CN109180951A - The preparation method of polyamines base organic-inorganic Hybrid compounds and application as hydrogen fluoride gas sensor - Google Patents
The preparation method of polyamines base organic-inorganic Hybrid compounds and application as hydrogen fluoride gas sensor Download PDFInfo
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Abstract
The invention discloses a kind of compound of the organic-inorganic heterozygosis of polyamines base, preparation method and as hydrogen fluoride gas sensor application, the compound of the organic-inorganic heterozygosis of polyamines base, using chromium ion as tie point, with 2,5- diamino-terephthalic acid (TPA) forms skeleton as ligand, porous, polyamino polymer material is formed, metal organic framework molecular structure is formed.The compound of the organic-inorganic heterozygosis of polyamines base of the present invention has metallo-organic framework, and stable structure, sensitive to hydrogen fluoride gas, good to gas-selectively.It can be used to prepare the novel hydrogen fluoride gas sensor of high-quality, be embedded into power battery management system, to monitor the micro-leakage of power battery electrolyte, early detection power battery leakage situation improves battery and safety of person vehicle.Gas sensor of the present invention has the application of gas sensor in industries such as medical treatment, environmental protection, military project, aerospace, industrial production, wearable devices.
Description
Technical field
The present invention relates to a kind of preparation method and applications of hydrogen fluoride gas sensitive material, especially further relate to a kind of metal
Organic framework compounds material, its application and preparation method, are applied to electrochemical function material, power battery technology field.
Background technique
China is a petroleum import big country, and China's Imported oil 80 about percent is used in the consumption of automobile, adds
Fuel vehicle using bringing troubling pollution problem, countries in the world have formulated substantially realize fuel vehicle before the year two thousand thirty at present
Quit listing, the development of new-energy automobile especially pure electric automobile has welcome opportunity.In addition people are to possessing Vehicular intelligent
Demand, electric car rapid development, ends " China Association for Automobile Manufacturers's data " in 2018, New Energy Sources In China automobile sales volume is
The continuous 3 years whole world first, publication in International Energy Agency 2016 " global electric car prospect in 2016 " require the year two thousand twenty whole world model
Will be reached by enclosing interior electric car quantity by 20,000,000.Only at just past 2017, New Energy Sources In China automobile sales volume just reaches
77.7 ten thousand.Pass through the market ploughing and weeding of new-energy automobile at present, degree of recognition of the new-energy automobile on market mountain has reached 90%
More than, the development of the new-energy automobile of the following pure electric vehicle will have great potential.
However power battery always exists certain risk in secure context, especially production, encapsulation and used
There are unreasonable operations in journey, will lead to the electrolyte leakage of battery.The current leakage for being directed to power battery electrolyte, BMS (electricity
Pond management system) solution be heat management monitoring, i.e., when battery exist leak when, abnormal operation will lead to battery mistake
Heat, so as to cause BMS alarm.But the monitoring of heat management system not can guarantee instantaneity, safety.Because power battery is from hair
It is several seconds to tens seconds the time required to heat to burning (explosion), and most of abnormal fever is usually irreversible, this
And why pure Electric power car has dieseling often.So there is asking for leakage in early detection power battery
Topic is more important.
The electrolyte of power battery can there are many, it is contemplated that the performance of battery, safety and recuperability,
Most power battery electrolytes are lithium hexafluoro phosphate (LiPF currently on the market6).Lithium hexafluoro phosphate once leaks into air
In will react with water vapor in air, generate hydrogen fluoride gas, related chemistry reaction equation are as follows: 2LiPF6+2H2O→
2PF5+2HF↑+2LiOH.Specific induction is carried out to the hydrogen fluoride gas of generation if be able to achieve, can more early realize electrolyte
The monitoring of leakage.Know that battery leakage occurs and can accomplish early discovery, early maintenance in advance, to reduce cell damage bring damage
It loses.In addition hydrogen fluoride is a kind of strong poisonous gas, realizes that early monitoring is a guarantee to the safety of operator.It is directed at present
The leakage of power battery electrolyte carries out the means of hydrogen fluoride gas detection temporarily without as it can be seen that being monitored to visit for hydrogen fluoride
Know whether power battery occurs leakage and belong to new project, so far there are no is applied to power for hydrogen fluoride gas detection sensitive material
The relevant report of battery technology field.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The organic-inorganic Hybrid compounds preparation method of polyamines base and as hydrogen fluoride gas sensor application, polyamines base of the present invention has
Machine inorganic hybrid compound has metallo-organic framework, and stable structure, sensitive to hydrogen fluoride gas, selects gas
Property is good.The compound of the organic-inorganic heterozygosis of polyamines base can be used to prepare the novel hydrogen fluoride gas sensor of high-quality, its is embedding
Enter in power battery management system (BMS), to monitor the micro-leakage of power battery electrolyte, early detection power battery is let out
Situation is leaked, battery and safety of person vehicle are improved.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of organic-inorganic Hybrid compounds of polyamines base, using chromium ion as tie point, with 2,5- diamino-terephthaldehyde
Acid forms skeleton as ligand, forms porous, polyamino polymer material, forms metal organic framework molecular structure.
As currently preferred technical solution, organic-inorganic heterozygosis that the organic-inorganic Hybrid compounds of polyamines base have
Material three-dimensional skeleton stereochemical structure includes following structural formula component:
As currently preferred technical solution, the compound of the organic-inorganic heterozygosis of polyamines base has organic-inorganic heterozygosis
The planar molecular structure formula of material is as follows:
A kind of application of the compound of the organic-inorganic heterozygosis of polyamines base of the present invention, can be used for hydrogen fluoride gas concentration not
Gas higher than 1000ppm is responded, and is detected to hydrogen fluoride gas.
As currently preferred technical solution, the application of the organic-inorganic Hybrid compounds of polyamines base can be used for fluorine
Change the gas that hydrogen gas concentration is 0.05ppm~100ppm to be responded, hydrogen fluoride gas is detected.
A kind of hydrogen fluoride gas sensor prepared by the organic-inorganic Hybrid compounds using polyamines base of the present invention, by polyamines
The compound of the organic-inorganic heterozygosis of base is coated in QCM quartz crystal microbalance, obtains QCM element, and QCM obtained is first
Part is set in hydrogen fluoride gas sensor module, and QCM hydrogen fluoride gas sensor is made.
A kind of application of hydrogen fluoride gas sensor of the present invention, is set to power battery management for hydrogen fluoride gas sensor
In system, power battery electrolyte leakage is monitored.
A kind of preparation method of hydrogen fluoride gas sensor of the present invention, includes the following steps:
(1) in deionized water by the organic-inorganic Hybrid compounds dissolution of polyamines base of the present invention, and ultrasonic disperse is carried out
At least after ten minutes, preparation concentration is not less than the hydrogen fluoride sensitive material slurry of 1mg/ml for processing;
(2) QCM element is coated in the hydrogen fluoride sensitive material slurry that micropipettor will be prepared in the step (1)
On, hydrogen fluoride sensitive material film is prepared, and with nitrogen as protection gas, carry out flash baking under the conditions of being not higher than 40 DEG C, Gu
Change;Then silver layer electrode is made in hydrogen fluoride sensitive material film surface, hydrogen fluoride sensitive material film is carried in silver electrode, is formed
Sandwich structure obtains QCM hydrogen fluoride sensing element;
(3) then, the QCM hydrogen fluoride sensing element prepared in the step (2) is supported on QCM fluorination hydrogen module
On, QCM hydrogen fluoride gas sensor is made.
A kind of preparation method of the organic-inorganic Hybrid compounds of polyamines base of the present invention, includes the following steps:
A. according to Cr3+: 2,5- diamino-terephthalic acid (TPA): the molar ratio of NaOH is the ratio of 1:1:2, takes solubility three
Valence chromic salts, 2,5- diamino-terephthalic acid (TPA) and NaOH are mixed together into deionized water, are stirred to molten as solute
Solution, obtains Cr3+The organic-inorganic mixed solution of polyamines base of the concentration not higher than 0.133mol/L;It is preferred that soluble chromic salt is
Cr(NO3)3、CrCl3、Cr2(SO4)3In any one salt or any a variety of salt-mixture;
B. then the organic-inorganic mixed solution of the polyamines base prepared in the step b is transferred in reaction kettle and carries out water
Heat treatment is being not less than 150 DEG C of progress hydro-thermal reaction at least 10h, is obtaining reaction product system solution;
C. by the reaction product system solution obtained in the step b carry out cooled to room temperature, then carry out from
The heart reuses DMF, ethyl alcohol and washs respectively at least 1 time, ethyl alcohol is then added in clean product, then be not higher than 100 DEG C of items
The alcohol mixture of product is kept at least 24 hours under part, then by overcritical vacuum drying method, by product mixtures
In solvent remove, obtain the compound products of the organic-inorganic heterozygosis of polyamines base.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the organic-inorganic Hybrid compounds of polyamines base of the present invention have metallo-organic framework, and stable structure,
It is sensitive to hydrogen fluoride gas, it is good to gas-selectively;
2. the compound of the organic-inorganic heterozygosis of polyamines base of the present invention is applied to hydrogen fluoride gas sensor, embed it in
On existing battery management system (BMS), to monitor the leakage situation of power battery electrolyte, guarantees safety of person vehicle, improve
Battery;Gas sensor testing result of the present invention is reliable, low in cost, is able to achieve long-term continuity detection, is suitble to
Apply the ongoing Security monitoring realized on power battery to hydrogen fluoride gas;
3. gas sensor is a high-tech, high skill present invention can apply in the preparation of hydrogen fluoride gas sensor
The application scenarios of the industry of art barrier, gas sensor are extensive, for example, medical treatment, environmental protection, military project, aerospace, industrial production, can
The industries such as wearable device have the application of gas sensor.
Detailed description of the invention
Fig. 1 is the three-dimensional framework configurational formula of the compound of the organic-inorganic heterozygosis of one polyamines base of the embodiment of the present invention.
Fig. 2 is bifluoride of embodiment of the present invention hydrogen body sensor successive steps sample introduction test chart.
Fig. 3 is bifluoride of embodiment of the present invention hydrogen Sensor Gas selectivity test figure.
Fig. 4 is bifluoride of embodiment of the present invention hydrogen body sensor reperformance test figure.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under:
Embodiment one
In the present embodiment, a kind of compound of the organic-inorganic heterozygosis of polyamines base, using chromium ion as tie point, with 2,5-
Diamino-terephthalic acid (TPA) forms skeleton as ligand, forms porous, polyamino polymer material, forms the organic bone of metal
Frame molecular structure.In the present embodiment, the organic-inorganic hybrid material three that the compound of the organic-inorganic heterozygosis of polyamines base has
Skeleton stereochemical structure is tieed up, includes following structural formula component:
In the present embodiment, the compound of the organic-inorganic heterozygosis of polyamines base has the plane point of organic-inorganic hybrid material
Subformula:
The Compound nomenclature of the organic-inorganic heterozygosis of the present embodiment polyamines base is NH2-MIL-002, is a kind of organic-inorganic heterozygosis
Sensitive material, planar molecular structure formula as described above, the compound referring to the organic-inorganic heterozygosis of Fig. 1 polyamines base three-dimensional bone
Frame configurational formula.The compound of the organic-inorganic heterozygosis of the present embodiment polyamines base has metallo-organic framework, and ties
Structure is stablized.
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, the application of the compound of the organic-inorganic heterozygosis of one polyamines base of embodiment, can be used for fluorination
Gas of the hydrogen gas concentration in 0.05ppm~1000ppm is responded, and is detected to hydrogen fluoride gas.
In the present embodiment, the hydrogen fluoride prepared using the compound of the organic-inorganic heterozygosis of polyamines base described in embodiment one
It is first to obtain QCM by the compound of the organic-inorganic heterozygosis of polyamines base coated in QCM quartz crystal microbalance for gas sensor
Part, and QCM element obtained is set in hydrogen fluoride gas sensor module, QCM hydrogen fluoride gas sensor is made.This reality
Applying example is a kind of USB interface class hydrogen fluoride gas sensor based on QCM element, is additionally provided in hydrogen fluoride gas sensor module
Display device can show the hydrogen fluoride gas concentration data of sample to be tested.Hydrogen fluoride gas sensor is set to power battery
In management system, power battery electrolyte leakage is monitored.
The preparation method of the present embodiment hydrogen fluoride gas sensor, includes the following steps:
(1) in deionized water by the compound dissolution of the organic-inorganic heterozygosis of polyamines base described in claim 1, it and carries out
Ultrasonic disperse processing after ten minutes, prepares the hydrogen fluoride sensitive material slurry that concentration is 1mg/ml;
(2) QCM element is coated in the hydrogen fluoride sensitive material slurry that micropipettor will be prepared in the step (1)
On, hydrogen fluoride sensitive material film is prepared, and with nitrogen as protection gas, flash baking is carried out under the conditions of 40 DEG C, is solidified;Then
Silver layer electrode is made in hydrogen fluoride sensitive material film surface, hydrogen fluoride sensitive material film is carried in silver electrode, forms sandwich
Structure obtains QCM hydrogen fluoride sensing element;
(3) then, the QCM hydrogen fluoride sensing element prepared in the step (2) is supported on QCM fluorination hydrogen module
On, QCM hydrogen fluoride gas sensor is made.The present embodiment can prepare a kind of USB interface class hydrogen fluoride gas based on QCM element
Sensor.
The analysis of sensor performance experimental test:
The present embodiment NH2- MIL-002 organic-inorganic heterozygosis metal organic framework molecule hydrogen fluoride gas sensor sensing material
This sensitive material of preparation is coated in QCM quartz crystal microbalance by the application of material, and QCM element obtained is final
Using in hydrogen fluoride gas sensor module.Step includes: that material obtained is dissolved in inside deionized water simultaneously ultrasound point
It dissipates, with micropipettor by sensitive material coated on QCM element, nitrogen is as protection gas, through flash baking in silver electrode
Sensitive membrane is made, QCM hydrogen fluoride element is successfully prepared.Later, the QCM by QCM element load in independent development is fluorinated hydrogen module
On, QCM hydrogen fluoride gas sensor is made.Obtained device stability is good.Successive steps sample introduction is carried out to sensor respectively
Test, gas respond selectivity test and response reperformance test, respectively referring to fig. 2, Fig. 3, Fig. 4.
Using the present embodiment hydrogen fluoride gas sensor, hydrogen is fluorinated to 500ppb, 1ppm, 2.5ppm, 5ppm, 10ppm
The test of body successive steps sample introduction, Fig. 2 are the present embodiment hydrogen fluoride gas sensor successive steps sample introduction test chart.Referring to fig. 2 may be used
To find out, hydrogen fluoride gas sensor manufactured in the present embodiment has good response, ladder to the hydrogen fluoride gas of 500ppb
During sample introduction, with the gradually intensification of concentration, response curve possesses good incremental and repeatability, possesses high sensitive
Degree.
Using the present embodiment hydrogen fluoride gas sensor, to the hydrogen fluoride of 1ppm, hydrogen sulfide, carbon dioxide, nitrogen dioxide,
Ammonia, nitric oxide, hydrogen, CO gas selectivity test.Fig. 3 is the choosing of the present embodiment hydrogen fluoride gas Sensor Gas
Selecting property test chart.Referring to Fig. 3 as can be seen that hydrogen fluoride gas sensor manufactured in the present embodiment possesses very various interference gas
Good selectivity, the response to hydrogen fluoride is 7 to 10 times of remaining common interference gas, and selection is had excellent performance.
Using the present embodiment hydrogen fluoride gas sensor, reperformance test is carried out to 500ppb hydrogen fluoride gas sensor,
Fig. 4 is the present embodiment hydrogen fluoride gas sensor reperformance test figure.Referring to fig. 4 as can be seen that fluorination manufactured in the present embodiment
Hydrogen body sensor is almost the same to its corresponding amplitude of the hydrogen fluoride gas response of 500ppb, has carried out 2000 circulating repetitions
Test, discovery response effect are almost the same.The NH of above-described embodiment2- MIL-002 organic-inorganic heterozygosis metal organic framework molecule
Synthesis and its in qcm sensor be used to detect hydrogen fluoride gas, be pioneer invention.This sensor of the present embodiment both utilized
This sensitive material to the high sensitivity and selectivity of hydrogen fluoride and the stability of molecule, and be utilized QCM element at
The advantages of this is low, device is simple, being easily integrated.At the same time, the preparation also for QCM sensing element sensitive material provides one
The new thinking of kind opens newly energy application field for the application of metal organic framework molecule.
In summary test result is it is found that embodiment two is prepared for quartz-crystal on the basis of sensitive material is succeeded in developing
The micro- balance of body (QCM) hydrogen fluoride gas sensor.The present invention had both widened metal organic framework compound material in gas sensing
It is sensitive also to provide a kind of stable, porous, high sensitivity polyamino for qcm sensor for application on device sensitive material
Design of material method.To the present embodiment two prepare hydrogen fluoride gas sensor carry out respectively selectivity, repeatability, sensitivity,
Detection of Stability, detection sensitivity.It carrying out being less than 500ppb, 2000 reperformance test performances are stablized, comparison and hydrogen sulfide,
The response of carbon dioxide, nitrogen dioxide, ammonia, nitric oxide, hydrogen, CO gas, hydrogen fluoride gas response are big
About their 7 times, it was demonstrated that selectivity is very well.Embodiment bifluoride hydrogen body sensor answering on power battery management system
With: on the basis of sensor element is succeeded in developing, in order to which hydrogen fluoride gas sensor to be embedded on BNS, realize fluorination
For the first time use of the hydrogen body sensor on power battery electrolyte leakage monitoring.
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of preparation method of the compound of the organic-inorganic heterozygosis of polyamines base of the present invention, including such as
Lower step:
A. according to Cr3+: 2,5- diamino-terephthalic acid (TPA): the molar ratio of NaOH is the ratio of 1:1:2, takes 2mmol solvable
Property chromic salt Cr (NO3)3·9H2O, the NaOH of 2,5- diamino-terephthalic acid (TPA) of 2mmol and 4mmol are as solute, and one
It rises and mixes into 15ml deionized water, be stirred to dissolution, obtain containing Cr3+Polyamines base organic-inorganic mixed solution;
B. the organic-inorganic mixed solution of the polyamines base prepared in the step b is then transferred to solvent is the anti-of 50ml
It answers and carries out hydro-thermal process in kettle, in 150 DEG C of progress hydro-thermal reaction 10h, obtain reaction product system solution;
C. by the reaction product system solution obtained in the step b carry out cooled to room temperature, then carry out from
The heart reuses DMF, ethyl alcohol and washs respectively 2 times, ethyl alcohol then is added in clean product, then to product under the conditions of 100 DEG C
Alcohol mixture kept for 24 hours, then by overcritical vacuum drying method, the solvent in product mixtures is removed, is obtained
To the compound products for the organic-inorganic heterozygosis for obtaining polyamines base.Molecular formula is referring to Fig. 1, it is seen that material obtained has polyamines
The structure of base, and stable structure.The present embodiment can prepare one NH of embodiment2The organic bone of-MIL-002 organic-inorganic heterozygosis metal
Frame molecule hydrogen fluoride gas sensor sensing material, preparation path is simple, efficiently, easily controllable, and yield is high, at low cost.
The NH2-MIL-002 MOF organic-inorganic heterozygosis sensitive material planar molecular structure formula of the present embodiment synthesis is as follows:
The compound of the organic-inorganic heterozygosis of polyamines base manufactured in the present embodiment, using chromium ion as tie point, 2,5- diaminos
Base-terephthalic acid (TPA) forms skeleton as ligand, is a kind of porous, polyamino polymer material.The porous offer of material compared with
For big specific surface area to be easy to adsorbed gas, the presence of polyamino improves the selectivity and sensitivity to hydrogen fluoride gas,
Entire skeleton possesses good stability, so that the use of material has good stability and repeatability.The present embodiment system
Standby sample is steady in a long-term, suitable for being used for a long time on power battery.
In conclusion the present invention is supervised to reach by detection hydrogen fluoride gas progress power battery electrolyte leakage
This purpose is surveyed, work of the invention is broadly divided into three parts: one, the preparation of hydrogen fluoride gas sensor sensing material;Two, fluorine
Change the preparation of hydrogen sensor element;Three, application of the hydrogen fluoride gas sensor on power battery management system (BMS).
Hydrogen fluoride gas sensor response of the present invention is sensitive, embeds it on existing battery management system (BMS), so that monitoring is dynamic
The leakage situation of power battery electrolyte guarantees safety of person vehicle, improves battery.The applied field of gas sensor of the present invention
Scape is extensive, such as the industries such as medical treatment, environmental protection, military project, aerospace, industrial production, wearable device have gas sensor
Using.Gas sensor testing result is reliable, low in cost, is able to achieve long-term continuity detection, is suitably applied in power battery
Upper realize monitors the ongoing Security of hydrogen fluoride gas.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
It is sensed without departing from the compound of the organic-inorganic heterozygosis of polyamines base of the present invention, preparation method and as hydrogen fluoride gas
The technical principle and inventive concept of device application, belong to protection scope of the present invention.
Claims (10)
1. a kind of compound of the organic-inorganic heterozygosis of polyamines base, which is characterized in that using chromium ion as tie point, with 2,5- diamino
Base-terephthalic acid (TPA) forms skeleton as ligand, forms porous, polyamino polymer material, forms metal organic framework point
Minor structure.
2. the compound of the organic-inorganic heterozygosis of polyamines base according to claim 1, it is characterised in that: the organic-inorganic having
Hybrid material three-dimensional framework stereochemical structure includes following structural formula component:
3. the compound of the organic-inorganic heterozygosis of polyamines base according to claim 2, it is characterised in that: have organic-inorganic miscellaneous
The planar molecular structure formula of condensation material:
4. a kind of application of the compound of the organic-inorganic heterozygosis of polyamines base described in claim 1, it is characterised in that: can be used for pair
Gas of the hydrogen fluoride gas concentration not higher than 1000ppm is responded, and is detected to hydrogen fluoride gas.
5. the application of the compound of the organic-inorganic heterozygosis of polyamines base according to claim 4, it is characterised in that: can be used for pair
Hydrogen fluoride gas concentration is that the gas of 0.05ppm~100ppm is responded, and is detected to hydrogen fluoride gas.
6. hydrogen fluoride gas sensing prepared by a kind of compound of organic-inorganic heterozygosis using polyamines base described in claim 1
Device, it is characterised in that: by the compound of the organic-inorganic heterozygosis of polyamines base coated in QCM quartz crystal microbalance, obtain QCM
Element, and QCM element obtained is set in hydrogen fluoride gas sensor module, QCM hydrogen fluoride gas sensor is made.
7. the application of hydrogen fluoride gas sensor described in a kind of claim 6, it is characterised in that: set hydrogen fluoride gas sensor
It is placed in power battery management system, power battery electrolyte leakage is monitored.
8. the preparation method of hydrogen fluoride gas sensor described in a kind of claim 6, which comprises the steps of:
(1) in deionized water by the compound dissolution of the organic-inorganic heterozygosis of polyamines base described in claim 1, and ultrasound is carried out
At least after ten minutes, preparation concentration is not less than the hydrogen fluoride sensitive material slurry of 1mg/ml to decentralized processing;
(2) it is coated on QCM element with the hydrogen fluoride sensitive material slurry that micropipettor will be prepared in the step (1),
Hydrogen fluoride sensitive material film is prepared, and with nitrogen as protection gas, carries out flash baking under the conditions of being not higher than 40 DEG C, solidifies;
Then silver layer electrode is made in hydrogen fluoride sensitive material film surface, hydrogen fluoride sensitive material film is carried in silver electrode, forms three
Mingzhi's structure obtains QCM hydrogen fluoride sensing element;
(3) then, the QCM hydrogen fluoride sensing element prepared in the step (2) is supported on QCM fluorination hydrogen module, system
Obtain QCM hydrogen fluoride gas sensor.
9. a kind of preparation method of the compound of the organic-inorganic heterozygosis of polyamines base described in claim 1, it is characterised in that:
A. according to Cr3+: 2,5- diamino-terephthalic acid (TPA): the molar ratio of NaOH is the ratio of 1:1:2, takes soluble trivalent chromium
Salt, 2,5- diamino-terephthalic acid (TPA) and NaOH are mixed together into deionized water as solute, are stirred to dissolution, obtain
To Cr3+The organic-inorganic mixed solution of polyamines base of the concentration not higher than 0.133mol/L;
B. then the organic-inorganic mixed solution of the polyamines base prepared in the step b is transferred in reaction kettle and is carried out at hydro-thermal
Reason is being not less than 150 DEG C of progress hydro-thermal reaction at least 10h, is obtaining reaction product system solution;
C. the reaction product system solution obtained in the step b is subjected to cooled to room temperature, is then centrifuged, then
It is washed respectively at least 1 time using DMF, ethyl alcohol, ethyl alcohol is then added in clean product, then under the conditions of being not higher than 100 DEG C
The alcohol mixture of product is kept at least 24 hours, it, will be in product mixtures then by overcritical vacuum drying method
Solvent removes, and obtains the compound products of the organic-inorganic heterozygosis of polyamines base.
10. the preparation method of the compound of the organic-inorganic heterozygosis of polyamines base according to claim 8, it is characterised in that:
In the step a, soluble chromic salt is Cr (NO3)3、CrCl3、Cr2(SO4)3In any one salt or any a variety of
Salt-mixture.
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