CN107029673A - A kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application - Google Patents
A kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of aluminium base MOFs/ graphene oxide composite materials and preparation method and application, comprise the following steps：(1) graphene oxide is scattered in low boiling point organic solvent, graphene oxide dispersion is obtained after being uniformly dispersed；(2) aluminum soluble salt and organic ligand are dissolved in graphene oxide dispersion, reactive matrix solution is obtained after dissolving completely；(3) isothermal reaction certain time under elevated pressure conditions after reactive matrix solution is heated up, head product is obtained；(4) head product is filtered, washed, activation produces aluminium based metal organic backbone/graphene oxide composite material after purification.The preparation method of the present invention is simple to operation, economic and environment-friendly, shortens the reaction time, reduces organic solvent usage amount, and obtain crystal formation and performance more preferably composite.Meanwhile, the toluene effect in composite absorption air significantly has good application prospect in terms of air pollution treatment.
Description
Technical field
The invention belongs to Materials Science and Engineering field, more particularly to a kind of aluminium base MOFs/ graphene oxide composite materials
And preparation method and application.
Background technology
With the fast development of China's economy, the continuous improvement of the level of urbanization, urgency occurs for the life style of people
The change of play, requirement of the people to interior decoration also more and more higher, various house decorative materials are widely used, and are caused tight
The room air pollution of weight.With regard to China presently, it is due to bad finishing to cause the main reason of room air pollution, that is, is existed
Used in fitment process and contain a large amount of harmful substances such as some ornament materials such as formaldehyde, benzene homologues, ammonia so that room air pollution
Problem becomes increasingly conspicuous.Serious room air pollution give people it is healthy bring huge threat, have impact on people normal
Working and learning.Therefore, room air pollution tool is reduced or eliminates to be of great significance
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) represent a class heterozygosis it is organic/
Inorganic supramolecular materials, are the ordered network structures being made up of the coordination of organic bridge ligand and inorganic metal ion.
The advantages of MOFs materials have the specific surface area of superelevation, relatively low crystalline density and hole size and function adjustability, in absorption
The fields such as separation show good potential application foreground.But it is due to that MOFs material atom density is low, it is impossible to provide enough
Dispersion force goes to capture small-molecule substance, therefore is usually combined with carbon-based material, overcomes or weakens this deficiency, so as to carry
The absorption property of high MOFs classes material.
Graphene is the carbon-based new material of discovered in recent years, possesses many excellent properties, such as higher mechanical strength, and heat is steady
Qualitative and electron mobility etc.；In addition, graphene also has regular two-dimensional structure, this makes it can be as preparing composite
Ideal carrier.Graphene oxide (graphene oxide, GO) is containing substantial amounts of on the important derivatives of graphene, GO monolithics
Epoxy radicals and hydroxyl, and contain carboxyl at monolithic edge, these features impart its good compound ability.These are graphene-based
Material had both possessed the excellent properties of graphene in itself with material made from organic or inorganic Material cladding, had organic or inorganic concurrently again
The self-characteristic of material, is that the preparation of specific function material opens new way.
The method of metal organic framework/graphene oxide composite material is prepared almost with N,N-dimethylformamide at present
(DMF) it is reaction dissolvent, after reaction terminates, DMF molecules can be remained in inside the duct of material or surface, and DMF boiling points
Higher than 150 DEG C, conventional heating (100 DEG C of ≈) volatilization purifying can not remove DMF molecules, it is therefore desirable to solvent is used for multiple times and carries out clearly
Wash, the material that can be just purified, meanwhile, organic solvent usage amount is big and easily causes environmental pollution.
The content of the invention
The primary and foremost purpose of the present invention is to overcome the shortcoming and deficiency of prior art, and there is provided a kind of organic bone of aluminium based metal
The preparation method of frame/graphene oxide composite material.
Another object of the present invention is to provide the aluminium based metal organic backbone/oxidation stone obtained by the preparation method
Black alkene composite.
A further object of the present invention is answering for aluminium based metal organic backbone/graphene oxide composite material described in offer
With.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of aluminium based metal organic backbone/graphene oxide composite material, comprises the following steps：
(1) graphene oxide is scattered in low boiling point organic solvent, is allowed to be uniformly dispersed, obtained graphene oxide and disperse
Liquid；
(2) aluminum soluble salt and organic ligand are dissolved in the graphene oxide dispersion obtained by step (1), dissolved
Reactive matrix solution is obtained after complete；
(3) by isothermal reaction certain time under elevated pressure conditions after the reactive matrix solution heating obtained by step (2), obtain
Aluminium based metal organic backbone/graphene oxide composite material head product；
(4) the aluminium based metal organic backbone for obtaining step (3)/graphene oxide composite material head product filtering, washing,
Activation, produces aluminium based metal organic backbone/graphene oxide composite material after purification.
The form of graphene oxide described in step (1) is preferably powder.
Scattered step described in step (1) is preferably disperseed by ultrasound.
The boiling point of low boiling point organic solvent described in step (1) is less than 100 DEG C；Preferably low boiling alcohols is organic molten
Agent；One kind or at least two more preferably in methanol, ethanol, propyl alcohol and isopropanol.
Graphene oxide described in step (1) is preferably 0.05mg/mL in the concentration of described low boiling point organic solvent
~0.2mg/mL.
Aluminum soluble salt described in step (2) is preferably one or both of aluminum nitrate and aluminium chloride.
Organic ligand described in step (2) is preferably terephthalic acid (TPA).
The proportioning preferred molar ratio of aluminum soluble salt and organic ligand described in step (2) is (2~6)：1.
Concentration of the aluminum soluble salt in graphene oxide dispersion described in step (2) is preferably 0.17~0.27g/
mL。
Aluminium based metal organic backbone described in step (3) is preferably MIL-68 (Al).
Condition of high voltage described in step (3) is preferably 1.6~10MPa；It is preferred that being realized by reactor.
Heating described in step (3) is preferably realized by gradient increased temperature；The condition of described gradient increased temperature is preferably：With
The temperature of reactive matrix solution is risen to 130~150 DEG C by 15~20 DEG C/h programming rate.
Isothermal reaction certain time described in step (3) is preferably 8~12h.
Washing described in step (4) is preferably to be cleaned 1 time or at least 2 times in water；More preferably 1~3 time；Institute
The time for the cleaning stated is preferably each at least 30min；More preferably 1~3h；Described water be preferably deionized water or
Ultra-pure water.
The concrete operations of activation described in step (4) are preferably that 10~12h is dried under the conditions of 100~120 DEG C.
A kind of aluminium based metal organic backbone/graphene oxide composite material, is prepared by methods described.
Described aluminium based metal organic backbone/graphene oxide composite material have three-decker (or be referred to as cladding knot
Structure), MIL-68 (Al) crystal homoepitaxial is in surface of graphene oxide.
Oxygen-containing functional group in described aluminium based metal organic backbone/graphene oxide composite material on graphene oxide with
Carboxyl on organic ligand there occurs competitive coordination.
The content of graphene oxide is preferably 2% in described aluminium based metal organic backbone/graphene oxide composite material
~10% (w/w).
The preparation method or described aluminium based metal of described aluminium based metal organic backbone/graphene oxide composite material have
Application of the machine skeleton/graphene oxide composite material in terms of toluene is adsorbed.
The present invention has the following advantages and effect relative to prior art：
(1) aluminium base MOFs/ graphene oxide composite material preparation methods of the invention, not only increase raw material especially oxygen
The utilization rate of graphite alkene, meanwhile, the crystallinity of the composite prepared by the present invention has also obtained notable optimization, obtains
Obtained the more excellent composite of performance.
(2) present invention is anti-using metal reaction kettle high pressure during aluminium base MOFs/ graphene oxide composite materials are prepared
Should, driving force is provided with the coordination of metal ion to come from the oxygen-containing functional group on organic ligand and graphene oxide, is contracted
The short reaction time, and composite crystalline form is more preferably, and performance is more excellent.
(3) present invention replaces conventional organic solvent N in composite material is prepared using low boiling alcohol organic solvent,
Dinethylformamide (DMF), purification step is more easy to carry out, and alcohols small molecule solvent is more beneficial for mass transfer, reduces anti-
The usage amount of organic solvent is answered, solvent further optimizes the structure and performance of gained composite using more abundant；The present invention
Organic solvent is replaced using deionized water or ultra-pure water in washing process, cost is lower, more environmentally friendly.
(4) metal machine framework material/graphene oxide composite material preparation method of the present invention is simple and can be large quantities of
Amount synthesis, the toluene effect used it in Adsorption air is notable.The material provides for the removal of air pollutants toluene
One efficiently, easily method.
Brief description of the drawings
Fig. 1 is aluminium based metal organic backbone/oxidation obtained by embodiment 1 and 3, embodiment 4~6 and comparative example 1
The XRD diffraction patterns of graphene composite material.
Fig. 2 is embodiment 5 and aluminium based metal organic backbone/graphene oxide composite wood obtained by comparative example 3,4
The XRD diffraction patterns of material.
Fig. 3 is embodiment 5 and aluminium based metal organic backbone/graphene oxide composite material obtained by comparative example 4
XPS sweep figure entirely.
Fig. 4 is the SEM figures of composite MIL-68 (Al)/GO-5 made from embodiment 5.
Fig. 5 is that aluminium based metal organic backbone made from embodiment 1,4 and 5/graphene oxide composite material removes toluene effect
The interpretation of result figure of fruit.
Fig. 6 is the knot that MOF materials made from composite prepared by embodiment 5 and comparative example 2 remove toluene effect
Fruit analysis chart.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Agents useful for same can routinely be bought from market unless otherwise specified in embodiment；Graphite oxide used in embodiment
Alkene powder is purchased from Shanghai Aladdin biochemical technology limited company (production code member G139803).
Embodiment 1 prepares aluminium based metal organic backbone/graphene oxide composite material
1.5mg graphene oxide powders are scattered in 21mL propyl alcohol, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
140 DEG C are risen to, 140 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 1h,
100 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-1.
Embodiment 2 prepares aluminium based metal organic backbone/graphene oxide composite material
1.5mg graphene oxide powders are scattered in 21mL propyl alcohol, after ultrasonic disperse, add 4.40g aluminium chloride and
After 1.53g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
140 DEG C are risen to, 140 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 3h,
110 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-2.
Embodiment 3 prepares aluminium based metal organic backbone/graphene oxide composite material
1.5mg graphene oxide powders are scattered in 21mL propyl alcohol, after ultrasonic disperse, add 6.68g aluminum nitrates and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
130 DEG C are risen to, 130 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 3h,
110 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-3.
Embodiment 4 prepares aluminium based metal organic backbone/graphene oxide composite material
1.5mg graphene oxide powders are scattered in 21mL isopropanols, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
130 DEG C are risen to, 130 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 1 time with deionized water, rinses 3h,
120 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-4.
Embodiment 5 prepares aluminium based metal organic backbone/graphene oxide composite material
2.0mg graphene oxide powders are scattered in 21mL isopropanols, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
150 DEG C are risen to, 150 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 1h,
110 DEG C of dry 12h, obtain sample labeled as MIL-68 (Al)/GO-5.
Embodiment 6 prepares aluminium based metal organic backbone/graphene oxide composite material
3.0mg graphene oxide powders are scattered in 21mL isopropanols, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
130 DEG C are risen to, 130 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 3h,
110 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-6.
Comparative example 1
1.5mg graphene oxide powders are scattered in 21mL DMF, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in reactor with 20 DEG C/h speed from 60 DEG C
130 DEG C are risen to, 130 DEG C of constant temperature 10h naturally cool to room temperature.Product after filtering is cleaned 3 times with deionized water, each 3h,
110 DEG C of dry 10h, obtain sample labeled as MIL-68 (Al)/GO-7.
Comparative example 2
4.40g Aluminium chloride hexahydrates and 0.61g terephthalic acid (TPA)s are dissolved in 21mL propyl alcohol, are placed in reactor and uniform
Stirring, obtained reaction solution rises to 130 DEG C from 60 DEG C with 20 DEG C/h speed, and 130 DEG C of constant temperature 5h naturally cool to room temperature.Cross
Product after filter is cleaned 3 times with deionized water, and 2h, 100 DEG C of dry 10h are cleaned every time, obtains sample labeled as MIL-68 (Al).
Comparative example 3
2.0mg graphene oxide powders are scattered in 21mL isopropanols, after ultrasonic disperse, add 4.40g aluminium chloride and
After 0.61g terephthalic acid (TPA)s, fully dissolving, obtained reactive group body fluid is placed in the flask with condensing reflux system, with
20 DEG C/h speed rises to 130 DEG C from 60 DEG C, and 130 DEG C of constant temperature 10h naturally cool to room temperature.Product deionization after filtering
Water is cleaned 3 times, each 3h, 110 DEG C of dry 10h, obtains sample labeled as MIL-68 (Al)/GO-8.
Comparative example 4
5.00g aluminium chloride and 5.0g terephthalic acid (TPA)s are dissolved in 300mL N, N '-dimethylformamide, uniform stirring makes
It is completely dissolved.Then 0.23g graphene oxide powders and ultrasonically treated, reaction mixture are added；Stirred under 130 DEG C of constant temperatures
Reaction 12 hours is mixed, room temperature is naturally cooled to.Product after filtering first uses N, and N '-dimethylformamide is rinsed 3 times, deionized water
Cleaning 3 times, in activating 12h under 110 DEG C of vacuum conditions, obtains sample labeled as MIL-68 (Al)/GO-9.
Effect example
1.XRD phenetic analysis
The sharp shadow X-ray diffractometers of Empyrean produced using Dutch PANalytical company are to the embodiment of the present invention 1 and 3, reality
The crystal structure for applying the preparation-obtained porous material of example 4~6 and comparative example 1,3 and 4 is characterized, as a result such as Fig. 1 and
Shown in Fig. 2, wherein operating condition is：Copper target, 40KV, 40mA, 0.02626 degree of step-length, 8.109 seconds/step of sweep speed.
Metal organic framework MIL-68 (Al) XRD characteristic diffraction peaks are 5,10,15 degree or so (WO/2008/129051),
It will be seen from figure 1 that metal organic framework made from embodiment 1,3 and embodiment 4~6/graphene oxide composite material performance
Go out MIL-68 (Al) feature peak position, illustrate the crystalline form that MIL-68 (Al) is remained in composite.MIL-68 (Al)/GO-4~
6 contrasts can be seen that with the increase of graphene oxide-loaded amount, and MIL-68 (Al) characteristic diffraction peak intensity gradually increases,
, can be by containing after graphene oxide excess, between them because contain substantial amounts of oxygen-containing high functional group on graphene oxide
Oxygen functional group is combined together rapidly, prevents occur coordination with metal ion, illustrates graphene oxide-loaded amount pair
MIL-68 (Al) crystallization has an impact.Additional embodiment 1,4 and comparative example 1 contrast it can be found that MIL-68 (Al)/GO-1,
4 XRD diffracted intensities are all higher than the diffracted intensity at MIL-68 (Al)/GO-7 correspondences peak, show to use low boiling point organic solvent system
Standby obtained MIL-68 (Al)/GO crystallinity is higher.
Figure it is seen that compared with MIL-68 (Al)/GO-5 prepared by embodiment 5, prepared by comparative example 3
MIL-68 (Al)/GO-8 XRD diffraction maximums have lacked MIL-68 (Al) in 5 degree or so of principal character peak, show parent metal
Organic backbone is not formed, and composite prepares failure, and inventor is by researching and analysing discovery, in composite preparation process
The pressure of generation has played important function.In addition, figure it is seen that MIL-68 (Al)/GO-5 materials prepared by embodiment 5
MIL-68 (the Al)/GO-9 materials prepared compared to comparative example 4, XRD diffraction maximums are stronger, show that its crystallinity is higher.
2.XPS is analyzed
The x-ray photoelectron spectroscopy (XPS, ESCALAB250Xi) produced using Sai Mofei companies of the U.S. is to of the invention real
Apply the composite prepared in example 5 and comparative example 4 to be swept entirely, determine the element species and content of composite.
From figure 3, it can be seen that two kinds of composites contain tetra- kinds of elements of C, H, O and Al.MIL-68 (Al)/GO-5 with
MIL-68 (Al)/GO-9 is compared, and the XPS signal intensities of MIL-68 (Al)/C and O elements contained by GO-5 are apparently higher than MIL-68
(Al)/GO-9, and the XPS signal intensities of Al elements are almost identical, these results suggest that MIL-68 (Al)/GO-5 phosphorus content and
Oxygen content is higher, shows that graphene oxide composition is higher, graphene oxide utilization rate is higher.
3.N2Adsorption/desorption is tested
The knot of composite prepared by embodiment 1 and embodiment 4~6 is tested using ASAP2020 specific-surface area detection instruments
Structure parameter, determines dry 12 hours in 100 DEG C in sample before 77K liquid nitrogen conditions, test, as a result as shown in table 1.Can be with by table 1
Find out, BET specific surface area, micropore specific area, total pore volume and the Micropore volume of MIL-68 (Al)/GO-4~6 are with oxidation
The load capacity increase of graphene shows a kind of trend for first increasing and reducing afterwards, shows the load capacity of graphene oxide to composite wood
The structural parameters of material have an impact, and the load capacity of graphene oxide has optimal proportion.
The composite structure parameter of table 1
4.SEM phenetic analysis
The aluminium prepared using MERLIN field emission scanning electron microscopes (Carl Zeiss companies, Germany) to embodiment 5
The surface topography of Base Metal organic backbone/graphene oxide composite material is characterized.As a result as shown in figure 4, composite is
Three-decker or clad structure, MIL-68 (Al) crystal homoepitaxials form similar sandwich structure in surface of graphene oxide.
5. absorption property is tested
Tabletting first is carried out to powdered aluminum Base Metal organic backbone/graphene oxide composite material using tablet press machine, broken into pieces
Screened using 200 mesh sieve, obtain fine granularity metal organic framework/graphene oxide composite material, weigh 0.5g graininess
Composite is in adsorption column, and adsorption column cross-sectional area is 5cm2, initial concentration is then passed to for 10mg/m3Toluene vapor, stream
Speed is 0.2m/s, and toluene vapor cycles through adsorption column, uses the concentration of gas-chromatography on-line testing toluene, 6 points of testing time
Clock/time.
Using the concentration of the model GC-2014 gas-chromatography on-line determination toluene of the Japanese Shimadzu Corporation's production in the U.S..Fig. 5
It is made with Fig. 6 for MIL-68 (the Al)/GO composites and comparative example 2 that under 298K, prepared by embodiment 1, embodiment 4 and 5
MIL-68 (Al) materials to Adsorption of Toluene curve map, composite is dried into 6h under the conditions of 100 DEG C before test.
MIL-68 (Al)/GO-1 and MIL-68 (Al)/GO-4 and 5 pair initial concentration are 10mg/m as shown in Figure 53Toluene
Absorption reached adsorption equilibrium at 120 minutes or so, and very fast in preceding 60 minutes rates of adsorption, and the clearance of final toluene is equal
More than 92% is reached, the clearance of wherein MIL-68 (Al)/final toluene of GO-5 reaches more than 95%, and this may be with material structure
Relating to parameters.
MIL-68 (Al)/GO-5 is better than individually in same time to the absorption property of toluene as seen from Figure 6
MIL-68 (Al) material.It is 10mg/m for initial concentration3Toluene vapor, adsorbed using MIL-68 (Al) through same time
Afterwards, the residual concentration of toluene is 1.57mg/m3, clearance is 84.3%；And use MIL-68 (Al)/GO-5 to be inhaled by 180min
It is attached toluene concentration is down to 0.48mg/m3, clearance is obviously improved, reaches 95.2%, illustrate that the introducing of graphene oxide is strong
Absorption of the material to toluene is changed, because the hexagonal carbon atomic plane in graphene oxide is enhanced and phenyl ring in toluene
π-π are acted on.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of aluminium based metal organic backbone/graphene oxide composite material, it is characterised in that including following step
Suddenly：
(1) graphene oxide is scattered in low boiling point organic solvent, is allowed to be uniformly dispersed, obtains graphene oxide dispersion；
(2) aluminum soluble salt and organic ligand are dissolved in the graphene oxide dispersion obtained by step (1), after dissolving completely
Obtain reactive matrix solution；
(3) by isothermal reaction certain time under elevated pressure conditions after the reactive matrix solution heating obtained by step (2), aluminium base is obtained
Metal organic framework/graphene oxide composite material head product；
(4) the aluminium based metal organic backbone for obtaining step (3)/graphene oxide composite material head product filtering, is washed, living
Change, produce aluminium based metal organic backbone/graphene oxide composite material after purification.
2. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：Low boiling point organic solvent described in step (1) is low boiling alcohol organic solvent.
3. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：Graphene oxide described in step (1) is 0.05mg/mL~0.2mg/ in the concentration of described low boiling point organic solvent
mL。
4. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：
Aluminum soluble salt described in step (2) is one or both of aluminum nitrate and aluminium chloride；
Organic ligand described in step (2) is terephthalic acid (TPA).
5. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：The proportioning of aluminum soluble salt and organic ligand described in step (2) is mol ratio (2~6)：1.
6. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：Condition of high voltage described in step (3) is 1.6~10MPa.
7. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：Heating described in step (3) is realized by gradient increased temperature.
8. the preparation method of aluminium based metal organic backbone/graphene oxide composite material according to claim 1, its feature
It is：Isothermal reaction certain time described in step (3) is 8~12h.
9. a kind of aluminium based metal organic backbone/graphene oxide composite material, it is characterised in that：It is any by claim 1~8
The preparation method of aluminium based metal organic backbone/graphene oxide composite material described in is prepared.
10. the preparation method or claim of aluminium based metal organic backbone/graphene oxide composite material described in claim 1
Application of the aluminium based metal organic backbone/graphene oxide composite material in terms of toluene is adsorbed described in 9.
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| CN108499534A (en) * | 2018-03-30 | 2018-09-07 | 南宁学院 | A kind of graphene-containing metal organic framework dense gas separation hybrid material and preparation method |
| CN109174019A (en) * | 2018-11-07 | 2019-01-11 | 东莞华工创为生物科技有限公司 | A kind of preparation method and application of aluminium based metal organic backbone@absorbent charcoal composite material |
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| CN114014311A (en) * | 2021-10-29 | 2022-02-08 | 广东极客亮技术有限公司 | Antibacterial and antiviral graphene and nano mirror aluminum composite material as well as preparation method and application thereof |
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| CN111621029A (en) * | 2020-05-29 | 2020-09-04 | 珠海市丝域生物科技有限公司 | Modified aluminum-based MOF material, preparation method and application thereof in hair products |
| CN111494240B (en) * | 2020-05-29 | 2023-01-31 | 珠海市丝域生物科技有限公司 | Composition containing aluminum-based MOFs material and application of composition in scalp care product |
| CN114014311A (en) * | 2021-10-29 | 2022-02-08 | 广东极客亮技术有限公司 | Antibacterial and antiviral graphene and nano mirror aluminum composite material as well as preparation method and application thereof |
| CN114570340A (en) * | 2022-03-11 | 2022-06-03 | 广东工业大学 | Application of graphene oxide/metal organic framework composite material in light-operated desorption of volatile organic compounds |
| CN114570340B (en) * | 2022-03-11 | 2024-04-05 | 广东工业大学 | Application of graphene oxide/metal organic framework composite material in light-controlled desorption of volatile organic compounds |
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