CN107497377A - A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere - Google Patents
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, this method mixes metal organic framework compound dispersion liquid with graphene oxide dispersion, complex microsphere is made in spray drying, the present invention obtains complex microsphere by the method for spray drying, obtained Microsphere Size is than more uniform, yield is high, yield is 70% 85%, Microsphere Size is average at 1.5 μm or so, the reunion of graphene oxide under hot conditions is avoided simultaneously, ZIF 8 can be transformed into nanoporous carbon under the high temperature conditions, the nanoporous carbon graphite alkene complex microsphere of N doping has higher specific surface area and high nitrogen content, after high temperature cabonization is handled, electric conductivity improves, it can apply to CO2Absorption, ultracapacitor, battery, catalysis, separation etc..
Description
Technical field
The present invention relates to a kind of preparation side of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere
Method, belong to technical field of new material preparation,
Background technology
Zeolitic imidazolate framework material (ZIFs) is a kind of metal-organic framework materials with skeleton structure of zeolite
(MOFs), transition metal therein is mainly Zn, Co of divalence etc., and organic ligand is imidazoles or imdazole derivatives.Boiled with tradition
Stone is compared, and transition metal ions instead of Si elements and Al elements in traditional zeolite, and imidazate instead of traditional boiling
Oxygen bridge in stone, be connected the zeolite structured material of a species formed by the nitrogen-atoms on imidazole ring.
ZIF-8 is zeolitic imidazolate framework material (ZIFs) one kind, is made up of most 2-methylimidazole and metallic atom Zn
Elementary cell, wherein the N Atomic coordinates on each Zn atoms and four 2-methylimidazole rings, forming one has positive tetrahedron knot
The ZnN of structure4Cluster, then using these clusters as node, be connected by the imidazole ring on 2-methylimidazole, forming one has
The cage coordination compound of regular hexahedron crystal formation.Compared with other inorganic particulates, there is ZIF-8 higher specific surface area (to reach for it
To 1947m2/ g), high heat endurance and the features such as good chemical stability.Due to these advantages, ZIF-8 widely should
For being catalyzed, gas separation and storage etc. field.
Graphene oxide (GO) can lose oxy radical during reduction and reunite, by by ZIF-8 materials and GO
It is compound not only effectively to reduce the reunions of GO under the high temperature conditions, it can also will be connected between ZIF, improve electric conductivity,
A part of N atoms can be protected simultaneously, prevent the loss of N atoms, ultimately form the porous carbon of the N doping with multiple avtive spots
Material, there is higher specific surface area, can be widely applied to CO2Absorption, ultracapacitor, battery, catalysis, the side such as separation
Face.The preparation method of ZIF-8 and GO composite has in-situ synthesis, ultrasonic method etc. at present, but is all only limitted to laboratory water
It is flat, yield poorly, it is impossible to produce in batches, and pattern heterogeneity, cause avtive spot skewness, to the physical chemistry of material
Matter causes very big influence.
The content of the invention
In view of the shortcomings of the prior art, a kind of homogeneous metal organic framework compound/graphene oxide of pattern of the present invention is multiple
The preparation method of microballoon is closed, obtained complex microsphere pattern is homogeneous, and yield is high.
The problem of existing for the preparation process of current ZIF-8 and GO composite, the invention solves technology ask
Topic：GO is added during synthesis ZIF-8 at present, obtained product pattern heterogeneity, it is difficult to control, and yield poorly, only
It is limited to laboratory level, it is difficult to industrialization.
The present invention solves above-mentioned technical problem and is achieved through the following technical solutions：
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, including：
Metal organic framework compound dispersion liquid mixes with graphene oxide dispersion, and spray drying prepares complex microsphere step
Suddenly.
It is 1-5mg/mL according to the concentration of currently preferred, described metal organic framework compound dispersion liquid.
It is 1-5mg/mL according to the concentration of currently preferred, described graphene oxide dispersion.
According to currently preferred, metal organic framework compound dispersion liquid and graphene oxide dispersion mixed volume ratio
For：(1-10)：1.
According to currently preferred, the actual conditions of spray drying is：EAT is more than or equal to 30 DEG C of solvent boiling point, enters
Material speed is 8~15mL/min, compressed air require 500-1000L/h, compressed air pressure 5-8bar, air-out air velocity
For 25-35m3/h。
It is further preferred that EAT is 140~160 DEG C, leaving air temp is 80~90 DEG C.
The present invention is spray-dried system after being mixed by metal organic framework compound dispersion liquid with graphene oxide dispersion
Standby complex microsphere, is dispersed into trickle droplet by material liquid by compressed gas, with hot air, moisture rapid vaporization, obtains
Dry products, particle is then separated from air-flow through cyclone separator, reach product collection vessel, can directly make solution, milkiness
Liquid dries powdering or particulate preparation, can save the processes such as devaporation, crushing, and the droplet that compressed gas disperses is done
The uniform particle of size distribution is can obtain after dry.
It is that there is catalytic containing Mn, Fe, Co, Ni, Cu according to currently preferred, described metal organic framework compound
The MOFs of energy.
It is further preferred that described metal organic framework compound is zeolitic imidazolate framework material.
It is further preferred that described zeolitic imidazolate framework material is ZIF-8 or ZIF-67.
ZIF-8 preparation method has a variety of, and synthetic method has room temperature synthetic method, hydrothermal synthesis method, solvent-thermal process method, micro-
Ripple synthetic method, ultrasonic, ion thermal synthesis method, electrochemical synthesis, mechanosynthesis etc..Methanol, N, N can be selected in solvent
Dimethylformamide, N, N diethylformamides etc., some surfactants can be added to change ZIF- during synthesis
8 pattern and size, it is different with pattern using the ZIF-8 sizes that different methods synthesizes.
According to currently preferred, ZIF-8 is to be prepared as follows to obtain：At room temperature, by 1-10g zinc nitrate hexahydrates
(Zn(NO3)·6H2O) aqueous solution is added to 10-100g 2-methylimidazole (C4H6N2) in the aqueous solution, magnetic agitation reaction 1-
24h, resulting solution is centrifuged, deionized water washing, ZIF-8 (complex that zinc is formed with 2-methylimidazole) nanometer is made
Particle.
According to currently preferred, the concentration of the zinc nitrate hexahydrate aqueous solution is 2-10g/L, 2-methylimidazole (C4H6N2)
The concentration of the aqueous solution is 8-40g/L.
ZIF-67 structures simply change Zn ions into Co ions as ZIF-8, can also serve as the porous of N doping
The presoma of carbon material, N-Co avtive spots can also be formed, can be applied to ORR, OER, HER etc..In addition, can be with
It is compound from MOFs and the GO progress containing Mn, Fe, Co, Ni, Cu etc. with catalytic performance, it will be combined the advantages of MOFs with GO, profit
With the electric conductivity of redox graphene, accelerate the transmission of proton, improve catalytic property, while the material has higher ratio table
Area, some carrier loaded noble metals can be used as, applied in terms of electro-catalysis.
Mixed according to currently preferred, described metal organic framework compound dispersion liquid with graphene oxide dispersion
Close, spray drying, which prepares complex microsphere step, is：Metal organic framework compound, graphene oxide are distributed to water respectively or had
In solvent, concentration is made respectively as 1-5mg/mL metal organic framework compound dispersion liquid and 1-5mg/mL graphite oxide
Alkene dispersion liquid, metal organic framework compound is disperseed to be slowly added into graphene oxide dispersion, stirs while adding, mixes
Closing volume ratio is：(1-10)：1, drying of then being sprayed to mixed solution, metal organic framework compound/graphene oxide is made
Complex microsphere；Described organic solvent is methanol or ethanol.
The preparation method yield of the present invention is in 70%-85%.From the mapping figures of ZIF-8/GO complex microspheres C, N, O,
The distribution situation of tetra- kinds of elements of Zn can be seen that ZIF-8 and GO is equably compound.
Compared with the prior art, beneficial effects of the present invention are embodied in：
1st, the present invention obtains ZIF-8/GO complex microspheres by the method for spray drying, and obtained Microsphere Size is more equal
One, yield is high, and for yield in 70%-85%, favorable repeatability can be with industrialization.Microsphere Size is average at 1.5 μm or so, microballoon
Size can be regulated and controled by experiment condition.
2nd, ZIF-8/GO complex microspheres prepared by the present invention can avoid the reunion of graphene oxide under hot conditions, ZIF-
8 can be transformed into nanoporous carbon under the high temperature conditions, the nanoporous carbon graphite alkene complex microsphere of this N doping have compared with
High specific surface area and high nitrogen content, after high temperature cabonization is handled, electric conductivity improves, and can apply to CO2Adsorb, be super
Capacitor, battery, catalysis, separation etc..
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of ZIF-8/GO complex microspheres made from ZIF-8 and embodiment 1.
Fig. 2 is ESEM (SEM) photo of ZIF-8/GO complex microspheres made from ZIF-8 and embodiment 1, wherein a
For 100nm ESEM (SEM) photo, b is 1 μm ESEM (SEM) photo.
Embodiment
Below by specific embodiment combination accompanying drawing, the invention will be further described, but not limited to this.
Raw materials used in embodiment is convenient source, commercial products.
Embodiment 1
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, step are as follows：
ZIF-8, graphene oxide are distributed in deionized water respectively, the ZIF-8 dispersion liquids that concentration is 2mg/mL are made
With 2mg/mL graphene oxide dispersion, ZIF-8 is disperseed to be slowly added into graphene oxide dispersion, stirred when adding
Mix, mixed proportion 1:1, then obtained mixed liquor is spray-dried, spray drying condition is：EAT is 150 DEG C,
Charging rate is adjusted by peristaltic pump, charging rate 10mL/min, compressed air require 600L/h, and compressed air pressure is
5-8bar, air-out air velocity are 35m3/ h, leaving air temp are 80 DEG C, and ZIF-8/GO complex microspheres are made.
ZIF-8 and obtained ZIF-8/GO complex microspheres X-ray diffractogram as shown in figure 1, ESEM (SEM) photo such as
Shown in Fig. 2.
ZIF-8 X-ray diffractogram as shown in figure 1, ESEM (SEM) photo as shown in Fig. 2 all diffraction maximums and mould
Plan ZIF-8 crystal datas are consistent, and display product is the good ZIF-8 of crystallinity, is spread out for the X ray of ZIF-8/GO complex microspheres
Figure is penetrated, 25 ° or so of broad peak corresponds to the crystal face of graphene, and other peaks correspond to ZIF-8, illustrates that ZIF-8 and GO are compound.
Homogeneous from Fig. 2 (a) SEM it can be seen from the figure that ZIF-8 nano-particle patterns, surface smoother, size is in 100nm
Left and right.It can be seen that ZIF-8/GO complex microsphere patterns are homogeneous from Fig. 2 (b), size is at 1.5 μm or so.
Embodiment 2
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, step are as follows：
ZIF-8, graphene oxide are distributed in deionized water respectively, the ZIF-8 dispersion liquids that concentration is 2mg/mL are made
With 2mg/mL graphene oxide dispersion, ZIF-8 is disperseed to be slowly added into graphene oxide dispersion, stirred when adding
Mix, mixed proportion 2:1, then obtained mixed liquor is spray-dried, spray drying condition is：EAT is 150 DEG C,
Charging rate is adjusted by peristaltic pump, charging rate 10mL/min, compressed air require 600L/h, and compressed air pressure is
5-8bar, air-out air velocity are 35m3/ h, leaving air temp are 80 DEG C, and ZIF-8/GO complex microspheres are made.
Embodiment 3
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, with embodiment 1
Shown, difference is：
Spray drying condition is：EAT is 160 DEG C, and charging rate is adjusted by peristaltic pump, and charging rate is
12mL/min, compressed air require 1000L/h, compressed air pressure 5-8bar, air-out air velocity are 35m3/ h, goes out wind-warm syndrome
Spend for 85 DEG C.
Embodiment 4
A kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, with embodiment 1
Shown, difference is：ZIF-8 is replaced with ZIF-67.
Comparative example 1
A kind of preparation method of metal organic framework compound/graphene oxide complex microsphere, step are as follows：
ZIF-8, graphene oxide are distributed in deionized water respectively, the ZIF-8 dispersion liquids that concentration is 2mg/mL are made
With 2mg/mL graphene oxide dispersion, ZIF-8 is disperseed to be slowly added into graphene oxide dispersion, stirred when adding
Mix, mixed proportion 1:1, to mixed solution heated-air drying, temperature setting is 150 DEG C, and metal organic framework compound/oxidation is made
Graphene complex.
Metal organic framework compound made from the heated-air drying of comparative example 1/graphene oxide composite sample pattern, size
Uncontrollable, density is low.And 1-4 of embodiment of the present invention spray drying process prepares speed faster, sample size is smaller, adjustable
Control, size uniformity, and can continuous production.
Claims (10)
1. a kind of preparation method of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere, including：
Metal organic framework compound dispersion liquid mixes with graphene oxide dispersion, and spray drying prepares complex microsphere step.
2. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, it is characterised in that the concentration of described metal organic framework compound dispersion liquid is 1-5mg/mL；Described graphite oxide
The concentration of alkene dispersion liquid is 1-5mg/mL.
3. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, metal organic framework compound dispersion liquid are with graphene oxide dispersion mixed volume ratio：(1-10)：1.
4. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, the actual conditions of spray drying are：EAT is more than or equal to 30 DEG C of solvent boiling point, and charging rate is 8~15mL/min,
Compressed air require 500-1000L/h, compressed air pressure 5-8bar, air-out air velocity are 25-35m3/h。
5. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 4
Method, EAT are 140~160 DEG C, and leaving air temp is 80~90 DEG C.
6. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, described metal organic framework compound are the MOFs for having containing Mn, Fe, Co, Ni, Cu catalytic performance.
7. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, described metal organic framework compound are zeolitic imidazolate framework material；Preferably, described zeolite imidazole ester skeleton
Material is ZIF-8 or ZIF-67.
8. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, ZIF-8 are to be prepared as follows to obtain：At room temperature, by 1-10g zinc nitrate hexahydrates (Zn (NO3)·6H2O) the aqueous solution
It is added to 10-100g 2-methylimidazole (C4H6N2) in the aqueous solution, magnetic agitation reaction 1-24h, by resulting solution centrifugation point
From, deionized water washing, obtained ZIF-8 (complex that zinc is formed with 2-methylimidazole) nano-particle；Zinc nitrate hexahydrate water
The concentration of solution is 2-10g/L, 2-methylimidazole (C4H6N2) concentration of the aqueous solution is 8-40g/L.
9. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 1
Method, described metal organic framework compound dispersion liquid mix with graphene oxide dispersion, and spray drying prepares compound micro-
Ball step is：Metal organic framework compound, graphene oxide are distributed in water or organic solvent respectively, concentration is made respectively
For 1-5mg/mL metal organic framework compound dispersion liquid and 1-5mg/mL graphene oxide dispersion, by the organic bone of metal
Frame compound is scattered to be slowly added into graphene oxide dispersion, is stirred while adding, mixed volume ratio is：(1-10)：1,
Then to mixed solution spraying drying, metal organic framework compound/graphene oxide complex microsphere is made.
10. the preparation of the homogeneous metal organic framework compound of pattern/graphene oxide complex microsphere according to claim 9
Method, it is characterised in that described organic solvent is methanol or ethanol.
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