CN114689664A - Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application - Google Patents

Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application Download PDF

Info

Publication number
CN114689664A
CN114689664A CN202011606147.7A CN202011606147A CN114689664A CN 114689664 A CN114689664 A CN 114689664A CN 202011606147 A CN202011606147 A CN 202011606147A CN 114689664 A CN114689664 A CN 114689664A
Authority
CN
China
Prior art keywords
mofs
amino
mil
prepare
substrate
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.)
Pending
Application number
CN202011606147.7A
Other languages
Chinese (zh)
Inventor
邓韦华
徐刚
姚明水
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujian Institute of Research on the Structure of Matter of CAS
Original Assignee
Fujian Institute of Research on the Structure of Matter of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Fujian Institute of Research on the Structure of Matter of CAS filed Critical Fujian Institute of Research on the Structure of Matter of CAS
Priority to CN202011606147.7A priority Critical patent/CN114689664A/en
Publication of CN114689664A publication Critical patent/CN114689664A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)

Abstract

The invention discloses a method for preparing a chemical resistance sensor by using an amino functionalized metal organic framework material, which comprises the following specific steps: s1: preparation or preparation of amino-functionalized Metal-organic frameworks (NH)2-MOFs) nanosheet powder; s2: reacting NH2Dissolving MOFs nanosheet powder in an organic solvent to prepare paste, uniformly coating the paste on a non-conductive substrate, fixedly connecting wires at two ends of the non-conductive substrate, and heating to prepare the chemical resistance sensor. NH prepared herein2The MOFs gas-sensitive material has an ultra-high specific surface area, so that the adsorption of the material to gas is greatly improved, and the amino functional group can selectively adsorb gas, so that the gas-sensitive performance and selectivity of the gas are improved, and the gas-sensitive material can detect nitro explosives and nitro-containing explosive raw materials on line in real time with high sensitivity and high selectivity.

Description

Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application
Technical Field
The invention relates to the field of functional material science and the field of chemical resistance type sensing, in particular to a method for preparing a chemical resistance type sensor by using an amino functionalized metal organic framework material for thin film electrical devices such as a gas sensor, a lithium sulfur battery, a fuel cell and the like and application thereof.
Background
The problem of environmental pollution caused by nitro explosives has always been a key focus of society. Nitro explosives such as trinitrotoluene (TNT), Dinitrotoluene (DNT), Picric Acid (PA) and hexogen (RDX) are important standard explosives, and the room-temperature saturated vapor pressure is very low, such as 9ppb, 180ppb, 0.97ppb and 4.9PPT of TNT, DNT, PA and RDX, so that a plurality of sensors are difficult to detect the atmosphere of the sensor on line in real time, and have low sensitivity and poor selectivity. The ammonium nitrate explosive is prepared by mixing an oxidant, a combustible agent and a sensitizing agent, wherein ammonium nitrate is a main oxidant of the ammonium nitrate explosive, urea nitrate is an explosive, and is also a raw material and an intermediate for preparing the explosive, and the explosive is prepared by mixing the raw material, the intermediate, an organic matter, a reducing agent and the like. Therefore, the detection of ammonium nitrate and urea nitrate can realize the detection of partial nitro explosive raw materials.
In the prior art, Metal Oxide (MOX) or other polymers are usually adopted as a chemical resistance type sensor to detect the atmosphere of the room-temperature nitro explosives, but the sensor has low sensitivity and selectivity, so that the detection precision of the atmosphere of the nitro explosives is reduced.
Metal Organic Frameworks (MOFs) are crystalline porous materials with a regular network structure that are self-assembled by inorganic nodes (metal ions or metal clusters) and organic ligands through coordination. The MOFs serving as a novel functional material has the advantages of ordered and diversified structures, high cuttability, ultrahigh specific surface area and the like, and has good application prospects in the fields of drug carriers, gas separation, gas adsorption storage and removal, catalysis, magnetism, sensors, optics and the like. And different functional groups can be introduced to endow the material with different properties. The amino group is a nucleophilic group, can regulate and control the band gap of the material to ensure that the material has visible light absorption, and simultaneously is used as Lewis base to ensure that the material has CO resistance2,NO2Nitro compounds and the like can selectively adsorb and functionalize amino groups on metal organic frameworks (NH)2MOFs) for gas detection are also increasingly widely studied.
Current NH2The research of MOFs for detecting nitro explosives based on fluorescence is many, but no relevant report of room temperature detection of nitro explosive atmosphere by chemical resistance type sensors exists so far.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for preparing a chemiresistive sensor by using an amino functionalized metal organic framework material, which comprises the following specific steps:
s1: preparation or preparation of amino-functionalized Metal-organic frameworks (NH)2-MOFs) nanosheet powder;
s2: reacting NH2Dissolving MOFs nanosheet powder in an organic solvent to prepare paste, uniformly coating the paste on a non-conductive substrate, fixedly connecting wires at two ends of the non-conductive substrate, and heating to prepare the chemical resistance sensor.
According to the technical scheme of the invention, the step S2 adopts a mode of evaporation plating or direct glue coating; specifically, one or more of spin coating, lifting, dipping, dripping, in-situ growth and layer-by-layer self-assembly methods can be adopted to prepare NH2-MOFs preparation of films.
According to the technical scheme of the invention, the non-conductive substrate is AL2O3The substrate comprises one of a substrate, a sapphire substrate, a chip-carrying substrate, a polytetrafluoroethylene substrate, a quartz substrate and a PDMS substrate.
According to the invention, the metal-organic framework (NH) is functionalized by an amino group in step S12-MOFs) powder is prepared by the following steps: dissolving organic ligand containing amino and metal salt in mixed solvent of anhydrous methanol and DMF, mixing uniformly, heating for reaction, drying, and preparing NH2-MOFs powders.
According to the technical scheme of the invention, the volume ratio of the anhydrous methanol to the DMF is (1-9): (9-1). Preferably 1: 9.
According to the technical scheme of the invention, the molar ratio of the organic ligand containing amino groups to the metal salt is (20-1):1, and preferably 1: 1.
According to the technical solution of the present invention, the NH2The specific surface area of the MOFs material is 1000-3000m2g-1The pore diameter is 0.2-2 nm.
According to the technical scheme of the invention, the heating temperature is 100-220 ℃; the heating time is 15-96 h; the drying temperature is 80-150 ℃, and the drying time is 12-48 h; preferably, drying is carried out at 80 ℃ for 12 h.
According to the technical scheme of the invention, the organic ligand for functionalizing the amino is diaminoterephthalic acid (NH)2-BDC), 2, 5-diaminoterephthalic acid ((NH)2)2-BDC), at least one of 2-amino-1, 4-benzenedicarboxylic Acid (ABDC)), preferably NH2-BDC。
According to the technical scheme of the invention, the metal In the metal salt is one or more of titanium (Ti), zirconium (Zr), iron (Fe), chromium (Cr), aluminum (Al), copper (Cu) or indium (In); preferably titanium (Ti) and zirconium (Zr); preferably, when the metal salt is a titanium (Ti) salt, it may be tetra-n-butyl titanate, titanium tetrachloride or titanium trichloride, preferably, tetra-n-butyl titanate; when the metal salt is a zirconium salt, it may be zirconium tetrachloride.
According to the technical solution of the present application, step S2 further includes: reacting NH2Dissolving MOFs nanosheet powder in an organic solvent to prepare paste, uniformly coating the paste on a non-conductive substrate, wherein two ends of the non-conductive substrate are fixedly connected with a wire to prepare NH2-a MOFs nanosheet thin film seed layer; dissolving organic ligand containing amino and metal salt in mixed solvent of anhydrous methanol and DMF to prepare mixed solution, and adding NH2And (3) immersing the MOFs nanosheet film seed crystal layer into the mixed solution, and heating to prepare the chemical resistance sensor.
The invention also provides a chemical resistance sensor prepared by the method.
The invention also provides application of the chemical resistance sensor, which is applied to detection of nitro explosive atmosphere, and the specific detection method comprises the following steps:
and connecting and electrifying the chemical resistance type sensor with a power supply, and applying voltage to detect the nitro explosive steam.
According to the technical scheme of the invention, the nitro explosive is TNT, DNT, PA, RDX or derivatives thereof.
According to the technical scheme of the invention, a solvothermal method is selected to obtain NH2MOFs, including NH2-MIL-125(Ti)，NH2-UIO-66(Zr)，NH2-MIL-101(Fe)，NH2-MIL-101(Cr)，NH2-MIL-101(Al)，NH2-MIL-53(Al)，Fe-MIL-88B-NH2，MOF-5-NH2，NH2-MIL-68(In)，NH2-CU3(BTC)2One or more of them.
The invention has the advantages of
(1) NH prepared herein2The MOFs gas-sensitive material has an ultra-high specific surface area, so that the adsorption of the material to gas is greatly improved, and the amino functional group can selectively adsorb gas, so that the gas-sensitive performance and selectivity of the gas are improved, and the gas-sensitive material can detect nitro explosives and nitro-containing explosive raw materials on line in real time with high sensitivity and high selectivity.
(2) NH of the present application2The MOFs film enhances the adsorption of nitro explosives according to the acid-base interaction with the increase of the number of amino groups of the ligand, and improves the sensitivity and selectivity of the MOFs film in detecting nitro explosives by combining the high specific surface area of the MOFs film and pre-enriching and concentrating the atmosphere of the nitro explosives with extremely low concentration. The response value at room temperature to 0.97ppb of trinitrophenol (PA) was 230%.
(3) The application uses a seed-assisted solvothermal process for the preparation of NH of controllable thickness, i.e. for the secondary growth of oriented continuous MOF films2-a MOF preferentially oriented film. The MOF nano particles prepared by a direct solvothermal method instead of a seed crystal assisted solvothermal method are prepared into a disordered thick film, and are not continuous preferred orientation films, and a device prepared by the disordered thick film of the particles is poor in mass transfer and conduction, low in sensitivity, slow in response speed and difficult to recover when the device is applied to a chemical resistance type sensor for detecting gas. When the continuous film with preferred orientation is applied to a chemical resistance type sensor to detect gas, the sensitivity and the response speed can be obviously improved.
Drawings
FIG. 1 shows the octahedral NH in example 12-scanning electron microscopy of MIL-125 (Ti);
FIG. 2 shows NH in example 22-scanning electron microscopy images of MIL-125(Ti) nanoplates;
FIG. 3 shows NH in example 32-scanning electron microscopy images of MIL-125(Ti) nanoplates;
FIG. 4 shows NH in example 42-scanning electron microscopy of MIL-125(Ti) nanoplates;
FIG. 5 shows NH in example 52-scanning electron micrographs of MIL-125(Ti) films;
FIG. 6 shows NH in example 52-PXRD pattern for MIL-125(Ti) films;
FIG. 7 is NH in comparative example 12-PXRD pattern of UiO-66 (Zr);
FIG. 8 shows NH in example 62-MOFs thin film performance test schematic;
FIG. 9 is a test chart of the response of the chemical resistance type sensor to the PA atmosphere in example 6;
FIG. 10 is a test chart of the response of the chemical resistance type sensor to the PA atmosphere in example 7;
FIG. 11 is a graph showing the response test of the chemical resistance type sensor to the PA atmosphere in example 8.
Detailed Description
The preparation and use of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
NH for chemical resistance type sensor to detect nitro explosive atmosphere2-synthesis of MOF material comprising the steps of:
a. 18ml of anhydrous DMF and 2ml of anhydrous methanol are taken and mixed uniformly, and then 1.086g of NH is added2BDC is dissolved in the mixed solvent, and the mixed solvent is completely dissolved by ultrasonic treatment for 5 min;
b. b, quickly adding 0.52ml of tetra-n-butyl titanate into the solution in the step a, and uniformly stirring;
c. transferring the solution in the step b into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a stainless steel autoclave, placing the stainless steel autoclave into an oven, maintaining the temperature at 150 ℃ for 72 hours, and taking out; and preparing a mixed solution.
d. C, centrifugally washing the mixed solution in the step c by using methanol, and drying at 80 ℃ for 12h to obtain octahedral NH2MIL-125(Ti), as shown in FIG. 1, in a scanning electron micrograph.
Example 2
NH for chemical resistance type sensor to detect nitro explosive atmosphere2-synthesis of MOF material comprising the steps of:
a. 18ml of anhydrous DMF and 2ml of anhydrous methanol were taken and mixed well, and 0.4344g of NH were added2BDC is dissolved in the mixed solvent, and the mixed solvent is completely dissolved by ultrasonic treatment for 5 min.
b. And (b) quickly adding 0.208ml of tetra-n-butyl titanate into the solution in the step a, and uniformly stirring.
c. And (c) pouring the solution in the step (b) into a polytetrafluoroethylene lining, paving the lining, then placing the lining into a stainless steel autoclave, and placing the stainless steel autoclave into an oven to maintain the temperature of 150 ℃ for 72 hours to prepare a mixed solution.
d. C, centrifugally washing the mixed solution in the step c by using methanol, drying at 80 ℃ for 12h, and NH2MIL-125(Ti) nanoplatelets having a thickness in the range of 100-150nm as shown in FIG. 2 by scanning electron microscopy.
Example 3
NH for chemical resistance type sensor to detect nitro explosive atmosphere2-synthesis of MOF material comprising the steps of:
a. 18ml of dried DMF and 2ml of dried methanol were taken and mixed well, and then 0.2172g of NH2-BDC was dissolved in the mixed solvent and was dissolved completely by sonication for 5 min.
b. And (b) quickly adding 0.104ml of tetra-n-butyl titanate into the solution in the step a, and uniformly stirring.
c. And (c) transferring the solution in the step (b) into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a stainless steel autoclave, placing the stainless steel autoclave into an oven, maintaining the temperature at 150 ℃ for 72 hours, and then taking out to prepare a mixed solution.
d. Using methanol to the mixed solution in the step cCentrifugally washing, drying at 80 ℃ for 12h to obtain NH2-MIL-125(Ti) nanoplatelets having a thickness in the range of 50-100nm as shown in fig. 3 by scanning electron microscopy.
Example 4
NH for chemical resistance type sensor to detect nitro explosive atmosphere2-synthesis of MOF material comprising the steps of:
a. 18ml of anhydrous DMF and 2ml of anhydrous methanol were taken and mixed well, and 2.715g of NH were added2BDC is dissolved in the mixed solvent, and the mixed solvent is completely dissolved by ultrasonic treatment for 5 min.
b. And (b) quickly adding 0.21ml of tetra-n-butyl titanate into the solution in the step a, and uniformly stirring.
c. Transferring the solution in the step b into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a stainless steel autoclave, placing the stainless steel autoclave into an oven, maintaining the temperature at 150 ℃ for 72 hours, and then taking out the stainless steel autoclave to prepare a mixed solution.
d. C, centrifugally washing the mixed solution in the step c by using methanol, and drying at 80 ℃ for 12h to obtain NH2-nanoplatelets of MIL-125(Ti) having a thickness in the range of 5-50nm as shown in figure 4 by scanning electron microscopy.
Example 5
A preparation method of an amino functionalized metal organic framework material comprises the following steps:
a. 18ml of anhydrous DMF and 2ml of anhydrous methanol were taken and mixed well, and 2.715g of NH were added2BDC is dissolved in the mixed solvent, and the mixed solvent is completely dissolved by ultrasonic treatment for 5 min;
b. b, quickly adding 0.21ml of tetra-n-butyl titanate into the solution in the step a, and uniformly stirring;
c. transferring the solution in the step b into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a stainless steel autoclave, placing the stainless steel autoclave into an oven, maintaining the temperature at 150 ℃ for 72 hours, and then taking out the stainless steel autoclave to prepare a mixed solution;
d. c, centrifugally washing the mixed solution in the step c by using methanol, and drying at 80 ℃ for 12h to obtain 5-50nm NH2-nanoplatelets of MIL-125 (Ti);
e. adding 5-50nm NH in the step d2Uniformly dripping nano sheets of-MIL-125 (Ti) on Al by adopting a spin coating method2O3Is not conductiveOn a substrate as growth-oriented NH2-a seed layer of MIL-125(Ti) thin film;
f.18ml of anhydrous DMF and 2ml of anhydrous methanol were mixed well, and 0.2172g of NH was added thereto2-BDC and 0.21ml tetra-n-butyl titanate, stirring and mixing well;
g. adding NH in step e2Putting a seed crystal layer of the-MIL-125 (Ti) film into the solution obtained in the step f, putting the seed crystal layer into a polytetrafluoroethylene lining, putting the lining into a stainless steel autoclave, putting the autoclave into an oven, carrying out solvent heating at 150 ℃ for 72h, finishing the reaction, washing the obtained product with methanol to obtain continuous preferentially oriented NH2A scanning electron micrograph of a MIL-125(Ti) film as shown in FIG. 5. Its PXRD pattern is shown in FIG. 6.
Example 6
The application of the chemical resistance sensor is applied to the detection of the atmosphere of the nitro explosives, and the specific detection method comprises the following steps:
s1, 5mg of NH in example 32Dissolving MIL-125(Ti) powder in methanol, and stirring for 24 hours to prepare a paste sample;
s2, adding Al2O3Connecting gold wires at two ends of an interdigital electrode of the substrate by using silver glue, and standing for 2 hours at 80 ℃;
s3, dripping the pasty sample in the step a on the substrate in the step b, and drying at 80 ℃ to obtain a chemical resistance type sensor for detecting the atmosphere of the nitro explosives;
s4, connecting the device with a Gibber's Virgilli source meter, introducing dry air, aging for 12h under the voltage of 5V, and then detecting the atmosphere of the nitro explosives;
s5, filling 2g of PA powder into a U-shaped glass tube, introducing dry air into two ends of the U-shaped glass tube, heating the U-shaped glass tube at 80 ℃ for 24 hours, and draining the adsorbed water vapor; then it was sealed and pre-enriched at room temperature for 24h to give 0.97ppb of PA vapour.
S6, introducing the steam in the step e into the device in the step d, monitoring the current change caused after the PA is introduced by using a Giaxle Li source meter, and testing the device as shown in the figure 8. The response of the chemiresistor sensor test to the PA atmosphere is shown in fig. 9, with a response of 42% for 0.97ppb of PA.
Example 7
The application of the chemical resistance sensor is applied to the detection of the atmosphere of the nitro explosives, and the specific detection method comprises the following steps:
a. NH in example 32Dissolving MOF powder in methanol, and stirring for 24 hours to obtain a paste sample;
b. at AL2O3Connecting gold wires at two ends of an interdigital electrode serving as a substrate by using silver glue, and standing at 80 ℃ for 2 hours;
c. and (c) dripping the paste sample obtained in the step (a) on the substrate obtained in the step (b), and standing at room temperature to naturally dry the paste sample. Obtaining a chemical resistance type sensor for detecting the atmosphere of the nitro explosives;
d. connecting the device with a Gicky-Times source meter, introducing dry air, aging for 12h under 5V voltage, and detecting the atmosphere of nitro explosives;
e. 2g of PA powder is filled into a U-shaped glass tube, dry air is introduced into two ends of the U-shaped glass tube, the U-shaped glass tube is heated for 24 hours at the temperature of 80 ℃, and adsorbed water vapor is discharged completely. Then the mixture is sealed and pre-enriched for 24h at 40 ℃ to obtain PA steam with the concentration of 7.3 ppb.
f. And (e) introducing the steam in the step (e) into the device in the step (d), and monitoring the current change caused by introducing the PA by using a Giaxle source meter. The response of the chemiresistor sensor test to the PA atmosphere is shown in fig. 10, with a response of 230% for 7.3ppb of PA.
Example 8
The application of the chemical resistance sensor is applied to the detection of the atmosphere of the nitro explosives, and the specific detection method comprises the following steps:
a. NH in example 32Dissolving MOF powder in methanol, and stirring for 24 hours to obtain a paste sample;
b. at AL2O3Connecting gold wires at two ends of an interdigital electrode serving as a substrate by using silver glue, and standing at 80 ℃ for 2 hours;
c. and (c) dripping the paste sample obtained in the step (a) on the substrate obtained in the step (b), and standing at room temperature to naturally dry. Obtaining a chemical resistance type sensor for detecting the atmosphere of the nitro explosives;
d. connecting the device with a Gicky-Times source meter, introducing dry air, aging for 12h under 5V voltage, and detecting the atmosphere of nitro explosives;
e. 2g of PA powder is filled into a U-shaped glass tube, dry air is introduced into two ends of the U-shaped glass tube, the U-shaped glass tube is heated for 24 hours at the temperature of 80 ℃, and adsorbed water vapor is discharged completely. Then the mixture is sealed and pre-enriched for 24h at 60 ℃ to obtain PA steam with the concentration of 82 ppb.
f. And (e) introducing the steam in the step (e) into the device in the step (d), and monitoring the current change caused by introducing the PA by using a Giaxle source meter. The response of the chemiresistor-type sensor test to the PA atmosphere is shown in fig. 11, with a 372% response to 82ppb of PA.
Example 9
The application of the chemical resistance type sensor is applied to the detection of the atmosphere of the nitro explosive, and the specific detection method comprises the following steps:
a. the crystal growth of example 5 was directly carried out on Al2O3Preferred orientation continuous NH on non-conductive substrates2MOF films (i.e. NH)2-MIL-125(Ti) thin film), gold electrodes were vapor-plated.
b. Connecting the two ends by a silver adhesive gold thread, and standing at 80 ℃ for 2h to obtain a chemical resistance sensor for detecting the atmosphere of the nitro explosives;
c. connecting the device with a Gicky-Times source meter, introducing dry air, aging for 12h under 5V voltage, and detecting the atmosphere of nitro explosives;
d. 2g of PA powder is filled into a U-shaped glass tube, dry air is introduced into two ends of the U-shaped glass tube, the U-shaped glass tube is heated for 24 hours at the temperature of 80 ℃, and adsorbed water vapor is discharged completely. Then the mixture is sealed and pre-enriched for 24h at room temperature to obtain PA steam with the concentration of 0.97 ppb.
e. And (c) introducing the steam in the step d into the device in the step b, and monitoring the current change caused by introducing the PA by using a Giaxle source meter. The chemical resistance type sensor tests the response to the PA atmosphere, and the response value to the PA with 0.97ppb is obviously higher than that of NH2The MIL-125 disordered particle-stacked thick film device has obviously improved response speed and recovery speed.
Comparative example 1
NH for chemical resistance type sensor to detect nitro explosive atmosphere2-synthesis of MOF material comprising the steps of:
a. 60ml of DMF and 0.19ml of water are taken and mixed uniformly, and then 0.1mmol of NH2BDC is dissolved in the mixed solvent, and the mixed solvent is completely dissolved by ultrasonic treatment for 5 min.
b. And (b) quickly adding 1.029mmol of zirconium tetrachloride into the solution (a), and uniformly stirring.
c. Transferring the solution b into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into a stainless steel autoclave, placing the stainless steel autoclave into an oven, maintaining the temperature of 120 ℃ for 24 hours, and then taking out the stainless steel autoclave to prepare a mixed solution;
d. c, centrifugally washing the mixed solution in the step c by using methanol, and drying at 80 ℃ for 12h to obtain NH2UIO-66(Zr), shown in FIG. 7, is the NH synthesized2PXRD of UiO-66 (Zr).
Comparative example 2
The application of the chemical resistance sensor is applied to the detection of the atmosphere of the nitro explosives, and the specific detection method comprises the following steps:
a. NH in comparative example 12Dissolving the-UiO-66 (Zr) powder in methanol, stirring for 24 hours, and making the sample into paste;
b. at AL2O3Connecting gold wires at two ends of a silver-palladium interdigital electrode serving as a substrate by using silver glue, and standing for 2 hours at 80 ℃;
c. and (c) dripping the paste sample obtained in the step (a) on the substrate obtained in the step (b), and standing at room temperature to naturally dry. Obtaining a chemical resistance type sensor for detecting the atmosphere of the nitro explosives;
d. connecting the device with a Gicky-Times source meter, introducing dry air, aging for 12h under 5V voltage, and detecting the atmosphere of nitro explosives;
e. 2g of PA powder is filled into a U-shaped glass tube, dry air is introduced into two ends of the U-shaped glass tube, the U-shaped glass tube is heated for 24 hours at the temperature of 80 ℃, and adsorbed water vapor is discharged completely. Then the mixture is sealed and pre-enriched for 24h at room temperature to obtain PA steam with the concentration of 0.97 ppb.
f. And e, introducing the steam in the step e into the device in the step d, and monitoring the current change caused by introducing the PA by using a Gilbert cell. The material has obvious response to 0.97ppb of PA even in a normal temperature environment.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for preparing a chemical resistance sensor by using an amino functionalized metal organic framework material is characterized by comprising the following specific steps:
s1: preparation or preparation of amino-functionalized Metal-organic frameworks (NH)2-MOFs) nanosheet powder;
s2: reacting NH2Dissolving MOFs nanosheet powder in an organic solvent to prepare paste, uniformly coating the paste on a non-conductive substrate, fixedly connecting wires at two ends of the non-conductive substrate, and heating to prepare the chemical resistance sensor.
2. The method according to claim 1, wherein evaporation or direct gluing is used in step S2; specifically, one or more of spin coating, pulling, dipping, dripping, in-situ growth and layer-by-layer self-assembly methods can be adopted to prepare NH2-MOFs preparation of films.
Preferably, the non-conductive substrate is AL2O3The substrate comprises one of a substrate, a sapphire substrate, a chip-carrying substrate, a polytetrafluoroethylene substrate, a quartz substrate and a PDMS substrate.
3. The method according to claim 1, wherein the amino-functionalized metal organic framework (NH) is functionalized in step S12-MOFs) powder is prepared by the following steps: dissolving organic ligand containing amino and metal salt in mixed solvent of anhydrous methanol and DMF, mixing uniformly, heating for reaction, drying, and preparing NH2-MOFs powders.
Preferably, the volume ratio of the anhydrous methanol to the DMF is (1-9): (9-1). Preferably 1: 9.
Preferably, the molar ratio of the amino-containing organic ligand to the metal salt is (20-1: 1), preferably 1: 1.
4. The method of claim 1, wherein the NH is2The specific surface area of the MOFs material is 1000-3000m2 g-1The aperture is 0.2-2 nm.
Preferably, the heating temperature is 100-220 ℃; the heating time is 15-96 h; the drying temperature is 80-150 ℃, and the drying time is 12-48 h; preferably, drying is carried out at 80 ℃ for 12 h.
5. The process according to claim 1, wherein the organic ligand functionalizing an amino group is diaminoterephthalic acid (NH)2-BDC), 2, 5-diaminoterephthalic acid ((NH)2)2-BDC), at least one of 2-amino-1, 4-benzenedicarboxylic Acid (ABDC)), preferably NH2-BDC。
Preferably, the metal In the metal salt is one or more of titanium (Ti), zirconium (Zr), iron (Fe), chromium (Cr), aluminum (Al), copper (Cu) or indium (In); preferably titanium (Ti) and zirconium (Zr); preferably, when the metal salt is a titanium (Ti) salt, it may be tetra-n-butyl titanate, titanium tetrachloride or titanium trichloride, preferably, tetra-n-butyl titanate; when the metal salt is a zirconium salt, it may be zirconium tetrachloride.
6. The method according to claim 1, wherein step S2 further comprises: reacting NH2Dissolving MOFs nanosheet powder in an organic solvent to prepare paste, uniformly coating the paste on a non-conductive substrate, wherein two ends of the non-conductive substrate are fixedly connected with a wire to prepare NH2-a MOFs nanosheet thin film seed layer; dissolving organic ligand containing amino and metal salt in mixed solvent of anhydrous methanol and DMF to prepare mixed solution, and adding NH2And (3) immersing the MOFs nanosheet film seed crystal layer into the mixed solution, and heating to prepare the chemical resistance sensor.
7. A chemiresistive sensor made by the method of any one of claims 1-6.
8. The use of a chemiresistor-type sensor according to any one of claims 1 to 7 for the detection of nitro-explosives in an atmosphere, the specific detection method being as follows:
and connecting and electrifying the chemical resistance type sensor with a power supply, and applying voltage to detect the nitro explosive steam.
9. Use according to claim 8, wherein the nitro-explosive is TNT, DNT, PA, RDX or a derivative thereof.
10. Use according to claim 8, characterised in that the solvothermal method is chosen to obtain NH2MOFs, including NH2-MIL-125(Ti)，NH2-UIO-66(Zr)，NH2-MIL-101(Fe)，NH2-MIL-101(Cr)，NH2-MIL-101(Al)，NH2-MIL-53(Al)，Fe-MIL-88B-NH2，MOF-5-NH2，NH2-MIL-68(In)，NH2-CU3(BTC)2One or more of them.
CN202011606147.7A 2020-12-28 2020-12-28 Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application Pending CN114689664A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011606147.7A CN114689664A (en) 2020-12-28 2020-12-28 Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011606147.7A CN114689664A (en) 2020-12-28 2020-12-28 Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application

Publications (1)

Publication Number Publication Date
CN114689664A true CN114689664A (en) 2022-07-01

Family

ID=82132504

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011606147.7A Pending CN114689664A (en) 2020-12-28 2020-12-28 Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application

Country Status (1)

Country Link
CN (1) CN114689664A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686002A (en) * 2020-12-28 2022-07-01 中国科学院福建物质结构研究所 MOX @ NH2-MOFs thin film material and preparation method and application thereof
CN115219572A (en) * 2022-07-13 2022-10-21 重庆工商大学 Method for detecting nitrate ions by MOFs electrode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686002A (en) * 2020-12-28 2022-07-01 中国科学院福建物质结构研究所 MOX @ NH2-MOFs thin film material and preparation method and application thereof
CN115219572A (en) * 2022-07-13 2022-10-21 重庆工商大学 Method for detecting nitrate ions by MOFs electrode
CN115219572B (en) * 2022-07-13 2023-05-19 重庆工商大学 Method for detecting nitrate ions by MOFs electrode

Similar Documents

Publication Publication Date Title
Wang et al. High performance formaldehyde detection based on a novel copper (II) complex functionalized QCM gas sensor
US10495592B1 (en) Use of metal-organic frameworks and metal oxides for sensing chemicals using electrical impedance spectroscopy
Wang et al. Single-walled carbon nanotube/cobalt phthalocyanine derivative hybrid material: preparation, characterization and its gas sensing properties
Lan et al. Thin metal organic frameworks coatings by cathodic electrodeposition for solid-phase microextraction and analysis of trace exogenous estrogens in milk
Zhang et al. In-situ polymerization of metal organic frameworks-derived ZnCo2O4/polypyrrole nanofilm on QCM electrodes for ultra-highly sensitive humidity sensing application
CN114689664A (en) Method for preparing chemiresistive sensor by using amino functionalized metal organic framework material and application
CN101434612B (en) Metal organic framework compound material, as well as preparation and application thereof
Wu et al. A humidity sensor based on ionic liquid modified metal organic frameworks for low humidity detection
CN110887874B (en) Moisture-sensitive sensor based on perovskite and preparation method and application thereof
Omarova et al. A review on preparation methods and applications of metal–organic framework-based solid-phase microextraction coatings
Chowdhury et al. Template-and etching-free fabrication of two-dimensional hollow bimetallic metal-organic framework hexagonal nanoplates for ammonia sensing
CN113176305B (en) Composite gas-sensitive material and preparation method thereof, ethanol gas sensor and preparation method thereof
Xu et al. A pyridine vapor sensor based on metal-organic framework-modified quartz crystal microbalance
Yang et al. A fluorescent sensor for highly selective sensing of nitro explosives and Hg (ii) ions based on a 3D porous layer metal–organic framework
Khurshid et al. Aryl fluoride functionalized graphene oxides for excellent room temperature ammonia sensitivity/selectivity
CN110749628A (en) Acetone-sensitive cobaltosic oxide/zinc oxide nano-meter rice heterojunction thin film
Wang et al. The detection of formaldehyde using microelectromechanical acoustic resonator with multiwalled carbon nanotubes-polyethyleneimine composite coating
Zhai et al. Capacitive gas sensors based on a ZIF-67/PAN nanofiber membrane to detect volatile organic compounds
André et al. Porous materials applied to biomarker sensing in exhaled breath for monitoring and detecting non-invasive pathologies
Li et al. Imine Bond-Based Fluorescent Nanofilms toward High-Performance Detection and Efficient Removal of HCl and NH3
Lian et al. Electrodeposition of zeolitic imidazolate framework coating on stainless steel wire for solid-phase microextraction of polycyclic aromatic hydrocarbons in water samples
Chowdhury et al. Hierarchical bimetallic metal-organic frameworks with controllable assembling sub-units and interior architectures for enhanced ammonia detection
Li et al. Synthesis of different inorganic acids doped polyaniline materials and behavior of enhancing NH3 gas sensing properties
Wen et al. Synthesis of size-controllable urchin-like covalent organic frameworks for adsorption of nitrophenols
Wang et al. Hydroxyapatite nanorods: a nanobiomaterial for chemical detection of aniline vapor

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