CN107790102A - A kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape and preparation method - Google Patents
A kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape and preparation method Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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Abstract
A kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape and preparation method, belong to oily water separation technique field.Including the three-dimensional redox graphene ball with pleated structure and it is immobilized on the metal-organic framework materials of accordion redox graphene piece interlayer；Specific method includes：Graphene oxide, metal salt and organic ligand are distributed in deionized water, make metal-organic framework materials growth in situ on stannic oxide/graphene nano piece, add reducing agent formed suspending liquid A；Or metal-organic framework materials are directly added into graphene oxide water solution, add reducing agent and form suspension B；By in suspending liquid A or suspension B press-in ultrasonic nozzles, the drop of micro/nano-scale is dispersed under ultrasonication and is deposited in high temperature organic solvent, stannic oxide/graphene nano piece issues in high temperature and reducing agent effect and is born from assembling.Composite prepared by the present invention has high oil-absorbing and cyclical stability.
Description
Technical field
The invention belongs to oily water separation technique field, and in particular to a kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape and
Preparation method.
Background technology
In recent years, because of industrial production and caused by oily waste water water be continuously increased, and marine oil spill event takes place frequently, profit point
It is extensively concerned from technology, but be a huge challenge simultaneously.Conventional oily water separation technique, such as flocculation, flotation, scrape slag, be broken
Breast and Gravity Separation etc., have that additive is more, easily causes chemical contamination, secondary pollution problems, and separation costs are high, separate
Efficiency is low.Absorption method has separative efficiency high, and cost is low, the advantages that can be recycled, its core be development adsorption capacity it is high, can
The high-performance adsorbent that stable circulation uses.
Graphene is with SP by carbon atom2A kind of New Two Dimensional atomic crystal that the monoatomic layer of hydridization connection is formed, reason
It is only 0.34nm by thickness, is the most thin nano material up to the present found, there is the specific surface area of super large and excellent power
The property learned.Because the intermolecular combination of water droplet internal water can be much larger than their energy of adsorptions between single-layer graphene surface, graphene
Certain hydrophobic property itself is shown, primitive, such as Nguyen can be constructed as super-hydrophobic-super oleophylic sorbing material
(D.D.Nguyen,N.H.Tai,S.B.Lee,W.S.Kuo,Energy Environ.Sci.,2012,5:7908-7912.) and
Gao etc. (Y.Liu, J.K.Ma, T.Wu, X.R.Wang, G.B.Huang, Y.Liu, H.X.Qiu, Y.Li, W.Wang, J.P.Gao,
ACS Appl.Mater.Interfaces.,2013,5:10018-10026.) using solution dipping method in commercial sponge table
The upper graphene sheet layer of face covering, make sponge material that there is super-hydrophobic-super oil-wet behavior, the absorbable about own wt of the composite
40~165 times of organic solvent or oil product.But oil molecule can only be transmitted by lamella duct, due to the two-dimensional characteristics of itself,
Mass transfer path is longer, and adsorption efficiency still has the space further lifted.If by physically or chemically acting on two-dimensional slice stone
Black alkene is transformed into the fold-like structures of three-dimensional, then being expected to can be further apart from shorter molecule transmission channels, while also for creation
Its hydrophobicity is improved, improves the separating property of sorbing material.
Metal-organic framework materials (Metal-Organic Frameworks, MOFs), are had by oxygen-containing or nitrogen rigidity
Machine part passes through the porous crystalline material of self assembling process formation with inorganic metal ion cluster, and its heat endurance is high, compares surface
Product is big, and porosity is high, and density is light, and a kind of potential super wetability oil absorption material.Such as Omary (Yang, C., Kaipa,
U.,Mather,Q.Z.,Wang,X.,Nesterov,V.,Venero,A.F.,Omary,M.A.,J.Am.Chem.Soc.,133
(45):18094-18097.) using fluorine-containing metal-organic framework materials (FMOF) as potential oil absorbent, applied to n-hexane,
In the reversible adsorption experiment of hexamethylene, benzene, toluene and paraxylene, it was demonstrated that also can not even in close under 100% relative humidity
Detect that water adsorbs, exhibit improvements over the hydrophobic performance of activated carbon and zeolite porous material.Therefore, suitable MOFs materials are selected
And be doped in graphene oxide and can combine both advantages, and self assembly be composite, for structure three-dimensional grapheme
Sorbing material provides may.Jayaramulu etc. [Jayaramulu, K., Datta, K.K.R.,C.,Petr,M.,
Otyepka,M.,Zboril,R.,Fischer,R.A.,Angew.Chem.Int.Edit.,2016,55(3):1178-1182.]
The composite that fluorine-containing graphene oxide is combined with ZIF-8 is impregnated on sponge, makes sponge that there is super-hydrophobic-super-oleophilic,
This sponge can absorb the organic solvent of itself 1.5-6 times of weight.But still a series of bottleneck problems be present, such as：Point of material
Still need further to be improved from efficiency and durability；The preparation of some materials needs fluorine-based polymer or modifying agent, and cost is high, easily
Cause secondary pollution etc..
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of preparation of the spherical MOFs@rGO materials of three-dimensional drape
Method, by graphene transition drape three-dimensional structure, the molecule transmission channels of graphene are enriched, it is rich to play MOF pore passage structures
Rich and the superpower mechanical property of graphene advantage, obtain strong super-hydrophobic-super oleophylic water-oil separating material of durability.Particular technique
Scheme is as follows：
The invention provides a kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape, it is characterised in that including with fold
The three-dimensional redox graphene ball of structure and the metal organic framework for being immobilized on accordion redox graphene piece interlayer
Material.
In the spherical MOFs@rGO oil absorption materials of described three-dimensional drape, the spherical redox graphene of three-dimensional drape is by two
Dimension stannic oxide/graphene nano piece is formed by high temperature reduction self assembly；Described metal-organic framework materials by growth in situ in
Redox graphene piece surface is immobilized in three-dimensional drape oxygen reduction by the physically encapsulation effect of redox graphene piece
In graphite alkene ball.
Specifically, the particle size range of the spherical MOFs@rGO oil absorption materials of described three-dimensional drape is 1~10 μm；Described gold
The particle size range for belonging to organic framework material is 1nm~1 μm.
Preferably, metal-organic framework materials be selected from class zeolite imidazole ester skeleton (ZIFs) material (including ZIF-1,
ZIF-2、ZIF-3、ZIF-4、ZIF-5、ZIF-6、ZIF-7、ZIF-8、ZIF-9、ZIF-10、ZIF-11、ZIF-12、ZIF-20、
ZIF-22, ZIF-67, ZIF-68, ZIF-69, ZIF-71, ZIF-78, ZIF-90, ZIF-95), IRMOF materials (including IRMOF-
0、IRMOF-1、IRMOF-2、IRMOF-3、IRMOF-4、IRMOF-5、IRMOF-6、IRMOF-7、IRMOF-8、IRMOF-9、
IRMOF-10, IRMOF-12, IRMOF-14, IRMOF-16, IRMOF-18), CPL series materials (including CPL-1, CPL-2),
MIL series materials (including MIL-23, MIL-24, MIL-47, MIL-53, MIL-68, MIL-77, MIL-88, MIL-100, MIL-
101), PCN series materials (including PCN-11, PCN-13, PCN-61, PCN-46, PCN-94, PCN-105, PCN-124, PCN-
222nd, PCN-888), at least one of UiO series materials (including UiO-66, UiO-67).
Specifically, in the spherical MOFs@rGO oil absorption materials of the three-dimensional drape, metal-organic framework materials are in reduction-oxidation
Load capacity on graphene is 0.1~5g/g.
The invention provides the preparation method of above-mentioned composite, comprise the following steps：
Step a, a certain amount of graphene oxide is distributed in deionized water, ultrasound makes its peeling, adds a certain amount of
Metal salt and organic ligand, make the metal-organic framework materials growth in situ of synthesis on stannic oxide/graphene nano piece, spend from
After sub- water eccentric cleaning, add a certain amount of reducing agent and form suspending liquid A；Or the graphene oxide after being uniformly dispersed is water-soluble
A certain amount of metal-organic framework materials are directly added into liquid, a certain amount of reducing agent is added and forms suspension B；
Step b, in the syringe with ultrasound, pressed by the suspending liquid A of formation or suspension B suctions by syringe pump
Enter in ultrasonic nozzle, suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 100-200 DEG C organic molten
In agent, stannic oxide/graphene nano piece issues in high temperature and reducing agent effect and is born from assembling, and makes metal-organic framework materials immobilized
In redox graphene piece interlayer；
Step c, the material of synthesis is centrifuged and cleaned, so as to obtain the described spherical MOFs@of three-dimensional drape
RGO oil absorption materials.
Specifically, in the step a, the concentration of original graphene oxide is 1-2g/L in suspending liquid A and suspension B；Enter
The concentration that metal salt is added in the preferred suspending liquid A of one step be 0.004~0.080mol/L, organic ligand concentration for 0.008~
6.00mol/L；The mass ratio of addition and graphene oxide that metal organic framework is directly added into suspension B is 0.1:1~
5:1.Added in step a in suspending liquid A and suspension B after reducing agent and there was only surface part graphene oxide in room temperature condition
Reduction.
Specifically, in the step a, 2-18h supersound process is carried out to the graphene oxide solution, ultrasonic power is not low
In 300w, per half an hour, stirring once, each ultrasonic 2-3h, makes the graphene oxide sheet footpath 50-500nm；Rotating speed during centrifugation
For 6000~10000rpm, 15~30 minutes time.
Preferably, in the step b, the reducing agent is ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, L- half
At least one of fat propylhomoserin, ammoniacal liquor, ammonia vapor, sodium borohydride, hydroiodic acid etc., the mass ratio with graphene oxide are 7:10
~100:10.
Specifically, in the step b, shower nozzle ultrasonic power is 0.5~1.5w；The injection rate of syringe pump be 0.2~
0.7ml/min；Syringe ultrasonic power is 0.5~1.5w；Shower nozzle direction is vertical downward direction.
Specifically, in the step b, the organic solvent is that the boiling points such as dimethyl silicone polymer, n-octyl alcohol are higher than 150 DEG C
And at least one of immiscible organic solvent of water, the temperature of organic solvent is preferably 120~200 DEG C.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：By high temperature reduction synchronization self assembly by oxygen
Graphite alkene and MOFs fast transformations into the spherical MOFs@rGO oil absorption materials of three-dimensional drape, MOFs ducts knot can be given full play to
The abundant advantage with the superpower performance of graphene of structure, forms it into multi-stage artery structure, optimizes oil molecule transmission channels, not only has
Stability Analysis of Structures, specific surface area are big, porosity is high and the characteristic such as super-hydrophobic, and do not need fluorine-based polymer, environment-friendly, into
This low, non-secondary pollution.
Brief description of the drawings
The spherical ZIF-8@rGO scanning of materials electron microscopes of three-dimensional drape prepared by Fig. 1 embodiment of the present invention 3；
The spherical ZIF-7@rGO scanning of materials electron microscopes of three-dimensional drape prepared by Fig. 2 embodiment of the present invention 4；
Spherical ZIF-67@rGO scanning of materials electron microscope (3-1) table of three-dimensional drape prepared by Fig. 3 embodiment of the present invention 5
Face and the amplification of (3-2) surface texture；
Scanning electron microscope (SEM) photograph is observed and determined using Hitachi S-4800 types SEM (SEM).
Below in conjunction with the drawings and the specific embodiments, the invention will be further described.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is described in further detail, but the present invention is not limited to following examples.
In a first aspect, the embodiments of the invention provide a kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape, including with
The three-dimensional redox graphene ball of pleated structure and be immobilized on accordion redox graphene piece interlayer metal it is organic
Framework material；
In the spherical MOFs@rGO oil absorption materials of described three-dimensional drape, the spherical redox graphene of three-dimensional drape is by two
Dimension stannic oxide/graphene nano piece is formed by high temperature reduction self assembly；Described metal-organic framework materials by growth in situ in
Redox graphene piece surface is immobilized in three-dimensional drape oxygen reduction by the physically encapsulation effect of redox graphene piece
In graphite alkene ball.
Specifically, can be with preferably, the particle size range of described metal organic framework complex material is 1nm~1 μm
For 10nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, by solid
The superficiality of the spherical MOFs@rGO materials of the three-dimensional drape can be regulated and controled by carrying the metal-organic framework materials of different-grain diameter size
Matter, regulate and control its water-oil separating performance.
Preferably, metal-organic framework materials be selected from class zeolite imidazole ester skeleton (ZIFs) material (including ZIF-1,
ZIF-2、ZIF-3、ZIF-4、ZIF-5、ZIF-6、ZIF-7、ZIF-8、ZIF-9、ZIF-10、ZIF-11、ZIF-12、ZIF-20、
ZIF-22, ZIF-67, ZIF-68, ZIF-69, ZIF-71, ZIF-78, ZIF-90, ZIF-95), IRMOF materials (including IRMOF-
0、IRMOF-1、IRMOF-2、IRMOF-3、IRMOF-4、IRMOF-5、IRMOF-6、IRMOF-7、IRMOF-8、IRMOF-9、
IRMOF-10, IRMOF-12, IRMOF-14, IRMOF-16, IRMOF-18), CPL series materials (including CPL-1, CPL-2),
MIL series materials (including MIL-23, MIL-24, MIL-47, MIL-53, MIL-68, MIL-77, MIL-88, MIL-100, MIL-
101), PCN series materials (including PCN-11, PCN-13, PCN-61, PCN-46, PCN-94, PCN-105, PCN-124, PCN-
222nd, PCN-888), at least one of UiO series materials (including UiO-66, UiO-67).
Specifically, in the spherical MOFs@rGO oil absorption materials of the three-dimensional drape, the load capacity of metal-organic framework materials is
0.1~5g/g, can be 0.1g/g, 0.2g/g, 0.3g/g, 0.4g/g, 0.5g/g, 0.6g/g, 0.7g/g, 0.8g/g, 0.9g/
G, 1.0g/g, 2g/g, 3g/g, 4g/g or 5g/g；Load capacity is too low, metal-organic framework materials effect unobvious, load capacity mistake
Height, the mechanical property effect of grapheme material is limited, and material is easily unstable, by the load capacity for controlling metal-organic framework materials
The surface nature and pore passage structure of the oil absorption material can be regulated and controled, and then optimize its water-oil separating performance.
Second aspect, the embodiments of the invention provide the preparation method of above-mentioned oil absorption material, including：
Step a, a certain amount of graphene oxide is distributed in deionized water, ultrasound makes its peeling, adds a certain amount of
Metal salt and organic ligand, make the metal-organic framework materials growth in situ of synthesis on stannic oxide/graphene nano piece, spend from
After sub- water eccentric cleaning, add a certain amount of reducing agent and form MOFs@rGO suspending liquid As；Or the oxidation stone after being uniformly dispersed
A certain amount of metal-organic framework materials are directly added into black aqueous solution, a certain amount of reducing agent is added and forms suspension B；
Step b, in the syringe with ultrasound, pressed by the suspending liquid A of formation or suspension B suctions by syringe pump
Enter in ultrasonic nozzle, suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 100-200 DEG C organic molten
In agent, stannic oxide/graphene nano piece issues in high temperature and reducing agent effect and is born from assembling, and makes metal-organic framework materials immobilized
In redox graphene piece interlayer；
Step c, the material of synthesis is centrifuged and cleaned, so as to obtain the described spherical MOFs@of three-dimensional drape
RGO oil absorption materials.
Preferably, in the step a, the concentration of graphene oxide is 0.1-2g/L in suspending liquid A and suspension B；It is dense
Degree is less less than graphene oxide amount in 0.1g/L suspension, increases its self assembly difficulty in high temperature reduction；Concentration is higher than 2g/
L, graphene oxide are difficult to be uniformly dispersed in aqueous.Specifically, the concentration can be 0.1g/L, 0.2g/L, 0.3g/L,
0.4g/L、0.5g/L、0.6g/L、0.7g/L、0.8g/L、0.9g/L、1g/L、1.1g/L、1.2g/L、1.3g/L、1.4g/L、
1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L or 2g/L, controlled by the graphene oxide solution for regulating and controlling various concentrations
The size for the composite that metallic framework material in situ is grown or doping is formed, and then control three-dimensional drape after high temperature reduction assembling
The size of spheroidal material.
Preferably, the concentration that metal salt is added in suspending liquid A is 0.004~0.080mol/L, can be 0.004mol/
L、0.006mol/L、0.008mol/L、0.010mol/L、0.020mol/L、0.030mol/L、0.040mol/L、0.050mol/
L, 0.060mol/L, 0.070mol/L or 0.080mol/L；Organic ligand concentration is 0.008~6.00mol/L, Ke Yishi
0.008mol/L、0.010mol/L、0.020mol/L、0.03mol/L、0.040mol/L、0.05mol/L、0.060mol/L、
0.070mol/L、0.080mol/L、0.090mol/L、0.100mol/L、0.200mol/L、0.300mol/L、0.400mol/L、
0.500mol/L、0.600mol/L、0.700mol/L、0.800mol/L、0.900mol/L、1.000mol/L、2.00mol/L、
3.000mol/L, 4.000mol/L, 5.000mol/L or 6.000mol/L；Metal organic framework material is directly added into suspension B
The mass ratio of material and graphene oxide is 0.1:1~5:1, can be 0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、
0.7:1、0.8:1、0.9:1、1.0:1、2:1、3:1、4:1 or 5:1.When metal organic framework supported quantity is too low, surface regulation and control effect
Fruit unobvious, supported quantity is too high, and graphene oxide amount is few, it is difficult to plays the advantage of its superpower performance.
Preferably, in the step a, 2-18h supersound process is carried out to the graphene oxide solution, ultrasonic power is not
Less than 300w, per half an hour, stirring once, each ultrasonic 2-3h, makes described graphene oxide sheet footpath 50-500nm or so.Pass through
The lamella that it can be made to reunite is ultrasonically treated to graphene oxide dispersion to disperse, and then controls the size of the composite formed.
Preferably, in the step a, rotating speed is 6000~10000rpm during centrifugation, can be 6000rpm,
7000rpm, 8000rpm, 9000rpm or 10000rpm；Centrifugation time 15~30 minutes, it can be 15 minutes, 20 minutes, 25 points
Clock or 30 minutes；It can fully be washed by increasing rotating speed and centrifugation time, uncombined material removed completely, makes oxidation stone
Black alkene and metal-organic framework materials suspension are more stable.
Preferably, in the step b, the reducing agent is ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, L- half
At least one of fat propylhomoserin, ammoniacal liquor, ammonia vapor, sodium borohydride, hydroiodic acid etc., the mass ratio with graphene oxide are 7:10
~100:10, can be 7:10、8:10、9:10、10:10、20:10、30:10、40:10、50:10、60:10、70:10、80:
10、90:10 or 100:10, the different mass ratios that reducing agent uses make reducing degree different, can regulate and control the composite wood
The surface hydrophilic and hydrophobic of material.
Preferably, in the step b, shower nozzle ultrasonic power is 0.5~1.5w, can be 0.5w, 0.6w, 0.7w,
0.8w, 0.9w, 1.0w, 1.1w, 1.2w, 1.3w, 1.4w or 1.5w；The injection rate of syringe pump is 0.2~0.7ml/min, can
Think 0.2ml/min, 0.3ml/min, 0.4ml/min, 0.5ml/min, 0.6ml/min or 0.7ml/min；Syringe ultrasound work(
Rate is 0.5~1.5w, can be 0.5w, 0.6w, 0.7w, 0.8w, 0.9w, 1.0w, 1.1w, 1.2w, 1.3w, 1.4w or 1.5w；
Ultrasonic nozzle direction is vertical downward direction；By controlling different injection rates and ultrasonic power to control the size of drop
And atomizing effect, and then control the size for forming composite.
Preferably, in the step b, the organic solvent is that the boiling points such as dimethyl silicone polymer, n-octyl alcohol are higher than 150
DEG C and at least one of with the immiscible organic solvent of water, the temperature of the organic solvent is 120~200 DEG C, can be 120
℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、
185 DEG C, 190 DEG C, 195 DEG C or 200 DEG C；The temperature difference of organic solvent can control graphene to form fold degree difference, control
Make the surface nature of the oil absorption material.
The present invention will be further described through by specific embodiment below.
In specific examples below, the unreceipted condition person of involved operation, according to normal condition or manufacturer
It is recommended that condition carry out.Raw materials used unreceipted production firm and specification person are can be by the conventional products of acquisition purchased in market.
Test in following examples on absorption property, condition are to use neat solvent, are tested under normal temperature and pressure conditionses
's.
Embodiment 1
Using class zeolitic imidazolate framework material ZIF-8, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl silicon
Oxygen alkane (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds
0.117g zinc nitrate hexahydrates, stirring make it be uniformly dispersed, and add 2.27g 2-methylimidazoles, after stirring reacts it,
6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reducing agents and form suspending liquid A；
Step b, the suspending liquid A of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-8@rGO oil absorption materials of fold.
SEM photograph (Fig. 1) the display doping ZIF-8 spherical ZIF-8@rGO oil absorption materials particle size of three-dimensional drape is 5 μm
Left and right.
The spherical ZIF-8@rGO oil absorption materials of the three-dimensional drape prepared are subjected to absorption property test, test condition is：Three
Chloromethanes.
Measuring absorption property is：Adsorb chloroform 3.01g/g.
Comparative example 1
Using class zeolitic imidazolate framework material ZIF-8
Preparation method and step：
0.117g zinc nitrate hexahydrate is added in 100ml deionized waters, stirring makes it be uniformly dispersed；Add
2.27g 2-methylimidazole, stirring make it generate ZIF-8；Using deionized water centrifuge washing 3 times, centrifugal rotational speed 10000rpm,
Time 30min, the ZIF-8 materials stablized.
The ZIF-8 materials prepared are subjected to absorption property test, test condition is：Chloroform.
Measuring absorption property is：Adsorb chloroform 1.91g/g.
Embodiment 2
Using class zeolitic imidazolate framework material ZIF-7, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl silicon
Oxygen alkane (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
ZIF-7 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reducing agents and formed
Suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-7@rGO oil absorption materials of fold.
The ZIF-7@rGO materials size that SEM photograph (Fig. 2) display doping ZIF-7 three-dimensional drape is spherical is 4 μm or so.
The spherical ZIF-7@rGO oil absorption materials of the three-dimensional drape prepared are subjected to absorption property test, test condition is：Three
Chloromethanes.
Measuring absorption property is：Adsorb chloroform 3.30g/g.
Embodiment 3
Using class zeolitic imidazolate framework material ZIF-67, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl
Siloxanes (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
ZIF-67 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reduction dosage forms
Into suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-67@rGO oil absorption materials of fold.
SEM photograph (Fig. 3) the display doping ZIF-67 spherical ZIF-67@rGO oil absorption materials size of three-dimensional drape is 4 μm of left sides
It is right.
The spherical ZIF-67@rGO oil absorption materials of the three-dimensional drape prepared are subjected to absorption property test, test condition is：
Chloroform.
Measuring absorption property is：Adsorb chloroform 3.21g/g.
Embodiment 4
Using class zeolitic imidazolate framework material ZIF-11, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl
Siloxanes (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
ZIF-11 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reduction dosage forms
Into suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-11@rGO oil absorption materials of fold.
By the carry out absorption property test of the spherical ZIF-11@rGO oil absorption materials of the three-dimensional drape prepared, test condition
For：Chloroform.
Measuring absorption property is：Adsorb chloroform 3.05g/g.
Embodiment 5
Using class zeolitic imidazolate framework material ZIF-12, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl
Siloxanes (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
ZIF-12 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reduction dosage forms
Into suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-12@rGO oil absorption materials of fold.
By the carry out absorption property test of the spherical ZIF-12@rGO oil absorption materials of the three-dimensional drape prepared, test condition
For：Chloroform.
Measuring absorption property is：Adsorb chloroform 3.55g/g.
Embodiment 6
Using class zeolitic imidazolate framework material MOF-5, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl silicon
Oxygen alkane (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
MOF-5 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reducing agents and formed
Suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical MOF-5@rGO oil absorption materials of fold.
By the carry out absorption property test of the spherical MOF-5@rGO oil absorption materials of the three-dimensional drape prepared, test condition is：
Chloroform.
Measuring absorption property is：Adsorb chloroform 3.80g/g.
Embodiment 7
Using class zeolitic imidazolate framework material ZIF-8, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl silicon
Oxygen alkane (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds
0.585g zinc nitrate hexahydrates, stirring make it be uniformly dispersed, and add 11.35g 2-methylimidazoles, after stirring reacts it,
6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reducing agents and form suspending liquid A；
Step b, the suspending liquid A of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.3ml/min speed
Rate is pressed into the shower nozzle of 1.5w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-8@rGO oil absorption materials of fold.
The absorption sponge of the spherical ZIF-8@rGO materials of the three-dimensional drape prepared is subjected to absorption property test, test
Condition is：Chloroform.
Measuring absorption property is：Adsorb chloroform 3.01g/g.
Embodiment 8
Using class zeolitic imidazolate framework material ZIF-68, reducing agent selects ascorbic acid, and organic solvent selects poly dimethyl
Siloxanes (PDMS).
Preparation method and step：
Step a, 150mg graphene oxides are distributed in 100ml deionized waters, ultrasonic 8h makes its peeling, adds 80mg
ZIF-68 powder, after stirring reacts it, 6000rpm centrifuge washings three times, 15 minutes every time, add 750mg reduction dosage forms
Into suspension B；
Step b, the suspension B of formation is sucked in the syringe of 1.0w ultrasounds, by syringe pump with 0.5ml/min speed
Rate is pressed into the shower nozzle of 1.1w ultrasounds, and suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposits to 165
DEG C PDMS in.
Step c, the material of synthesis is centrifuged and cleaned 3 times (rotating speed 6000rpm), so as to obtain described three
Tie up the spherical ZIF-68@rGO oil absorption materials of fold.
By the carry out absorption property test of the spherical ZIF-68@rGO oil absorption materials of the three-dimensional drape prepared, test condition
For：Chloroform.
Measuring absorption property is：Adsorb chloroform 3.65g/g.
Comparative example 2
Undope metal-organic framework materials, and reducing agent selects ascorbic acid, and organic solvent selects dimethyl silicone polymer
(PDMS)。
Preparation method and step：
Step a, 150mg graphene oxide is distributed in 100ml deionized waters, stirred, after ultrasonic 8h, added
750mg reducing agent, obtain stable graphene oxide dispersion.
Step b, by graphene oxide dispersion, suck in 10ml syringes, sprayed into blend solution by ultrasonic nozzle
In 165 DEG C of PDMS, the reduction and self assembly of graphene oxide are completed, so as to obtain the spherical rGO materials of three-dimensional drape.
The spherical rGO materials of the three-dimensional drape prepared are subjected to absorption property test, test condition is：Chloroform.
Measuring absorption property is：Adsorb chloroform 1.52g/g.
Presently preferred embodiments of the present invention is the foregoing is only, the protection domain being not intended to limit the invention is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc., protection scope of the present invention should be included in
Within.
Claims (10)
1. a kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape, it is characterised in that including the three-dimensional reduction with pleated structure
Graphene oxide ball and the metal-organic framework materials for being immobilized on accordion redox graphene piece interlayer.
2. according to the spherical MOFs@rGO oil absorption materials of a kind of three-dimensional drape described in claim 1, it is characterised in that three-dimensional drape
Spherical redox graphene is to be formed by two dimensional oxidation graphene nanometer sheet by high temperature reduction self assembly；Described metal has
Machine framework material is by growth in situ in redox graphene piece surface or the physically encapsulation by redox graphene piece
Act on immobilized in three-dimensional drape redox graphene ball.
3. according to the spherical MOFs@rGO oil absorption materials of a kind of three-dimensional drape described in claim 1, it is characterised in that described grain
Footpath scope is 1~10 μm；The particle size range of described metal-organic framework materials is 1nm~1 μm.
4. according to the spherical MOFs@rGO oil absorption materials of a kind of three-dimensional drape described in claim 1, it is characterised in that metal is organic
Framework material is selected from class zeolite imidazole ester skeleton (ZIFs) material, IRMOF materials, CPL series materials, MIL series materials, PCN
At least one of series material, UiO series materials.
5. according to a kind of spherical MOFs@rGO oil absorption materials of three-dimensional drape of claim 1, it is characterised in that metal organic framework
Load capacity of the material on redox graphene is 0.1~5g/g.
6. preparing the method for the spherical MOFs@rGO oil absorption materials of three-dimensional drape described in claim any one of 1-5, its feature exists
In comprising the following steps：
Step a, a certain amount of graphene oxide is distributed in deionized water, ultrasound makes its peeling, adds a certain amount of metal
Salt and organic ligand, the metal-organic framework materials growth in situ of synthesis is set to use deionized water on stannic oxide/graphene nano piece
After eccentric cleaning, add a certain amount of reducing agent and form suspending liquid A；Or in the graphene oxide water solution after being uniformly dispersed
A certain amount of metal-organic framework materials are directly added into, a certain amount of reducing agent is added and forms suspension B；
Step b, in the syringe with ultrasound, it is pressed into by the suspending liquid A of formation or suspension B suctions by syringe pump super
In sound shower nozzle, suspension is dispersed into the drop of micro/nano-scale under ultrasonication and deposited in 100-200 DEG C of organic solvent,
Stannic oxide/graphene nano piece issues in high temperature and reducing agent effect and is born from assembling, and metal-organic framework materials is immobilized on reduction
Between graphene oxide layer；
Step c, the material of synthesis is centrifuged and cleaned, inhaled so as to obtain the spherical MOFs@rGO of described three-dimensional drape
Light wood material.
7. according to the method for claim 6, it is characterised in that in step a, original graphene oxide in suspending liquid A and suspension B
Concentration be 1-2g/L, the concentration that metal salt is added in suspending liquid A is 0.004~0.080mol/L, and organic ligand concentration is
0.008~6mol/L；The metal-organic framework materials and the mass ratio of graphene oxide being directly added into suspension B are 0.1:1
~5:1.
8. according to the method for claim 5, it is characterised in that methods described also includes：In step a, to the graphene oxide
Solution carries out 2-18h supersound process, and ultrasonic power is not less than 300w, and per half an hour, stirring once, each ultrasonic 2-3h, makes described
Graphene oxide sheet footpath 50-500nm or so；Rotating speed is 6000~10000rpm during centrifugation, 15~30 minutes time；The step
In b, the reducing agent is ascorbic acid, hydrazine hydrate, ethylenediamine, sodium citrate, half fat propylhomoserins of L-, ammoniacal liquor, ammonia vapor, boron hydrogen
Change at least one of sodium, hydroiodic acid, the mass ratio with graphene oxide is 7:10~100:10.
9. according to the method for claim 5, it is characterised in that in the step b, shower nozzle ultrasonic power is 0.5~1.5w；Injection
The injection rate of pump is 0.2~0.7ml/min；Syringe ultrasonic power is 0.5~1.5w；Shower nozzle direction is side vertically downward
To.
10. according to the method for claim 5, it is characterised in that in the step b, the organic solvent is polydimethylsiloxanes
At least one of higher than 150 DEG C and with the immiscible organic solvent of water, the temperature of organic solvent is the boiling points such as alkane, n-octyl alcohol
120~200 DEG C.
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