CN112960686A - Preparation method of flaky ZnO and application of flaky ZnO in gas chromatography detector - Google Patents
Preparation method of flaky ZnO and application of flaky ZnO in gas chromatography detector Download PDFInfo
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- CN112960686A CN112960686A CN201911288762.5A CN201911288762A CN112960686A CN 112960686 A CN112960686 A CN 112960686A CN 201911288762 A CN201911288762 A CN 201911288762A CN 112960686 A CN112960686 A CN 112960686A
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- C—CHEMISTRY; METALLURGY
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
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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
- C01P2002/70—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
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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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The application discloses a preparation method of flaky ZnO, which comprises the following steps: a) will contain Zn2+Reacting with a solution of a ligand to obtain a precursor; b) calcining the ZIFs precursor to obtain the flaky ZnO; wherein the precursor is a layered two-dimensional porous material. And methods of using the same on portable gas chromatography detectors.
Description
Technical Field
The invention belongs to the field of synthesis and application of nano materials, and particularly relates to preparation and application of a gas-sensitive material of a gas chromatography semiconductor detector.
Background
At present, the development of portable gas chromatography detectors has been greatly developed, and various small detectors which can be used for portable gas chromatography have been developed so far, including solid state thermal conductivity detectors (SSD) which use different substances with different thermal conductivity coefficients for detection, have a wide range of applications and respond to most permanent gases and pollutants, but have general sensitivity, which is difficult to realize ppb level concentration detection, and high purity hydrogen or helium is generally required as a carrier gas for the thermal conductivity detectors. The hydrogen Flame Ionization Detector (FID), which is the most common gas chromatography detector, has the characteristics of high sensitivity, wide linear range and wide detection range and is widely used, but it requires hydrogen and clean air to work at the same time, and is not favorable for portable application. In addition, the size of the flame also affects ionization efficiency, and thus sensitivity. Another type of Photo Ionization Detector (PID), which does not require additional gas and has high detection sensitivity, is limited by the energy of the photo ion source and different ionization efficiencies for different species resulting in different responses, and water molecules destroy the salt window.
Because of its simple synthesis, low cost and high sensitivity, semiconductor metal oxide has been widely used in various gas detection. Seiyama et al first tried to use a ZnO film based sensor as a gas chromatography detector instead of a conventional detector, although achieving higher sensitivity, but with longer response and recovery times. Since then, there have been reports on semiconductors as gas chromatography detectors, but there still exist some problems such as significant peak broadening and peak tailing, and the fundamental requirements of chromatographic detection on response speed cannot be satisfied. In has also been studied In our laboratory2O3As a material for detecting gas chromatography detectors, the structure of the detector is optimized to reduce the dead volume, further shorten the response and recovery time and reduce the peak broadening, and better detection effect is obtained (Sensors and activators B2015,216,511 and 517). On the basis, the semiconductor materials with different morphologies are expected to be purposefully synthesized through reasonable material design, and the semiconductor materials are applied to a gas chromatography detector to eliminate the phenomena of chromatographic peak tailing and broadening.
Disclosure of Invention
According to one aspect of the present application, a synthesis of two-dimensional ZIFs materials and methods of using the same on portable gas chromatography detectors are provided.
The ZIFs material as one member of MOFs family has the characteristics of stable property, convenient synthesis, large specific surface area, regular and adjustable pore structure and the like. However, ZIFs are generally present in the form of three-dimensional nanoparticles, and the three-dimensional nanoparticles are easily aggregated to form a bulk structure due to the high temperature during the calcination process. Compared with the three-dimensional ZIF, the two-dimensional ZIFs have stronger in-plane interaction in the material layer, and weak van der Waals acting force exists between layers, so that the diffusion barrier is lower than that of the three-dimensional ZIF, and the active site and the component to be detected generate good interaction. In summary, the use of two-dimensional ZIFs materials for gas chromatography detectors is a viable attempt to reduce peak broadening and tailing. The high sensitivity and ideal chromatographic peak signal make it hopeful to be used in portable chromatographic detector.
The preparation method of the flaky ZnO is characterized by comprising the following steps of:
a) will contain Zn2+Reacting with a solution of a ligand to obtain a precursor;
b) calcining the ZIFs precursor to obtain the flaky ZnO;
wherein the precursor is a layered two-dimensional material.
Optionally, the precursor in step a) is a ZIFs material.
Optionally, the ligand in step a) is an imidazole ligand;
the imidazole ligand is selected from any one of 2-methylimidazole, benzimidazole and imidazole-2-formaldehyde.
Optionally, said Zn in step a)2+The source of (A) is zinc salt;
the zinc salt is at least one selected from zinc nitrate, zinc acetate and zinc chloride.
Optionally, the solvent of the solution in step a) is selected from at least one of water, methanol and ethanol.
Optionally, the Zn is contained in the step a)2+And Zn in solution with a ligand2+The concentration of (A) is 1-4M;
said Zn contained in step (a)2+And the concentration of the ligand in the solution of the ligand is 4-16M.
Alternatively, the reaction conditions in step a) are: the reaction temperature is 20-35 ℃, and the reaction time is 0.5-8 hours.
Optionally, the reaction in step a) is carried out under stirring conditions.
Alternatively, the conditions of the calcination in step b) are:
the calcination temperature is 200-600 ℃, and the calcination time is 0.5-4 h.
As an embodiment, the method for synthesizing the flaky ZnO includes:
dissolving metal ions and ligands in a solvent, standing for a period of time to enable the metal ions and the ligands to undergo a self-assembly process, then stirring for a plurality of hours at room temperature, washing and drying. And (3) calcining the synthesized ZIF precursor in a high-temperature furnace to obtain a white product, namely the flaky ZnO.
According to another aspect of the present application, there is provided a use of the flaky ZnO prepared by any one of the above methods in a gas sensitive material.
According to another aspect of the application, the application of the flaky ZnO prepared by any one of the methods in gas chromatography detection is provided.
Optionally, the application comprises the steps of:
and coating the suspension containing the flaky ZnO on the detection electrode of the gas chromatography, drying, and then placing the detection electrode coated with the ZnO in a gas chromatography detector to detect a sample to be detected.
Optionally, the concentration of ZnO in the suspension containing the flaky ZnO is 1-5 mg/mL;
the solvent in the suspension containing the flaky ZnO is selected from at least one of water, methanol and ethanol;
the dosage of the turbid liquid is 0.1-1 mu L.
Optionally, the detection conditions of the gas chromatography detection are as follows:
the variation range of the heating voltage is 4-6.5V, the variation range of the tail blowing gas is 2-10 ml/min, and the variation range of the temperature of the detector is 50-90 ℃.
Optionally, the sample to be tested comprises an oxygen-containing organic substance;
at least one of the oxygen-containing organic alcohols, aldehydes, ketones and acids.
Optionally, the sample to be tested is a mixture of ethanol, propanol and butanol.
As an embodiment, the application of the flaky ZnO in a gas chromatography detector: and (3) preparing the synthesized ZnO into suspension, dripping the suspension on the interdigital electrode of the ceramic chip, and installing the suspension on a gas chromatography detector after the suspension is naturally dried. And then, optimizing the heating voltage, the tail gas blowing and the temperature of the detector, performing sample testing after all conditions are determined, and acquiring data.
In the present application, "ZIFs" refers to a zeolite-like imidazolate framework material, and is a porous material having a zeolite topology structure formed by connecting a transition metal atom Zn or Co with imidazole or an imidazole derivative.
The beneficial effects that this application can produce include:
1) according to the preparation method of the flaky ZnO, the two-dimensional ZIFs material is used as the template to synthesize the flaky ZnO, and the method is simple, convenient, easy, low in cost, green and economical.
2) The flaky ZnO used as the portable gas chromatography detector has high sensitivity, and obviously reduced peak broadening and tailing phenomena.
3) The portable gas chromatography detector is made to slice ZnO that this application provided, only needs pure air to make carrier gas and tail blow, and does not need other auxiliary gas, has promoted the practicality greatly.
4) Compared with hydrocarbons, the flaky ZnO used as the portable gas chromatography detector has better detection performance on oxygen-containing organic matters such as alcohols, aldehydes, ketones, acids and the like.
Drawings
FIG. 1 is a schematic diagram of an embodiment of a detector;
FIG. 2 is an XRD characterization of the platy ZnO in the examples of the present application;
FIG. 3 is a Scanning Electron Microscope (SEM) characterization of the flaky ZnO in the examples of the present application;
FIG. 4 is a heating voltage optimization of a sheet ZnO as a gas chromatography detector in the present example;
FIG. 5 is a graph showing the temperature optimization of a gas chromatography detector using sheet ZnO in the present example;
FIG. 6 is a tail blow optimization of the sheet ZnO as a gas chromatography detector in the present example;
FIG. 7 is a chromatogram separation chart and a working curve of flaky ZnO ethanol, propanol and butanol in the embodiment of the application; wherein a is a chromatographic separation chart of flaky ZnO on ethanol, propanol and butanol; b is an ethanol working curve; c is a propanol working curve; d is the butanol working curve.
List of parts and reference numerals: in fig. 1, a is an interdigital electrode of a ceramic wafer.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
XRD analysis was carried out using a PANALYTICAL X' Pert PRO X-ray diffractometer at a test voltage of 40kV and a test current of 40 mA.
Gas chromatography was performed using agilent 7890A gas chromatography.
In the examples, "room temperature" means 20 to 35 ℃.
Example 1: synthesizing flaky ZnO by taking two-dimensional ZIFs as a template:
0.595g of Zn (NO) are weighed out3)2·6H2Dissolving O in 40ml water, weighing 1.31g 2-methylimidazole in another beaker, dissolving in 40ml water, stirring to clarify, adding Zn2+The solution is added into 2-methylimidazole solution, stirred for 4 hours at room temperature, centrifuged for 5min at 6500 rpm and washed with water for three times. And drying the washing product, transferring the washed product into a quartz boat, heating to 500 ℃ at the heating rate of 5 ℃/min, keeping for 2 hours, naturally cooling, collecting the product, and marking as a sample 1.
Example 2: synthesizing flaky ZnO by taking two-dimensional ZIFs as a template:
0.595g of Zn (NO) are weighed out3)2·6H2Dissolving O in 40ml water, weighing 1.31g 2-methylimidazole in another beaker, dissolving in 40ml water, stirring to clarify, adding Zn2+Adding the solution into 2-methylimidazole solution, and stirring at room temperature8 hours, 6500 rpm centrifugation for 5min, water washing three times. And drying the washing product, transferring the dried washing product into a quartz boat, heating to 500 ℃ at the heating rate of 10 ℃/min, keeping for 2 hours, naturally cooling, collecting the product, and marking as a sample 2.
Example 3: synthesizing flaky ZnO by taking two-dimensional ZIFs as a template:
the other operation was the same as that of example 1 except that the calcination temperature was 200 ℃ and the calcination time was 6 hours, and the obtained product was designated as sample 3.
Example 4: synthesizing flaky ZnO by taking two-dimensional ZIFs as a template:
the other operation was the same as that of example 1 except that the calcination temperature was 600 ℃ and the calcination time was 0.5 hours, and the obtained product was designated as sample 4.
Example 5: synthesizing flaky ZnO by taking two-dimensional ZIFs as a template:
the other procedure is the same as in example 1 except that benzimidazole was used as the ligand, and the obtained product was designated as sample 5.
Example 6: characterization of samples 1 to 5
XRD tests are carried out on the samples 1-5, and a typical XRD spectrogram is shown in figure 2 and corresponds to the sample 1. The XRD patterns of the other samples were similar to those of fig. 2. XRD shows that the synthesized flaky ZnO completely conforms to the standard card, and the synthesized material is proved to be ZnO.
The shape of the samples 1 to 5 is tested, taking the sample 1 as an example, the scanning electron microscope images are shown in fig. 3, and the scanning electron microscope images of other samples are similar to fig. 3.
Example 7: and (3) optimizing the heating voltage of the flaky ZnO as a gas chromatography detector:
the ZnO synthesized in example 1 was suspended at a concentration of 5mg/ml, 0.5 μ L was applied dropwise to the interdigital electrode of the ceramic wafer, and after naturally drying, it was mounted on a gas chromatography detector. Keeping the tail gas blowing rate of the gas chromatography detector at 10ml/min, keeping the heating temperature of the detector at 50 ℃, injecting 2000ppm ethanol into the gas chromatography detector to make the heating voltage values respectively at 4V,4.5V,5V,5.5V and 6V, reading the chromatographic peak heights, plotting the chromatographic peak heights as ordinate and the heating voltage values as abscissa, and determining the optimal heating voltage to be 6V as shown in FIG. 4.
Example 8: and (3) optimizing the detector temperature of the flaky ZnO as a gas chromatography detector:
the ZnO synthesized in example 1 was suspended at a concentration of 5mg/ml, 0.5 μ L was applied dropwise to the interdigital electrode of the ceramic wafer, and after naturally drying, it was mounted on a gas chromatography detector. Keeping the heating voltage of the gas chromatography detector at 6V, keeping the tail gas blowing of the gas chromatography detector at 10ml/min, injecting 2000ppm ethanol into the gas chromatography detector to make the detector temperature values at 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, and 90 deg.C, reading the chromatographic peak height, plotting the chromatographic peak height as ordinate and the detector temperature as abscissa, and determining the optimal detector temperature as 80 deg.C as shown in FIG. 5.
Example 9: tail blowing optimization of flaky ZnO as gas chromatography detector
The ZnO synthesized in example 1 was suspended at a concentration of 5mg/ml, 0.5 μ L was applied dropwise to the interdigital electrode of the ceramic wafer, and after naturally drying, it was mounted on a gas chromatography detector. Keeping the heating voltage of the gas chromatography detector at 6V and the temperature of the gas chromatography detector at 80 ℃, injecting 2000ppm ethanol into the gas chromatography detector to make the tail gas blowing flow rate values respectively 2ml/min, 4ml/min, 6ml/min, 8ml/min and 10ml/min, reading the chromatographic peak height, plotting by taking the chromatographic peak height as an ordinate and the tail gas blowing flow rate as an abscissa, and determining the optimal detector tail gas blowing flow rate to be 2ml/min as shown in FIG. 6.
Example 10: chromatographic separation of flaky ZnO from ethanol, propanol and butanol
The ZnO synthesized in example 1 was suspended at a concentration of 5mg/ml, 0.5 μ L was applied dropwise to the interdigital electrode of the ceramic wafer, and after naturally drying, it was mounted on a gas chromatography detector. Maintaining the heating voltage of the gas chromatography detector at 6V, the temperature of the gas chromatography detector at 80 deg.C, and the flow rate of the gas blown from the tail of the chromatography detector at 2ml/min, and injecting 5ppm, 10ppm, 50ppm, 100ppm, and 200ppm of ethanol, propanol, and butanol into the gas chromatography, respectively, to obtain a chromatogram, as shown in FIG. 7. Fig. 7 shows that the peak shape of the chromatographic peak is symmetrical, and there is almost no phenomenon of peak broadening and peak tailing. And reading the chromatographic peak height, and drawing by taking the peak height as a vertical coordinate and the concentration of the substance to be detected as a horizontal coordinate to obtain three working curves with good linearity. For ethanol: 1.2203x-0.2475, R2 0.9987; p-propanol: y is 1.557x-0.2271, and R2 is 0.9994; p-butanol: y is 1.3214x-0.8081 and R2 is 0.9998.
The separation performance of samples 2-5 was similar to that of sample 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A preparation method of flaky ZnO is characterized by comprising the following steps:
a) will contain Zn2+Reacting with a solution of a ligand to obtain a precursor;
b) calcining the ZIFs precursor to obtain the flaky ZnO;
wherein the precursor is a layered two-dimensional material.
2. The method for preparing according to claim 1, wherein the precursor in step a) is a ZIFs material.
3. The method of claim 1, wherein the ligand in step a) is an imidazole ligand;
the imidazole ligand is selected from any one of 2-methylimidazole, benzimidazole and imidazole-2-formaldehyde.
4. The method according to claim 1, wherein the Zn is added in step a)2+The source of (A) is zinc salt;
the zinc salt is at least one selected from zinc nitrate, zinc acetate and zinc chloride.
5. The method according to claim 1, wherein the solvent of the solution in step a) is at least one selected from water, methanol and ethanol.
6. The method according to claim 1, wherein the Zn is contained in the step (a)2+And Zn in solution with a ligand2+The concentration of (A) is 1-4M;
said Zn contained in step (a)2+And the concentration of the ligand in the solution of the ligand is 4-16M.
7. The method according to claim 1, wherein the reaction conditions in step a) are: the reaction temperature is 20-35 ℃, and the reaction time is 0.5-8 hours;
preferably, the reaction in step a) is carried out under stirring conditions.
8. The method of claim 1, wherein the calcining conditions in step b) are:
the calcination temperature is 200-600 ℃, and the calcination time is 0.5-4 h.
9. Use of the flaky ZnO prepared by the process of any one of claims 1 to 8 in a gas sensitive material.
10. Use of the flaky ZnO prepared by the method of any one of claims 1 to 8 in gas chromatography detection;
preferably, the application comprises the steps of:
coating the suspension containing the flaky ZnO on a detection electrode of the gas chromatography, drying, and then placing the detection electrode coated with the ZnO in a gas chromatography detector to detect a sample to be detected;
preferably, the concentration of ZnO in the suspension containing the flaky ZnO is 1-5 mg/mL;
the solvent in the suspension containing the flaky ZnO is selected from at least one of water, methanol and ethanol;
the using amount of the suspension is 0.1-1 mu L;
preferably, the detection conditions of the gas chromatography detection are as follows:
the variation range of the heating voltage is 4-6.5V, the variation range of the tail blowing gas is 2-10 ml/min, and the variation range of the temperature of the detector is 50-90 ℃;
preferably, the sample to be tested comprises an oxygen-containing organic substance;
at least one of the oxygen-containing organic alcohols, aldehydes, ketones and acids;
preferably, the sample to be tested is a mixture of ethanol, propanol and butanol.
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Application publication date: 20210615 |