CN115870009A - Preparation method and application of double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs (volatile organic compounds) - Google Patents
Preparation method and application of double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs (volatile organic compounds) Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 34
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- 238000000034 method Methods 0.000 claims description 11
- GVHCUJZTWMCYJM-UHFFFAOYSA-N chromium(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GVHCUJZTWMCYJM-UHFFFAOYSA-N 0.000 claims description 10
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a double-MOFs functional composite material for methane preparation through VOCs gas adsorption degradation, wherein a double-MOFs heterostructure can be used as a height-adjustable platform through adjusting the molar ratio of metal particles, and the pore structure is adjusted according to adsorbed target gas, so that selective adsorption is realized. Second NH 2 UIO-66 is used as an adsorption degradation material with low cost, no toxicity and high catalytic activity, and can effectively ensure the degradation efficiency of VOCs gas molecules.
Description
Technical Field
The invention belongs to the technical field of industrial VOCs gas adsorption and degradation, and particularly relates to a preparation method and application of a dual-MOFs functional composite material for methane preparation through VOCs gas adsorption and degradation.
Background
Volatile Organic Compounds (VOCs) are the main exhaust gas species emitted in industrial processes, including many alkanes, alkenes, alcohols, aldehydes, ketones, esters, terpenes, carbonyl compounds and organic acids. The toxic volatile organic compound gas can cause serious environmental pollution and even harm to human health, the removal of toxic gas pollutants in the air is vital to improve the air quality of indoor environment and maintain human health, and toluene (so-called phenyl methane and methyl benzene) is one of the main components of VOCs in the air, and acute contact with the compound can affect the central nervous system, and cause headache, runaway, spasm, coma and even death. Due to the inherent characteristics of high oxidation potential and high stable structure of the toluene, the degradation of the toluene by photocatalysis is an effective way with high efficiency and energy saving.
Metal Organic Frameworks (MOFs), a new class of porous materials, are assembled from metal ions or clusters and organic linkers, such as carboxylates or phosphonates, interconnected. Has large surface area, high porosity, chemical stability and controllable structure, and has great potential in the fields of drug delivery, catalysis, gas storage, selective adsorption and the like. MIL-101 (Cr) is used as a porous material mainly because it has high specific surface area and porosity, high concentration of open metal sites (-3.0 mmol/g 45-46), and high chemical stability, and can effectively trap VOCs gas molecules.
NH 2 UIO-66 as a novel MOF material has excellent hydrothermal and physicochemical stability, and the narrow band gap of 2.6-2.9 eV enables NH 2 UIO-66 has excellent visible light excitation characteristics, which enable good utilization and separation of photogenerated electrons and holes. NH contained on the surface 2 Functional groups, which can further enhance the selective adsorption characteristics thereof to target gases, and can effectively carry out photocatalytic degradation on low-concentration toxic gases.
On the basis, the invention constructs a double-MOFs functional composite material for methane preparation through VOCs gas adsorption and degradation, prepares a chromium-zirconium bimetallic MOFs heterostructure through in-situ loading by combining unique structures and properties of chromium-based MOF systems and zirconium-based MOF systems, has hierarchical porous properties, and can systematically design a hierarchical porous structure consisting of micropores and mesopores by adjusting the molar ratio of Zr/Cr in the MOF. NH (NH) 2 UIO-66 has large surface area and rich active sites, improving its photocatalytic performance, and the high porosity of MIL-101 allows VOCs gas molecules to stay on TiO 2 The surface is enriched in a large amount, and the degradation efficiency of VOCs gas is further improved.
Disclosure of Invention
Aiming at a large amount of VOCs gas generated in the current coal chemical production process, a double-MOFs functional composite material for methane adsorption and degradation is constructed, a double-MOFs heterostructure can be used as a height-adjustable platform by adjusting the molar ratio of metal particles, and the pore structure is adjusted according to the adsorbed target gas to realize selective adsorption. Second NH 2 UIO-66 asThe adsorption degradation material is low in cost, non-toxic and high in catalytic activity, and can effectively ensure the degradation efficiency of VOCs gas molecules.
The technical scheme of the invention is as follows:
a preparation method of a double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs comprises the following steps:
s1, synthesizing a chromium-based metal organic framework substrate material
S1-1, adding chromium nitrate nonahydrate and phthalic acid into deionized water, and preparing a uniform mixed solution through ultrasonic dispersion;
s1-2, transferring the mixed solution prepared in the S1-1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
s1-3, after the hydrothermal kettle in the S1-2 is cooled to room temperature, cleaning the hydrothermal kettle by using a centrifugal machine by using deionized water firstly, then cleaning the hydrothermal kettle by using a methanol solution, transferring the green precipitate into a vacuum oven for vacuum drying, and obtaining green powder: MIL-101;
s2, preparing the double-MOFs functional composite material for preparing methane by gas adsorption and degradation of VOCs
S2-1, adding the MIL-101 powder obtained in the S1-3 into an N, N-dimethylformamide solution, and preparing a uniform mixed solution through sealed ultrasonic dispersion;
s2-2, weighing zirconium chloride, 2-amino terephthalic acid and acetic acid, adding into the mixed solution of S2-1, and preparing a uniform mixed solution through sealed ultrasonic dispersion;
s2-3, transferring the mixed solution prepared in the S2-2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
s2-4, after the hydrothermal kettle in the S2-2 is cooled to room temperature, firstly cleaning by using N, N-dimethylformamide through a centrifugal machine, then cleaning by using an ethanol solution, and transferring the green precipitate into a vacuum oven for vacuum drying to obtain yellow-green powder: MIL-101@ NH 2 -UIO-66。
Preferably, in step S1:
the mixing ratio of the chromium nitrate nonahydrate to the phthalic acid in the step S1-1 is a molar ratio: 1, stirring for no less than 30 minutes;
the hydrothermal reaction temperature in the step S1-2 is 180 ℃, and the reaction time is not less than 15 hours;
in the step S1-3, the methanol and the deionized water are used successively for centrifugal cleaning, and the cleaning frequency is not less than 3 times.
Preferably, in step S2:
in the step S2-1, the MIL-101 and the N, N-dimethylformamide solution are stirred for not less than 20 minutes;
the mixing ratio of the zirconium chloride and the 2-amino terephthalic acid in the step S2-2 is a molar ratio: 1, stirring for no less than 30 minutes;
in the step S2-2, the mixing ratio of MIL-101 to chromium nitrate nonahydrate is at least three of the following:
the molar ratio is as follows: 4;
in the step S2-3, the hydrothermal reaction temperature is 120 ℃, and the reaction time is not less than 24 hours;
in the step S2-4, N-dimethylformamide and ethanol are used successively for centrifugal cleaning, the cleaning frequency is not less than 3 times, and the vacuum drying temperature is 70 ℃.
The application of the double-MOFs functional composite material for methane preparation through adsorption and degradation of VOCs obtained by the preparation method.
The specific steps of the application are as follows: the method comprises the following steps:
SA1, mixing MIL-101@ NH 2 The UIO-66 is placed in a double-layer photocatalytic reactor with the volume of 100ml, VOCs gas is connected to the input part of the reactor, and a flow meter is added in the gas path to control the flow rate; the output port of the reactor is connected with a gas washing bottle to collect waste gas;
SA2, in order to ensure that the air in the reactor is uniformly distributed, flowing air for 30min under the condition that a light source is closed, and then closing an input end and an output end to form a closed space filled with VOCs gas;
SA3, place the light source vertically in the upper part of the reactor, towards the center, turn on the light source.
SA4, injecting 200ml of gas from a gas inlet of the reactor into a gas chromatograph for quantitative measurement every 30min, and exploring the removal efficiency;
SA5, deionized water is added into the lower layer of the reactor to serve as a hydrogen source, and a degradation product cleaning and recycling way is explored.
Preferably, in step SA1, the reactor is charged with 0.2mg mL-1 of MIL-101@ NH2-UIO-66.
Preferably, in step SA2, the VOCs gas used is toluene gas, and the flow rate of the gas is 100ml min -1 。
Preferably, in step SA3, the light source used is an Ultraviolet (UV) lamp with a power of 8W and a maximum emission and intensity of 365nm and 1.52mW/cm, respectively 2 。
Preferably, in step SA5, deionized water is added in an amount corresponding to MIL-101@ NH 2 The relationship of-UIO-66 is 2g/mL.
Compared with the prior art, the invention can achieve the following beneficial effects:
1. the height-adjustable platform constructed by adjusting the molar ratio of the bimetal can adjust the pore structure to realize selective adsorption of different gases.
2. The generation rate of the dual MOFs functional composite material to methane gas is 18.63342 mu mol/g, and the dual MOFs functional composite material has an extremely large specific surface area of 1859.5290m 2 /g。
Drawings
FIG. 1 is an X-ray diffraction pattern of examples 1,2, 3 as shown in FIG. 1;
FIG. 2 is a scanning electron microscope image (SEM) of examples 1,2, 3;
FIG. 3 is a plot of the N2 adsorption isotherms (BET) for examples 1,2, 3;
FIG. 4 is a graph of the methane generation rates for examples one, two, and three and comparative examples one and two.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. .
The first embodiment is as follows:
the synthesis process of the composite material M-1 comprises the following specific steps:
MIL-101 Synthesis: chromium nitrate nonahydrate (Cr (NO) was weighed at 0.625mM 3 ) 3 ·9H 2 O) and 0.625mM terephthalic acid (C) 8 H 6 O 4 ) Adding the mixture into 10mL of deionized water, performing ultrasonic dispersion for 20 minutes, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating the mixed solution to 180 ℃, and performing hydrothermal reaction for 15 hours. Cooling to room temperature, centrifuging, collecting precipitate, washing with deionized water and methanol for 3 times, and vacuum drying at 70 deg.C.
Preparing a dual-MOFs functional composite material for methane preparation through VOCs gas adsorption and degradation:
0.09g of MIL-101 powder was weighed into 50mL of N, N-dimethylformamide solution, and the solution was mixed well by ultrasonic sealing for 20 minutes. Then 0.074g of zirconium chloride, 0.072g of 2-amino terephthalic acid and 5.5mL of acetic acid are weighed and added into the solution, and the solution is sealed and ultrasonically dispersed for 30 minutes continuously to prepare a uniform mixed solution; the reaction mixture was then transferred to a stainless steel autoclave with a teflon liner and subjected to hydrothermal reaction at 120 ℃ for 24 hours. And after the hydrothermal kettle is cooled to room temperature, respectively cleaning the hydrothermal kettle for 3 times by using N, N-dimethylformamide and an ethanol solution through a centrifugal machine, then transferring the yellow-green precipitate into a vacuum oven, and performing vacuum drying at 70 ℃ to finally obtain M-1.
Example two:
the synthesis process of the composite material M-2 comprises the following specific steps:
MIL-101 Synthesis: chromium nitrate nonahydrate (Cr (NO) was weighed at 0.625mM 3 ) 3 ·9H 2 O) and 0.625mM terephthalic acid (C) 8 H 6 O 4 ) Adding the mixture into 10mL of deionized water, carrying out ultrasonic dispersion for 20 minutes, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 180 ℃, and carrying out hydrothermal reaction for 15 hours. Cooling to room temperature, centrifuging to collect precipitate, washing with deionized water and methanol for 3 times, and vacuum drying at 70 deg.C。
Preparing a dual-MOFs functional composite material for methane preparation through VOCs gas adsorption and degradation:
0.045g of MIL-101 powder was weighed into 50mL of N, N-dimethylformamide solution, and the solution was mixed well by ultrasonic sealing for 20 minutes. Then 0.074g of zirconium chloride, 0.072g of 2-amino terephthalic acid and 5.5mL of acetic acid are weighed and added into the solution, and the solution is sealed and ultrasonically dispersed for 30 minutes continuously to prepare a uniform mixed solution; the reaction mixture was then transferred to a stainless steel autoclave with a teflon liner and subjected to hydrothermal reaction at 120 ℃ for 24 hours. And after the hydrothermal kettle is cooled to room temperature, respectively cleaning the hydrothermal kettle for 3 times by using N, N-dimethylformamide and an ethanol solution through a centrifugal machine, then transferring the yellow-green precipitate into a vacuum oven, and performing vacuum drying at 70 ℃ to finally obtain M-2.
Example three:
the synthesis process of the composite material M-3 comprises the following specific steps:
MIL-101 synthesis: chromium nitrate nonahydrate (Cr (NO) weighed 0.625mM 3 ) 3 ·9H 2 O) and 0.625mM terephthalic acid (C) 8 H 6 O 4 ) Adding the mixture into 10mL of deionized water, performing ultrasonic dispersion for 20 minutes, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating the mixed solution to 180 ℃, and performing hydrothermal reaction for 15 hours. Cooling to room temperature, centrifuging, collecting precipitate, washing with deionized water and methanol for 3 times, and vacuum drying at 70 deg.C.
Preparing a double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs:
0.18g of MIL-101 powder was weighed into 50mL of N, N-dimethylformamide solution, sealed and sonicated for 20 minutes, and the solution was mixed well. Then 0.074g of zirconium chloride, 0.072g of 2-amino terephthalic acid and 5.5mL of acetic acid are weighed and added into the solution, and the solution is sealed and ultrasonically dispersed for 30 minutes continuously to prepare a uniform mixed solution; the reaction mixture was then transferred to a stainless steel autoclave lined with teflon and subjected to hydrothermal reaction at 120 ℃ for 24 hours. And after the hydrothermal kettle is cooled to room temperature, respectively cleaning the hydrothermal kettle for 3 times by using N, N-dimethylformamide and an ethanol solution through a centrifugal machine, then transferring the yellow-green precipitate into a vacuum oven, and performing vacuum drying at 70 ℃ to finally obtain M-3.
Comparative example 1:
MIL-101 Synthesis: chromium nitrate nonahydrate (Cr (NO) was weighed at 0.625mM 3 ) 3 ·9H 2 O) and 0.625mM terephthalic acid (C) 8 H 6 O 4 ) Adding the mixture into 10mL of deionized water, carrying out ultrasonic dispersion for 20 minutes, transferring the mixed solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 180 ℃, and carrying out hydrothermal reaction for 15 hours. Cooling to room temperature, centrifuging, collecting precipitate, washing with deionized water and methanol for 3 times, and vacuum drying at 70 deg.C.
Comparative example 2:
NH 2 UIO-66 synthesis: weighing 0.074g of zirconium chloride, 0.072g of 2-aminoterephthalic acid and 5.5mL of acetic acid, adding the zirconium chloride, the 2-aminoterephthalic acid and the acetic acid into 50mL of N, N-dimethylformamide solution, and sealing and ultrasonically dispersing for 30 minutes to prepare uniform mixed solution; the reaction mixture was then transferred to a stainless steel autoclave with a teflon liner and subjected to hydrothermal reaction at 120 ℃ for 24 hours. After the hydrothermal kettle is cooled to room temperature, respectively cleaning the hydrothermal kettle for 3 times by using N, N-dimethylformamide and an ethanol solution through a centrifugal machine, then transferring the light yellow precipitate into a vacuum oven, and performing vacuum drying at 70 ℃ to finally obtain light yellow powder: NH (NH) 2 -UIO-66。
The specific surface areas of examples one, two and three and comparative examples one and two are shown in table 1;
FIG. 1 is an X-ray diffraction pattern of example three versus comparative examples one and two, with 2 θ =5 ° -30 ° assigned to typical MIL-101 (Cr) and NH 2 -UiO-66 (Zr), indicating successful synthesis of comparative example one and two, NH in example three 2 The peak of-UiO-66 (Zr) also appears in MIL-101 (Cr), indicating NH 2 -UiO-66 (Zr) was successfully introduced into MIL-101 (Cr). NH introduced compared to pure MIL-101 (Cr) 2 There are still many high and sharp peaks of-UiO-66 (Zr), which indicates that after two-phase compounding, the crystallinity is not changed and still goodGrain size and high crystallinity.
FIG. 2 is SEM images of example III and comparative examples I and II, where a and b in FIG. 2 show pure MIL-101 (Cr) and NH, respectively 2 Morphology of UiO-66, average grain size of MIL-101 (Cr) of about 120nm 2 The average grain size of the-UiO-66 is about 140nm. Reacting NH 2 NH after introduction of-UiO-66 into MIL-101 (Cr) 2 The grain size of the-UiO-66 is significantly reduced, which is likely that the presence of MIL-101 (Cr) suppresses NH 2 -UiO-66 grain growth results. NH in each phase along with different introduced amount of MIL-101 (Cr) 2 The grain size of the-UiO-66 also varies, NH in M-1 2 Average grain size of-UiO-66 was about 65nm (FIG. 2 c), NH in M-2 2 Average grain size of-UiO-66 was about 35nm (FIG. 2 d), NH in M-3 2 The average grain size of the-UiO-66 was about 40nm (FIG. 2 e), while the grain size of the MIL-101 (Cr) did not change significantly. In the photocatalytic reaction, the smaller particle size can shorten the diffusion distance of photo-generated charge carriers in MOFs, enrich the reaction sites on the surface and be more beneficial to the photocatalytic reaction.
FIG. 3 is a nitrogen adsorption curve for examples one, two, three and comparative examples one, two, all showing type IV curves, indicating mesoporous structure. MIL-101 (Cr), NH 2 Specific surface areas of-UiO-66, M-1, M-2 and M-3 were 1733.5870M, respectively 2 /g、571.9770m 2 /g、1859.5290m 2 /g、1208.1580m 2 /g、1,101.88m 2 (ii) in terms of/g. In addition, MIL-101 (Cr), NH 2 The average pore diameter of the-UiO-66 is 2.9nm and 7.2nm, and the larger pore diameter is greatly reduced by the average pore diameters of M-1, M-2 and M-3 after two-phase compounding, namely 4.2, 4.3nm and 3.4nm. The specific surface area of MIL-101 (Cr) is greater than that of M-2 and M-3, probably because the pore surface is coated with NH 2 -UiO-66 is occupied and NH 2 The pore size of the-UiO-66 is larger than that after the two phases are combined probably due to NH 2 Clogging of the-UiO-66 by MIL-101 (Cr), results which also demonstrate NH 2 The successful introduction of-UiO-66 into MIL-101 (Cr).
FIG. 4 shows that in the case of adding deionized water, the examples I, II and III and the comparative examples I and II are used for preparing CH by photocatalytic reduction of toluene in the process of illumination for 8h 4 Performance testing of (2). CH in the Presence of a Single MIL-101 4 Slow in growth rate, and after the two are combined, CH 4 The generation efficiency is greatly improved, and pure MIL-101 (Cr) and NH 2 Average hourly CH production of-UiO-66 4 The amounts of (A) and (B) were 7.59. Mu. Molh, respectively -1 g -1 And 3.24. Mu. Molh -1 g -1 M-1 average hourly CH production 4 In an amount of 18.63. Mu. Molh -1 g -1 . M-1 Generation of CH 4 The amounts are pure MIL-101 (Cr) and NH, respectively 2 About 3 times and 5 times of-UiO-66. The phenomenon shows that MIL-101 (Cr) and NH benefit from the synergistic effect of the two after the two are possibly compounded 2 Accelerated electron transport between the interfaces of the-UiO-66, the electron-hole recombination between the interfaces is suppressed, and the separation efficiency of excited electron-hole pairs is improved.
Claims (9)
1. A preparation method of a double-MOFs functional composite material for methane preparation through gas adsorption and degradation of VOCs is characterized by comprising the following steps: the method comprises the following steps:
s1, synthesizing a chromium-based metal organic framework substrate material
S1-1, adding chromium nitrate nonahydrate and phthalic acid into deionized water, and preparing a uniform mixed solution through ultrasonic dispersion;
s1-2, transferring the mixed solution prepared in the S1-1 into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
s1-3, after the hydrothermal kettle in the S1-2 is cooled to room temperature, washing with deionized water by using a centrifugal machine, washing with a methanol solution, transferring the green precipitate into a vacuum oven for vacuum drying to obtain green powder: MIL-101;
s2, preparing the double-MOFs functional composite material for preparing methane by gas adsorption and degradation of VOCs
S2-1, adding the MIL-101 powder obtained in the S1-3 into an N, N-dimethylformamide solution, and preparing a uniform mixed solution through sealed ultrasonic dispersion;
s2-2, weighing zirconium chloride, 2-amino terephthalic acid and acetic acid, adding into the mixed solution of S2-1, and preparing a uniform mixed solution through sealed ultrasonic dispersion;
s2-3, transferring the mixed solution prepared in the S2-2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction;
s2-4, after the hydrothermal kettle in the S2-2 is cooled to room temperature, firstly cleaning by using N, N-dimethylformamide through a centrifugal machine, then cleaning by using an ethanol solution, and transferring the green precipitate into a vacuum oven for vacuum drying to obtain yellow-green powder: MIL-101@ NH 2 -UIO-66。
2. The method of claim 1, wherein: in the step S1:
the mixing ratio of the chromium nitrate nonahydrate to the phthalic acid in the step S1-1 is a molar ratio: 1, stirring for no less than 30 minutes;
the hydrothermal reaction temperature in the step S1-2 is 180 ℃, and the reaction time is not less than 15 hours;
in the step S1-3, the methanol and the deionized water are used successively for centrifugal cleaning, and the cleaning frequency is not less than 3 times.
3. The method of claim 1, wherein: in the step S2:
in the step S2-1, the MIL-101 and the N, N-dimethylformamide solution are stirred for not less than 20 minutes;
the mixing ratio of the zirconium chloride and the 2-amino terephthalic acid in the step S2-2 is a molar ratio: 1, stirring for no less than 30 minutes;
in the step S2-2, the mixing ratio of MIL-101 to chromium nitrate nonahydrate is at least three of the following:
the molar ratio is as follows: 4;
in the step S2-3, the hydrothermal reaction temperature is 120 ℃, and the reaction time is not less than 24 hours;
in the step S2-4, N-dimethylformamide and ethanol are used successively for centrifugal cleaning, the cleaning frequency is not less than 3 times, and the vacuum drying temperature is 70 ℃.
4. Application of the dual MOFs functional composite material for methane preparation by VOCs gas adsorption degradation, which is obtained by the preparation method of any one of claims 1 to 3.
5. Use according to claim 4, characterized in that: the method comprises the following specific steps: the method is characterized by comprising the following steps:
SA1, mixing MIL-101@ NH 2 The UIO-66 is placed in a double-layer photocatalytic reactor with the volume of 100ml, VOCs gas is connected to the input part of the reactor, and a flow meter is added in the gas path to control the flow rate; the output port of the reactor is connected with a gas washing bottle to collect waste gas;
SA2, in order to ensure that the air in the reactor is uniformly distributed, air flows for 30min at a flowing speed under the condition that a light source is turned off, and then an input end and an output end are turned off to form a closed space filled with VOCs gas;
SA3, place the light source vertically in the upper part of the reactor, towards the center, turn on the light source.
SA4, injecting 200ml of gas from a gas inlet of the reactor into a gas chromatograph for quantitative measurement every 30min, and exploring the removal efficiency;
SA5, deionized water is added into the lower layer of the reactor to serve as a hydrogen source, and a degradation product cleaning and recycling way is explored.
6. Use according to claim 5, characterized in that: in step SA1, 0.2mg mL of the solution was placed in the reactor -1 MIL-101@ NH of 2 -UIO-66。
7. Use according to claim 5, characterized in that: in step SA2, the VOCs gas is toluene gas, and the flow rate of the gas is 100ml min -1 。
8. Use according to claim 5, characterized in that: in step SA3, the light source used is an Ultraviolet (UV) lamp with a power of 8W, and the maximum emission and intensity of the lamp are 365nm and 1.52mW/cm respectively 2 。
9. According to claim 5The use is characterized in that: in the step SA5, the amount of deionized water and MIL-101@ NH are added 2 The relationship of-UIO-66 is 2g/mL.
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