CN106513056B - A kind of preparation method of hybrid material and hybrid material, application - Google Patents
A kind of preparation method of hybrid material and hybrid material, application Download PDFInfo
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- CN106513056B CN106513056B CN201611068525.4A CN201611068525A CN106513056B CN 106513056 B CN106513056 B CN 106513056B CN 201611068525 A CN201611068525 A CN 201611068525A CN 106513056 B CN106513056 B CN 106513056B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a kind of preparation method of hybrid material and hybrid material, applications, wherein preparation method includes, using hydrofluoric acid selectively corrode MAX be combined to MXene, after by MXene be added to synthesis metal-organic framework materials precursor solution in synthesize hybrid material.MXene need to only be added during synthesizing metal organic framework and carry out hydridization preparation by the two-dimensional metallic carbonitride MXene and metal organic framework hybrid material of the present invention, and method is simple, can significantly improve the hydrothermal stability of metal-organic framework materials.
Description
Technical field
The invention belongs to chemical separating, catalysis technical fields, and in particular to a kind of preparation method and hydridization of hybrid material
Material, application.
Background technology
Before at the end of the 20th century, porous material is generally divided into two types：Inorganic material and carbonaceous material, in inorganic material
Using zeolite molecular sieve as representative, global economy is largely dependent upon application of the material in many industrial processes,
And activated carbon is just found as carbonaceous artificial material behind 1900 and 1901, because of its excellent absorbing and deodorizing function
So that in the second half in 20th century, environmental protection industry becomes the rich and influential family of activated carbon application.But it is with the development of the times, traditional porous
Material cannot increasingly meet the industrial requirement in the present age, at this moment, a kind of novel hybrid inorganic-organic materials metal organic framework
Material is born.
Nineteen ninety-five, first material for being named as metal organic framework (Metal-Organic Frameworks, MOFs)
Material is reported in Nature magazines.It is developed by YaghiOM, the complex with two-dimensional structure, by rigidity
Organic ligand trimesic acid synthesized with transition metal Co.In later 20 years, the Coordinative Chemistry of MOFs materials is with frightened
The speed and vigor of people is developed into an individual branches, and 1999, Yaghi OM were reported on Science magazines original
On the basis of be improved, with rigid organic ligand terephthalic acid (TPA) and transition metal zn synthesis with simple cubic structure
Three-dimensional MOF materials --- MOF-5.2002, for Yaghi again using MOF-5 as prototype, the organic union body for changing MOF-5 obtained one
Series has the micropore metal organic coordination compound IRMOF materials with MOF-5 similar structures, such as：IRMOF-8, IRMOF-1l and
IRMOF-18 realizes the leap from crystalline microporous material to crystal mesoporous material.
Metal-organic framework materials (MOFs) are a kind of porous nanometer materials being widely noticed at present, have high-ratio surface
The advantages that long-pending, adjustable duct, regular structure and abundant chemical mobility of the surface, gas storage, adsorbing separation, catalysis,
Biomedicine etc. has broad application prospects.However the stability of studies have shown that major part MOFs is poor.When these
When MOFs is exposed in wet environment, structure can occur it is irreversible cave in, this disadvantage limits the application of MOFs.
Invention content
The purpose of this part is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferably to implement
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of the above-mentioned and/or existing skill for preparing two-dimensional metallic carbonitride MXene and metal organic framework hybrid material
Art blank, it is proposed that the present invention.
Therefore, the one of purpose of the present invention is to solve deficiency in the prior art, provides a kind of good hydrothermal stability
Two-dimensional metallic carbonitride MXene and metal organic framework hybrid material preparation method.
In order to solve the above technical problems, the present invention provides following technical solutions：A kind of preparation method of hybrid material, packet
Include, using hydrofluoric acid selectively corrode MAX be combined to MXene, after by MXene be added to synthesis metal-organic framework materials before
It drives in liquid solution and synthesizes hybrid material, it is post-treated to obtain product.
A kind of preferred embodiment of preparation method as hybrid material of the present invention, wherein：It is described to be added to MXene
Synthesize metal-organic framework materials precursor solution in synthesize hybrid material, be by molar ratio be 1~2:1 metal salt and
Organic ligand is dissolved in solvent, adds MXene stirrings, 6~100h is reacted at 60~200 DEG C；The metal salt, wherein
Metal ion includes Zr4+、Cr3+、Al3+、Fe3+、Zn2+、Cu2+Or Mg2+One or more of；The organic ligand includes pyrrole
One or more of pyridine, imidazoles, trimesic acid or terephthalic acid (TPA)；The solvent includes water, methanol, ethyl alcohol, N, N- diformazans
One or more of base formamide, n,N-dimethylacetamide, dimethyl sulfoxide (DMSO), acetone or chloroform；The stirring, rotating speed
For 1000~2000rpm.
A kind of preferred embodiment of preparation method as hybrid material of the present invention, wherein：It is described selective using HF
Corrode MAX phases synthesis MXene, be that HF is added in MAX phases, under room temperature react 2~for 24 hours, number is washed with deionized
It is secondary, until the pH of aqueous solution close to neutrality, is put into 70~90 DEG C of vacuum drying chamber drying 12~for 24 hours.
A kind of preferred embodiment of preparation method as hybrid material of the present invention, wherein：A concentration of the 45 of the HF
~55wt%, additive amount are that 8~12mL is added per gMAX.
A kind of preferred embodiment of preparation method as hybrid material of the present invention, wherein：The post-processing, be by
The hybrid material of synthesis is washed with n,N-Dimethylformamide and soaked in absolute ethyl alcohol, then impregnates 3~7d with dichloromethane, then
Filtration drying.
Another object of the present invention is to solve deficiency in the prior art, provides a kind of two-dimensional metallic of good hydrothermal stability
Carbonitride MXene and metal organic framework hybrid material.
As a kind of preferred embodiment of hybrid material of the present invention, wherein：The two-dimensional metallic carbonitride and metal
The mass ratio of organic backbone is 0.005~0.5:1.
As a kind of preferred embodiment of hybrid material of the present invention, wherein：The two-dimensional metallic carbonitride and metal
The mass ratio of organic backbone is 0.01~0.20:1.
Further object of the present invention is to provide a kind of hybrid material using described in claim 6 and is used for catalysis oxidation benzene second
The method of alkene system is added after vacuumizing hybrid material at 115~125 DEG C in styrene oxide system, at 55~65 DEG C,
It is stirred to react under 900~1100r/min.
Further object of the present invention is to provide a kind of two-dimensional metallic carbonitride MXene and metal organic framework hybrid material
Application in terms of ultracapacitor.
Further object of the present invention is to provide a kind of hybrid material using described in claim 6 and is used for catalysis oxidation benzene second
The method of alkene system after hybrid material is vacuumized 2~4h of pretreatment at 140~160 DEG C, carries out gas absorption.
Beneficial effects of the present invention：
(1) two-dimensional metallic carbonitride MXene of the invention and metal organic framework hybrid material only need to be in synthesis metals
MXene is added during organic backbone and carries out hydridization preparation, method is simple, can significantly improve the water of metal-organic framework materials
Thermal stability.
(2) yield that hybrid material is made in preparation method provided by the invention is 70~90%.
(3) effect of the metal organic framework hybrid material produced by the present invention as catalyst in catalytic oxidation system
Fruit is splendid.
(4) effect pole of the metal organic framework hybrid material made from the invention as adsorbent in adsorbing separation system
Good, highest is adsorbed as CO2Adsorption capacity be 9.46mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 7.3:1, CO2/N2
Adsorptive selectivity be 40:1.
(5) hybrid material enhances compared to pure MOF electric conductivity, is used as ultracapacitor excellent.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without having to pay creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is associated materials X-ray diffraction spectrogram of the embodiment of the present invention, wherein：
1 is the spectrogram before the processing of HKUST-1 stability tests；
2 be HKUST-1 stability tests treated spectrogram；
3 be the spectrogram before the hybrid material stability test processing of embodiment 1；
4 for embodiment 1 hybrid material stability test treated spectrogram；
5 be the spectrogram before the hybrid material stability test processing of embodiment 2；
6 for embodiment 2 hybrid material stability test treated spectrogram；
7 be the spectrogram before the hybrid material stability test processing of embodiment 3；
8 for embodiment 3 hybrid material stability test treated spectrogram；
9 be the spectrogram before the hybrid material stability test processing of embodiment 4；
10 for embodiment 4 hybrid material stability test treated spectrogram；
11 be the spectrogram before the hybrid material stability test processing of embodiment 5；
12 for embodiment 5 hybrid material stability test treated spectrogram；
13 be the X-ray diffraction spectrogram of MXene-Ti3C2.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to specific embodiment pair
The specific implementation mode of the present invention is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention can be with
Implemented different from other manner described here using other, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Secondly, " one embodiment " or " embodiment " referred to herein refers to that may be included at least one realization side of the present invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiment.
The preparation of metal organic framework HKUST-1：Weigh the Gerhardite of 0.5000g and the equal benzene three of 0.2500g
N,N-Dimethylformamide, absolute ethyl alcohol and the water of 4.25mL is added in formic acid, 1h is stirred, by above-mentioned solution in 85 DEG C of temperature
Under be stirred to react, reaction time 21h.Sample filtering is taken out, is washed with n,N-Dimethylformamide and absolute ethyl alcohol, warp is taken out
Dichloromethane dries after impregnating, you can obtains metal organic framework HKUST-1.
The preparation of metal organic framework MOF-5：Weigh the zinc nitrate hexahydrate of 1.2100g and the terephthaldehyde of 0.3400g
40mL n,N-Dimethylformamide is added in acid, stirs 15min, is stirred to react at a temperature of 120 DEG C, and the reaction time is for 24 hours.It takes
Go out sample filtering, metal organic framework MOF-5 can be obtained after being washed with n,N-Dimethylformamide.
The preparation of metal organic framework MIL-53Al：Weigh 0.7900g ANN aluminium nitrate nonahydrate and 0.3400g to benzene two
40mL hydrofluoric acid (48wt%) and 20mL water is added in formic acid, and stirring 15min is stirred to react at 150 DEG C, and the reaction time is
80h.Sample filtering is taken out, is dried after being washed with water, you can obtains metal organic framework MIL-53Al.
The preparation of metal organic framework MIL-53Cr, weigh 0.8200g Chromium nitrate (Cr(NO3)3),nonahydrate and 0.3400g to benzene two
40mL hydrofluoric acid (48wt%) and 20mL water is added in formic acid, and stirring 15min is stirred to react at 180 DEG C, and the reaction time is
80h.Sample filtering is taken out, is dried after being washed with water, you can obtains metal organic framework MIL-53Cr.
The preparation of metal organic framework MIL-100Fe weighs the iron powder of 0.1330g and the trimesic acid of 0.2500g, adds
Enter 20mL hydrofluoric acid (48wt%) and 10mL water, stirs 15min, be stirred to react at 200 DEG C, reaction time 10h.Take out sample
Product filter, and are dried after being washed with water, you can obtain metal organic framework MIL-100Fe.
The preparation of metal organic framework MIL-101Cr, weigh 0.8900g six nitric hydrate chromium and 0.3400g to benzene
40mL hydrofluoric acid (48wt%) and 20mL water is added in dioctyl phthalate, and stirring 15min is stirred to react at 180 DEG C, and the reaction time is
10h.Sample filtering is taken out, is dried after being washed with water, you can obtains metal organic framework MIL-101Cr.
Embodiment 1
MXene-Ti3C2Preparation：Weigh 1g Ti3AlC210mL HF (49wt%) are added in powder, after reaction for 24 hours, use
Deionized water is washed several times, until solution ph is 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti3C2。
Weigh the Gerhardite of 0.5000g, the trimesic acid of 0.2500g and the MXene-Ti of 0.0075g3C2, point
Not Jia Ru 4.25mL n,N-Dimethylformamide, absolute ethyl alcohol and water, stir 1h, above-mentioned solution is stirred at a temperature of 85 DEG C
Mix reaction 1000-2000rpm, reaction time 21h.Sample filtering is taken out, with n,N-Dimethylformamide and soaked in absolute ethyl alcohol
Washing, taking-up are dried after dichloromethane impregnates, you can obtain metal organic framework HKUST-1 and MXene-Ti3C2Hydridization material
Material, it is 85% to calculate its yield.
Embodiment 2
MXene-Ti3C2Preparation：Weigh 1g Ti3AlC210mL HF (49wt%) are added in powder, after reaction for 24 hours, use
Deionized water is washed several times, until solution ph is 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti3C2。
Weigh the Gerhardite of 0.5000g, the trimesic acid of 0.2500g and the MXene-Ti of 0.0225g3C2, point
Not Jia Ru 4.25mL n,N-Dimethylformamide, absolute ethyl alcohol and water, stir 1h, above-mentioned solution is stirred at a temperature of 85 DEG C
Mix reaction, reaction time 21h.Sample filtering is taken out, is washed with n,N-Dimethylformamide and absolute ethyl alcohol, is taken out through dichloromethane
Alkane dries after impregnating, you can obtains metal organic framework HKUST-1 and MXene-Ti3C2Hybrid material, calculating its yield is
74%.
Embodiment 3
MXene-Ti3C2Preparation：Weigh 1g Ti3AlC210mL HF (49wt%) are added in powder, after reaction for 24 hours, use
Deionized water is washed several times, until solution ph is 6.12-24h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-
Ti3C2。
Weigh the Gerhardite of 0.5000g, the trimesic acid of 0.2500g and the MXene-Ti of 0.0375g3C2, point
Not Jia Ru 4.25mL n,N-Dimethylformamide, absolute ethyl alcohol and water, stir 1h, above-mentioned solution is stirred at a temperature of 85 DEG C
Mix reaction, reaction time 21h.Sample filtering is taken out, is washed with n,N-Dimethylformamide and absolute ethyl alcohol, is taken out through dichloromethane
Alkane dries after impregnating, you can obtains metal organic framework HKUST-1 and MXene-Ti3C2Hybrid material, calculating its yield is
80%.
Embodiment 4
MXene-Ti3C2Preparation：Weigh 1g Ti3AlC210mL HF (49wt%) are added in powder, after reaction for 24 hours, use
Deionized water is washed several times, until solution ph is 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti3C2。
Weigh the Gerhardite of 0.5000g, the trimesic acid of 0.2500g and the MXene-Ti of 0.0525g3C2, point
Not Jia Ru 4.25mL n,N-Dimethylformamide, absolute ethyl alcohol and water, stir 1h, above-mentioned solution is stirred at a temperature of 85 DEG C
Mix reaction, reaction time 21h.Sample filtering is taken out, is washed with n,N-Dimethylformamide and absolute ethyl alcohol, is taken out through dichloromethane
Alkane dries after impregnating, you can obtains metal organic framework HKUST-1 and MXene-Ti3C2Hybrid material, calculating its yield is
90%.
Embodiment 5
MXene-Ti3C2Preparation：Weigh 1g Ti3AlC210mL HF (49wt%) are added in powder, after reaction for 24 hours, use
Deionized water is washed several times, until solution ph is 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti3C2。
Weigh the Gerhardite of 0.5000g, the trimesic acid of 0.2500g and the MXene-Ti of 0.0750g3C2, point
Not Jia Ru 4.25mL n,N-Dimethylformamide, absolute ethyl alcohol and water, stir 1h, above-mentioned solution is stirred at a temperature of 85 DEG C
Mix reaction, reaction time 21h.Sample filtering is taken out, is washed with n,N-Dimethylformamide and absolute ethyl alcohol, is taken out through dichloromethane
Alkane dries after impregnating, you can obtains metal organic framework HKUST-1 and MXene-Ti3C2Hybrid material, calculating its yield is
82%.
Embodiment 6
MXene-Ti3The preparation of CN：Weigh 1g Ti310mL HF (49wt%) are added in AlCN powder, after reacting 18h, use
Deionized water is washed several times, until solution ph is 7.18h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti3CN。
Weigh the MXene-Ti of the zinc nitrate hexahydrate of 1.2100g, the terephthalic acid (TPA) of 0.3400g and 0.1550g3CN,
The n,N-Dimethylformamide of 40mL is added, stirs 15min, is stirred to react at a temperature of 120 DEG C, the reaction time is for 24 hours.It takes out
Sample filtering dries after being washed with n,N-Dimethylformamide, you can obtains metal organic framework MOF-5 and MXene-Ti3CN's
Hybrid material, it is 75% to calculate its yield.
Embodiment 7
MXene-Ti2The preparation of C：Weigh 1g Ti210mL HF (49wt%) are added in AlC powder, after reacting 10h, spend
Ion water washing several times, until solution ph be 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti2C。
Weigh the MXene-Ti of the ANN aluminium nitrate nonahydrate of 0.7900g, the terephthalic acid (TPA) of 0.3400g and 0.1130g2C adds
Enter 40mL hydrofluoric acid (48wt%) and 20mL water, stirs 15min, be stirred to react at 150 DEG C, reaction time 80h.Take out sample
Product filter, and are dried after being washed with water, you can obtain metal organic framework MIL-53Al and MXene-Ti2The hybrid material of C, calculates it
Yield is 82%.
Embodiment 8
MXene-V2The preparation of C：Weigh 1g V210mL HF (49wt%) are added in AlC powder, after reacting 8h, use deionization
Water washing several times, until solution ph be 5~7.12-24h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-V2C。
Weigh the MXene-V of the Chromium nitrate (Cr(NO3)3),nonahydrate of 0.8200g, the terephthalic acid (TPA) of 0.3400g and 0.1160g2C adds
Enter 40mL hydrofluoric acid (48wt%) and 20mL water, stirs 15min, be stirred to react at 180 DEG C, reaction time 80h.Take out sample
Product filter, and are dried after being washed with water, you can obtain metal organic framework MIL-53Cr and MXene-V2The hybrid material of C, calculates it
Yield is 77%.
Embodiment 9
MXene-Nb2The preparation of C：Weigh 1g Ti210mL HF (49wt%) are added in AlC powder, after reacting 90h, spend
Ion water washing several times, until solution ph be 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ti2C。
Weigh the MXene-Nb of the iron powder of 0.1330g, the trimesic acid of 0.2500g and 0.040g220mL hydrogen is added in C
Fluoric acid (48wt%) and 10mL water stir 15min, are stirred to react at 200 DEG C, reaction time 10h.Sample filtering is taken out,
It is dried after being washed with water, you can obtain metal organic framework MIL-100Fe and MXene-Nb2The hybrid material of C, calculating its yield is
81%.
Embodiment 10
MXene-Ta4C3Preparation：Weigh 1g Ta4AlC310mL HF (49wt%) are added in powder, after reacting 72h, use
Deionized water is washed several times, until solution ph is 6.20h is dried in 80 DEG C of vacuum drying chambers, you can obtains MXene-Ta4C3。
Weigh six nitric hydrate chromium, the terephthalic acid (TPA) of 0.3400g and the MXene-Ta of 0.1230g of 0.8900g4C3, add
Enter 40mL hydrofluoric acid (48wt%) and 20mL water, stirs 15min, be stirred to react at 180 DEG C, reaction time 10h.Take out sample
Product filter, and are dried after being washed with water, you can obtain metal organic framework MIL-101Cr and MXene-Ta4C3Hybrid material, calculate
Its yield is 84%.
Embodiment 11
Dimension carbonitride MXene and metal organic framework hybrid material produced by the present invention can be used as catalyst and urging
It is applied in oxidation system.
Catalytic applications are tested：Weigh 0.1000g metal-organic framework materials be put into it is closed in the three-necked flask of 50mL,
It is closed at 120 DEG C to vacuumize pretreatment, the styrene oxide of 0.3065g is weighed, 15mL absolute methanols is measured, is injected to flask
In, at a temperature of 60 DEG C, 1000r/min rotating speeds and logical N2Confined reaction under protective condition takes supernatant liquor to pass through after reacting 2.5h
Cross -2 benzyl carbinol of gas chromatographic analysis product 2- methoxyl groups.
Use No. 1 sample as catalyst, under the same reaction conditions, the yield for obtaining -2 benzyl carbinol of 2- methoxyl groups is
26.2%.
Use MXene-Ti3C2As catalyst, under identical reaction conditions, the yield of 2- methoxyl groups -2 phenylethyl alcohol is obtained
It is 0%.
It uses the hybrid material of embodiment 1 as catalyst, under the same reaction conditions, obtains -2 benzyl carbinol of 2- methoxyl groups
Yield is 60.6%.
It uses the hybrid material of embodiment 2 as catalyst, under the same reaction conditions, obtains -2 benzyl carbinol of 2- methoxyl groups
Yield is 63.5%.
It uses the hybrid material of embodiment 3 as catalyst, under the same reaction conditions, obtains -2 benzyl carbinol of 2- methoxyl groups
Yield is 80.6%.
It uses the hybrid material of embodiment 4 as catalyst, under the same reaction conditions, obtains -2 benzyl carbinol of 2- methoxyl groups
Yield is 78.5%.
It uses the hybrid material of embodiment 5 as catalyst, under the same reaction conditions, obtains -2 benzyl carbinol of 2- methoxyl groups
Yield is 52.4%.
Embodiment 12
Two-dimensional metallic carbonitride MXene and metal organic framework hybrid material produced by the present invention can be used as adsorbent and exist
It is applied in adsorbing separation system.
Adsorption applications are tested：It weighs a certain amount of metal-organic framework materials and is put into 2020 adsorption tester devices of ASAP
In sample cell, pretreatment 3h is vacuumized at 150 DEG C, the CO of 0~760mmHg pressure limits is tested at a temperature of 273K2, CH4With
N2Adsorption/desorption isotherms.Use No. 1 sample as adsorbent, under identical testing conditions, CO2Adsorption capacity be
7.94mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 6.6:1, CO2/N2Adsorptive selectivity be 41:1.Use MXene-
Ti3C2As adsorbent, under identical testing conditions, CO2Adsorption capacity be 0.09mmol/g adsorbents.With embodiment 1
Hybrid material is as adsorbent, and under identical testing conditions, the adsorption capacity of CO2 is 9.15mmol/g adsorbents, CO2/CH4
Adsorptive selectivity be 6.8:1, CO2/N2Adsorptive selectivity be 39:1.
Use the hybrid material of embodiment 2 as adsorbent, under identical testing conditions, CO2Adsorption capacity be
9.46mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 7.3:1, CO2/N2Adsorptive selectivity be 40:1.
Use the hybrid material of embodiment 3 as adsorbent, under identical testing conditions, CO2Adsorption capacity be
8.84mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 6.7:1, CO2/N2Adsorptive selectivity be 37:1.
Use the hybrid material of embodiment 4 as adsorbent, under identical testing conditions, CO2Adsorption capacity be
8.48mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 6.3:1, CO2/N2Adsorptive selectivity be 33:1.
Use the hybrid material of embodiment 5 as adsorbent, under identical testing conditions, CO2Adsorption capacity be
7.68mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 5.7:1, CO2/N2Adsorptive selectivity be 30:1.
Embodiment 13
Two-dimensional metallic carbonitride MXene and metal organic framework hybrid material produced by the present invention can be used as super capacitor
Device.The electric conductivity that MXene enhances MOF materials is introduced in metal-organic framework materials, to enhance the electrification of MOF materials
Learn performance.
Performance of the supercapacitor is tested：Electrode slice is made in sample, in 0.5M Na2SO4It is close that different electric currents are tested in solution
Unit capacitance values under degree.
Use No. 1 sample as electrode slice, it is 0.2Fg to measure specific capacitance-1。
Use MXene-Ti3C2As electrode slice, it is 50Fg to measure unit capacitance values-1。
Use the sample of embodiment 1 as electrode slice, it is 25Fg to measure specific capacitance-1。
Use the sample of embodiment 2 as electrode slice, it is 75Fg to measure specific capacitance-1。
Use the sample of embodiment 3 as electrode slice, it is 180Fg to measure specific capacitance-1。
Use the sample of embodiment 4 as electrode slice, it is 165Fg to measure specific capacitance-1。
Use the sample of embodiment 5 as electrode slice, it is 140Fg to measure specific capacitance-1。
Embodiment 14
Stability is tested：The HKUST-1 and Examples 1 to 5 its hybrid material for weighing about 0.02g, are positioned over one and open
It is placed in closed reaction kettle with 5mL water segregations in the container put, is placed in 70 DEG C of baking ovens and handles 12h.Respectively to processing before
Sample afterwards carries out X-ray diffraction test.
The MOF-5 and embodiment 6 its hybrid material for weighing about 0.02g, be positioned over 6h in air, respectively to before and after the processing
Sample carries out X-ray diffraction test.
The MIL-53Al and embodiment 7 its hybrid material for weighing about 0.02g, are positioned in an open container and 5mL
Water segregation is placed in closed reaction kettle, is placed in 90 DEG C of baking ovens and is handled 12h.X is carried out to sample before and after the processing respectively to penetrate
Line diffraction is tested.
The MIL-53Cr and embodiment 8 its hybrid material for weighing about 0.02g, are positioned in an open container and 5mL
Water segregation is placed in closed reaction kettle, is placed in 90 DEG C of baking ovens and is handled 12h.X is carried out to sample before and after the processing respectively to penetrate
Line diffraction is tested.
The MIL-100Fe and embodiment 9 its hybrid material for weighing about 0.02g, are positioned in an open container and 5mL
Water segregation is placed in closed reaction kettle, is placed in 90 DEG C of baking ovens and is handled 12h.X is carried out to sample before and after the processing respectively to penetrate
Line diffraction is tested.
The MIL-101Cr and embodiment 10 its hybrid material for weighing about 0.02g, be positioned in an open container with
5mL water segregations are placed in closed reaction kettle, are placed in 90 DEG C of baking ovens and are handled 12h.X is carried out to sample before and after the processing respectively
X ray diffraction is tested.
Sample structure is indicated with main peak intensity in X-ray diffraction spectrogram, by the peak intensity of sample after processing and sample before processing
The ratio between degree (0~100%) indicates the holding situation of structure.Ratio is bigger to illustrate that sample is more stable, and ratio is smaller to illustrate sample
It is more unstable.The ratio between peak intensity is 100% if sample structure is not destroyed, if it is 0% to destroy completely.The result is shown in Figure 1, table
1。
The stability of table 1. metal-organic framework materials and hybrid material
| Sample | Main peak intensity ratio before and after sample treatment |
| HKUST-1 | 21.7% |
| Embodiment 1 | 66.7% |
| Embodiment 2 | 87.8% |
| Embodiment 3 | 100% |
| Embodiment 4 | 100% |
| Embodiment 5 | 58.3% |
| MOF-5 | 12% |
| Embodiment 6 | 100% |
| MIL-53Al | 37% |
| Embodiment 7 | 100% |
| MIL-53Cr | 32% |
| Embodiment 8 | 100% |
| MIL-100Fe | 43% |
| Embodiment 9 | 100% |
| MIL-101Cr | 47% |
| Embodiment 10 | 100% |
It can be seen that two-dimensional metallic carbonitride MXene produced by the present invention and metal organic framework hybrid material only need
MXene is added during synthesizing metal organic framework and carries out hydridization preparation, method is simple, can significantly improve the organic bone of metal
The hydrothermal stability of frame material；The yield that hybrid material is made using preparation method provided by the invention is 70~90%；This hair
Bright excellent of the metal organic framework hybrid material as catalyst in catalytic oxidation system obtained；The invention system
Excellent of the metal organic framework hybrid material obtained as adsorbent in adsorbing separation system, highest are adsorbed as CO2's
Adsorption capacity is 9.46mmol/g adsorbents, CO2/CH4Adsorptive selectivity be 7.3:1, CO2/N2Adsorptive selectivity be 40:
1；Hybrid material enhances compared to pure MOF electric conductivity, is used as ultracapacitor excellent.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to preferable
Embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the technology of the present invention
Scheme is modified or replaced equivalently, and without departing from the spirit of the technical scheme of the invention and range, should all be covered in this hair
In bright right.
Claims (8)
1. a kind of preparation method of hybrid material, it is characterised in that：Including,
Selectively corrode MAX using hydrofluoric acid and be combined to MXene, after MXene is added to synthesis metal-organic framework materials
Hybrid material is synthesized in precursor solution, it is post-treated to obtain product；
Described MXene is added in the precursor solution of synthesis metal-organic framework materials synthesizes hybrid material, is that will rub
You are than being 1 ~ 2:1 metal salt and organic ligand is dissolved in solvent, add MXene stirring, at 60 ~ 200 DEG C react 6 ~
100 h；
The metal salt, wherein metal ion includes Zr4+、Cr3+、Al3+、Fe3+、Zn2+、Cu2+Or Mg2+One or more of；
The organic ligand includes one or more of pyridine, imidazoles, trimesic acid or terephthalic acid (TPA)；
The solvent include water, methanol, ethyl alcohol,N, NDimethylformamide,N, NDimethylacetylamide, dimethyl sulfoxide (DMSO), third
One or more of ketone or chloroform；
The stirring, rotating speed are 1000 ~ 2000rpm.
2. the preparation method of hybrid material according to claim 1, it is characterised in that：It is described selectively to be corroded using hydrofluoric acid
The synthesis MXene of MAX phases is that hydrofluoric acid is added in MAX phases, and 2 ~ 24 h are reacted under room temperature, number is washed with deionized
It is secondary, until the pH of aqueous solution close to neutrality, is put into 70 ~ 90 DEG C of vacuum drying chamber drying 12 ~ for 24 hours.
3. the preparation method of hybrid material according to claim 1 or claim 2, it is characterised in that：A concentration of the 45 of the hydrofluoric acid ~
55wt%, additive amount are that every gram of MAX adds 8 ~ 12mL.
4. the preparation method of hybrid material according to claim 1, it is characterised in that：The post-processing will synthesize
Hybrid material n,N-Dimethylformamide and absolute methanol washing by soaking, then 3 ~ 7d is impregnated with dichloromethane, it then crosses and is filtered dry
It is dry.
5. a kind of two-dimensional metallic carbonitride MXene and metal organic framework hybrid material, it is characterised in that：The two-dimensional gold
The mass ratio for belonging to carbonitride and metal organic framework is 0.005 ~ 0.5:1；Wherein, the hybrid material is made by the following method
,
Selectively corrode MAX using hydrofluoric acid and be combined to MXene, after MXene is added to synthesis metal-organic framework materials
Hybrid material is synthesized in precursor solution, it is post-treated to obtain product；
Described MXene is added in the precursor solution of synthesis metal-organic framework materials synthesizes hybrid material, is that will rub
You are than being 1 ~ 2:1 metal salt and organic ligand is dissolved in solvent, add MXene stirring, at 60 ~ 200 DEG C react 6 ~
100 h；
The metal salt, wherein metal ion includes Zr4+、Cr3+、Al3+、Fe3+、Zn2+、Cu2+Or Mg2+One or more of；
The organic ligand includes one or more of pyridine, imidazoles, trimesic acid or terephthalic acid (TPA)；
The solvent include water, methanol, ethyl alcohol,N, NDimethylformamide,N, NDimethylacetylamide, dimethyl sulfoxide (DMSO), third
One or more of ketone or chloroform；
The stirring, rotating speed are 1000 ~ 2000rpm.
6. hybrid material according to claim 5, it is characterised in that：The two-dimensional metallic carbonitride and the organic bone of metal
The mass ratio of frame is 0.01 ~ 0.20:1.
7. a kind of method that hybrid material using described in claim 5 is used for catalysis oxidation polystyrene systems, it is characterised in that：
By hybrid material 115 ~ 125oIt is added in styrene oxide system after being vacuumized under C, 55 ~ 65oC, 900 ~ 1100r/min
Under be stirred to react.
8. a kind of method that hybrid material using described in claim 5 can be applied to gas absorption, it is characterised in that：By hydridization
Material is 140 ~ 160oAfter vacuumizing 2 ~ 4 h of pretreatment under C, gas absorption is carried out.
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