method and application thereof | |
| CN112362701B (en) | N-amyl alcohol sensor of Au-loaded ZnO nano composite material synthesized based on one-step solvothermal method and preparation method thereof | |
| CN113219010A (en) | Ethanol sensor of ZnO double-shell hollow structure microsphere sensitive material and preparation | |
| CN113433174A (en) | Ethanol sensor based on ZnO porous structure microsphere sensitive material, preparation method and application thereof | |
| CN111252816A (en) | Nb-NiO nano material and preparation method and application thereof | |
| CN110988052A (en) | Based on Fe2O3Acetone sensor of sensitive material and preparation method thereof | |
| CN113671010B (en) | In based on mesoporous2O3Triethylamine gas sensor of-NiO sensitive material and preparation method thereof | |
| CN111650252A (en) | High-sensitivity gas detection sensor | |
| CN114324499B (en) | Core-shell structure based ZnCr 2 O 4 Xylene gas sensor of microsphere sensitive material and preparation method thereof | |
| CN107673355A (en) | A kind of gas sensing material for low-power-consumptiohigh-sensitivity high-sensitivity methane transducer | |
| CN115541666B (en) | Heterojunction composite material for trimethylamine gas sensor and preparation method thereof | |
| CN113281383B (en) | Ethanol gas sensor of heterojunction composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |