CN105126783B - Metal-organic framework materials parcel graphene parcel sponge and preparation method thereof - Google Patents
Metal-organic framework materials parcel graphene parcel sponge and preparation method thereof Download PDFInfo
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- CN105126783B CN105126783B CN201510467999.5A CN201510467999A CN105126783B CN 105126783 B CN105126783 B CN 105126783B CN 201510467999 A CN201510467999 A CN 201510467999A CN 105126783 B CN105126783 B CN 105126783B
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Abstract
The invention discloses a kind of preparation method of metal-organic framework materials parcel graphene parcel sponge, it is characterised in that：Sponge is immersed in graphene oxide solution, after centrifugal drying, is put into the synthesis mother liquid of metal-organic framework materials and grows, drying is taken out after certain time, produces metal-organic framework materials parcel graphene parcel sponge.The present invention utilizes the active force between metal-organic framework materials and graphene oxide, so that material raised growth and parcel in the sponge that graphene wraps up, and using the hydrophobic oleophilic oil characteristic of metal-organic framework materials, so that the sponge obtained can be used for water oil separation, simulation Crude Oil at Sea recovery.
Description
Technical field
The invention belongs to technical field of nano material, more particularly to a kind of metal-organic framework materials parcel graphene parcel
The preparation method of sponge.
Background technology
How to solve organic solvent pollution in water environment, particularly ocean Central Plains oily pollution, more and more closed
Note.High efficiency, the oleophilic oil material of recyclability have huge application prospect in materials chemistry and Environmental Chemistry field.It is more
The adsorbent of the hydrophobic oleophilic oil in hole has the ability of the selective absorption greasy dirt in aqueous phase well, passes through what is distilled or squeeze
Method, the oil of absorption is reclaimed, so as to reach the purpose that water oil separation recycles.But this method is relatively cumbersome, take compared with
It is long, the intrinsic disadvantages of the recovery of unsustainable property be present.
Prior art discloses a variety of methods for preparing hydrophobic oleophilic oil adsorbent, such as：Polydimethylsiloxane wraps up
Graphene wraps up sponge adsorbent, but the hydrophobic oleophilic oil adsorbent being fabricated to using metal-organic framework materials is not yet invented.
Metal-organic framework materials are mainly used in gas storage and separation, catalysis, sensing, medicament transport, constructed as template at present
New material etc., most of metal-organic framework materials are unstable in water, or even exposure will decompose in atmosphere,
Limit their development and application, thus invention is stablized, is easily-synthesized, the metal-organic framework materials of acid and alkali-resistance have it is huge
Application potential and value.
The content of the invention
The present invention is to avoid the weak point present in above-mentioned prior art, there is provided a kind of water oil separation, is particularly simulated
The method of Crude Oil at Sea recovery, it can not only improve oil absorption but also preparation technology can be simplified, improve organic efficiency.
In one aspect of the invention, there is provided a kind of sponge product, the sponge product include：
Sponge matrix；
Graphene oxide；With
Wrap up and be grown in the metallo organic material on graphene oxide sponge.
In one embodiment of the invention, the metallo organic material is to be used as tie point by metal ion, is had
The framework material that machine part is self-assembly of with metal.
In one embodiment of the invention, the metal is selected from copper, zinc and chromium；And/or wherein organic ligand is selected from
Terephthalic acid (TPA), equal benzene tricarbonic acid and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acids.
Another aspect of the present invention provides a kind of preparation method of sponge product, and methods described includes：
A, sponge is immersed in graphene oxide solution,
B, by the sponge centrifugal drying after immersion；
C, the dried sponge with graphene oxide is put into the mother liquor of metallo organic material and grown.
In one embodiment of the invention, the step of cleaning sponge is also included before step a.
In one embodiment of the invention, graphene oxide concentration described in step a is 0.5-10mg/mL, preferably
2-5mg/mL, further preferably 2-3mg/mL, most preferably 2.5mg/mL.
In one embodiment of the invention, centrifugal drying described in step b is gone to per minute per minute 1000
Carried out under 8000 turns of centrifugal rotational speed, preferably 2000-6000 turns, and further preferably 2500-4000 turns, most preferably 3000 turns.
In one embodiment of the invention, metal-organic framework materials are used as by metal ion described in step c
Tie point, organic ligand are self-assembly of with metal.
In one embodiment of the invention, the metal is selected from copper, zinc and chromium；And/or wherein organic ligand is selected from
Terephthalic acid (TPA), equal benzene tricarbonic acid and 4,4 '-(hexafluoroisopropylidenyl) two anhydride phthalic acids.
In one embodiment of the invention, the mother liquor of metal-organic framework materials described in step c is by the following
Configuration forms：
Mass ratio 2: 1 to 2: 5, preferably 2: 1 to 2: 4, further preferably 2: 2 to 2: 4, most preferably 2: 3 copper chloride and organic match somebody with somebody
Body；
Volume ratio is 3: 1 to 1: 3, preferably 3: 1 to 1: 1, further preferably 3: 1 to 2: 1, most preferably 3: 1 N, N- dimethyl methyls
Acid amides and water.
In one embodiment of the invention, 60 DEG C to 100 DEG C, preferably 70 DEG C to 90 DEG C are grown in described in step c,
Further preferably 80 DEG C to 85 DEG C, most preferably 85 DEG C, carry out growing 12-48 hours, preferably 18-42 hours, further preferably 24-36 hours,
Most preferably 24 hours.
Compared with the prior art, beneficial effects of the present invention include, but are not limited to：
1st, the present invention utilizes the active force between metal-organic framework materials and graphene oxide so that hydrophobic metals have
Machine framework material is wrapped up and grown in the sponge that graphene oxide wraps up, and synthetic method is simple, is prepared quick；The gold obtained
Category organic framework material parcel graphene parcel sponge hydrophobicity is strong, and oil absorption is big, is separated available for water oil, can also simulate sea
Crude oil separates.
2nd, metal-organic framework materials used in the present invention are in neutral, slant acidity and the meta-alkalescence aqueous solution, equal energy
It is stabilized.
Brief description of the drawings
The powder x-ray diffraction characterize data for the metal-organic framework materials that Fig. 1 is obtained by the embodiment of the present invention 1；
The scanning electricity for the metal-organic framework materials parcel graphene parcel sponge that Fig. 2 is obtained by the embodiment of the present invention 1
Sub- microscope photograph；
Fig. 3 is that the optical camera of sponge cosmetic variation in the building-up process of the embodiment of the present invention 1 is taken pictures picture；
Metal-organic framework materials powder and the metal-organic framework materials parcel that Fig. 4 is obtained by the embodiment of the present invention 1
Graphene parcel sponge material surveys its contact angle picture with water respectively；
Fig. 5 is carried out waterborne by the metal-organic framework materials parcel graphene parcel sponge that the embodiment of the present invention 1 obtains
Water oil separation experiment picture；
Fig. 6 is carried out underwater by the metal-organic framework materials parcel graphene parcel sponge that the embodiment of the present invention 1 obtains
Water oil separation experiment picture；
The graphene that Fig. 7 is obtained by the embodiment of the present invention 2 wraps up sponge and metal-organic framework materials wrap up graphene
Parcel sponge is individually positioned in filler neck part, enters water-filling oil separation experiment picture；
Fig. 8 is carried out using pump by the metal-organic framework materials parcel graphene parcel sponge that the embodiment of the present invention 3 obtains
Take out the diesel oil recovery experiment picture of 70% crude oil 30%；
Fig. 9 is simulated by the metal-organic framework materials parcel graphene parcel sponge that the embodiment of the present invention 3 obtains
Offshore oil-absorbing recovery experiment picture；
Embodiment
In one embodiment of the invention, the preparation of metal-organic framework materials parcel graphene parcel sponge
Method is carried out as follows：
A, after sponge is cleaned and dried, it is immersed in graphene oxide solution, is absorbed into saturation,
B, the sponge centrifugal drying of graphene oxide will be soaked, obtains graphene oxide/sponge；
C, graphene oxide/sponge is put into the mother liquor of metal-organic framework materials and grown,
D, the sponge after growth is taken out into drying, produces metal-organic framework materials/graphene/sponge.
In one embodiment of the invention, sponge described in step a is commercially available sponge.
In one embodiment of the invention, cleaning condition is described in step a：Use deionized water, ethanol
Cleaning 3-5 times.
In one embodiment of the invention, the condition dried described in step a is：100 DEG C of dry 12-24 are small
When.
In one embodiment of the invention, graphene oxide concentration described in step a is 1-4mg/mL.
In one embodiment of the invention, centrifugal rotational speed described in step b is 3000 rpms.
In one embodiment of the invention, drying condition described in step b is 100 DEG C of dry 12-24 hours.
In one embodiment of the invention, the mother liquor of metal-organic framework materials described in step c is two water
Copper chloride 450mg, part 300mg, deionized water 10ml, DMF 30ml, ultrasound fully mix.
In one embodiment of the invention, growth conditions described in step c is by above-mentioned mother liquor and oxidation stone
Black alkene/sponge is put into 100mL reactors, places into standing 12-24 hours in 85 DEG C of baking ovens.
In one embodiment of the invention, drying condition described in step d is to vacuumize dry 12- at 25 DEG C
24 hours.
Embodiment
Embodiment 1
The preparation method of the present embodiment metal-organic framework materials parcel graphene parcel sponge is to carry out as follows：
A, after sponge is cleaned and dried, it is immersed in graphene oxide solution, is absorbed into saturation,
B, by the sponge centrifugal drying after immersion, graphene oxide/sponge is obtained；
C, graphene oxide/sponge is put into the mother liquor of metal-organic framework materials and grown,
D, the sponge after growth is taken out into drying, produces metal-organic framework materials/graphene/sponge.
The metal-organic framework materials obtained to the present embodiment are immersed in different solutions, and powder is carried out after a period of time
X-ray diffraction characterizes, and as a result referring to Fig. 1, as shown in Figure 1, the metal-organic framework materials that the present embodiment is obtained are in the aqueous solution
Middle stabilization is equally stable in the acid solution that pH is 2 and in alkaline solution that pH is 10.
The metal-organic framework materials parcel graphene parcel sponge obtained to the present embodiment uses scanning electron microscopy
Sem observation, as a result referring to Fig. 2.As shown in Figure 2, the metal-organic framework materials parcel graphene parcel sea that the present embodiment is obtained
In silk floss, metal-organic framework materials raised growth, spongin surface is wrapped in.
Change to sponge outward appearance in the present embodiment building-up process is photographed to record with optical camera, as a result referring to Fig. 3.By scheming
3 understand, the white of sponge script becomes the khaki of graphene oxide after step a, b, becomes metal after step c, d
The blueness of organic framework material.
Metal-organic framework materials powder and metal-organic framework materials are used the present embodiment to wrap up graphene parcel
Sponge material, its contact angle with water is surveyed respectively, as a result referring to Fig. 4.As shown in Figure 4, the water of metal-organic framework materials powder
It is 132 ° to drip contact angle, and the water droplet contact angle of metal-organic framework materials parcel graphene parcel sponge material is 121 °.
Metal-organic framework materials parcel graphene parcel sponge progress water oil separation waterborne is obtained to the present embodiment to survey
Examination, as a result referring to Fig. 5.As shown in Figure 5, this material is placed in the aqueous solution of oil slick, oil can be siphoned away by material, and water is not
It can be siphoned away by material；By squeezing, the oil of absorption can be recycled.
The underwater water oil separation of metal-organic framework materials parcel graphene parcel sponge progress is obtained to the present embodiment to survey
Examination, as a result referring to Fig. 6.It will be appreciated from fig. 6 that when the density of oil is more than water, by this material be pressed onto it is underwater contacted with oily, oily equally meeting
Siphoned away by material, and water can't be siphoned away by material.
From above-mentioned experiment, metal-organic framework materials parcel graphene parcel sponge provided by the invention, have steady
The features such as fixed, hydrophobic, oleophylic.
Embodiment 2
The preparation method of the present embodiment metal-organic framework materials parcel graphene parcel sponge is to carry out as follows：
A, after sponge (2cm*2cm*2cm) is cleaned and dried, it is immersed in graphene oxide solution, is absorbed into saturation,
B, by the sponge centrifugal drying after immersion, graphene oxide/sponge is obtained；
C, graphene oxide/sponge is put into the mother liquor of metal-organic framework materials and grown,
D, the sponge after growth is taken out into drying, produces metal-organic framework materials/graphene/sponge.
The present embodiment is obtained into graphene parcel sponge and metal-organic framework materials parcel graphene parcel sponge
Separatory funnel neck is respectively charged into, the oil that density is more than water is then poured into above funnel, as a result referring to Fig. 7.As shown in Figure 7,
The sponge hydrophilic and oleophilic of common graphene oxide parcel, it is impossible to carry out water-oil separating；And metal-organic framework materials parcel graphite
Alkene wraps up sponge hydrophobic oleophilic oil, and oil infiltration is gone down, and water is retained in funnel.
From above-mentioned experiment, metal-organic framework materials parcel graphene parcel sponge provided by the invention, have steady
The features such as fixed, hydrophobic, oleophylic.
Embodiment 3
The preparation method of the present embodiment metal-organic framework materials parcel graphene parcel sponge is to carry out as follows：
A, after sponge (2cm*2cm*2cm) is cleaned and dried, it is immersed in graphene oxide solution, is absorbed into saturation,
B, by the sponge centrifugal drying after immersion, graphene oxide/sponge is obtained；
C, graphene oxide/sponge is put into the mother liquor of metal-organic framework materials and grown,
D, the sponge after growth is taken out into drying, produces metal-organic framework materials/graphene/sponge.
Metal-organic framework materials parcel graphene parcel sponge is obtained to the present embodiment to carry out using pumping crude oil recovery
Experiment, as a result referring to Fig. 8.As shown in Figure 8, continuously taken out by using pump, the crude oil to be floated on the surface in the container of the left side turns
Move on in the recovery beaker on the right, and water can't be pumped；Treat that crude oil recovery finishes, the beaker on the right can successively emerge
Bubble, illustrate that the material oil suction on the left side finishes beginning suck, do not absorb water.
Metal-organic framework materials parcel graphene parcel sponge is obtained to the present embodiment to carry out simulating offshore oil-absorbing time
Experiment is received, as a result referring to Fig. 9.As shown in Figure 9, when analog sea constantly teetertotters, oil can equally be shifted with pumping
Into recovery beaker, and water can't be sucked away；Treat that oil recovery finishes, reclaim the bubble that equally can successively be emerged in beaker,
Prove that left side material oil suction finishes beginning suck, do not absorb water.
From above-mentioned experiment, metal-organic framework materials parcel graphene parcel sponge material provided by the invention, exhibition
Reveal good hydrophobic oleophilic oil characteristic, and by improving oil suction technique, can successively, conveniently and efficiently by water-oil separating simultaneously
Recovery, illustrates on the sea for having stormy waves, rocking, and recovery oil suction experiment can equally be carried out.
Experiment shows metal-organic framework materials parcel graphene parcel sponge prepared by the present invention, have stable, thin
The advantages that water, oleophylic, synthetic method is safe and simple, can enter well for organic solvent of the density more than water and less than water
Row separation；And by further improving oil suction technique, it can realize that profit is successive, convenient and swift by the way of pumping
Ground recovery separation, it is practical, simple to operate, offshore oil-absorbing can be simulated, still there is good effect on the sea rocked.
Claims (6)
1. a kind of sponge product, the sponge product includes：
Sponge matrix；
Graphene oxide in the sponge matrix；With
The metallo organic material on graphene oxide sponge is wrapped up and is grown in,
Wherein described metallo organic material is to be used as tie point, the bone that organic ligand is self-assembly of with metal by metal ion
Frame material, wherein the metal is selected from copper, zinc and chromium；The organic ligand is selected from terephthalic acid (TPA), equal benzene tricarbonic acid and 4,4'-
(hexafluoroisopropylidenyl) two anhydride phthalic acid.
2. a kind of preparation method of sponge product, methods described include：
A, sponge is immersed in graphene oxide solution,
B, the sponge after immersion is dried；
C, the dried sponge with graphene oxide is put into the mother liquor of metal-organic framework materials and grown,
Metal-organic framework materials are used as tie point, organic ligand and metal from group by metal ion wherein described in step c
Dress is formed, wherein the metal is selected from copper, zinc and chromium；The organic ligand is selected from terephthalic acid (TPA), equal benzene tricarbonic acid and 4,4'-
(hexafluoroisopropylidenyl) two anhydride phthalic acid.
3. preparation method according to claim 2, wherein：
The step of also including cleaning sponge before step a；And/or
Graphene oxide concentration described in step a is 0.5-10mg/mL.
4. preparation method according to claim 2, wherein described in step b drying be gone to per minute 1000 it is per minute
The centrifugal drying carried out under 8000 turns of centrifugal rotational speed.
5. preparation method according to claim 2, the mother liquor of metal-organic framework materials is by following wherein described in step c
Items configuration forms：
Mass ratio 2:1 to 2:5 copper chloride and organic ligand；
Volume ratio is 3:1 to 1:3 N,N-dimethylformamide and water.
6. preparation method according to claim 2, it is small that 60 DEG C to 100 DEG C progress 12-48 are wherein grown in described in step c
When.
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