A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereofTechnical field
The present invention relates to a kind of efficient intercalation formula nanofiber filter membranes, belong to air cleaning and membrane material technology of preparing neckDomain.
Background technique
Due to economic rapid growth and industrialization and the automobile to increase sharply uses and urbanization, and China is just by serious bigThe influence of pellet (PM) in gas, global air pollution is increasingly severe, and the health of the mankind is on the hazard, weatherDeteriorate and the damage of the ecosystem is also on the rise.Efficiently, economic, energy-efficient filter membrane is to solve the problems, such as the ideal handSection.However the shortcomings that can not overcoming there are many existing fiber filter films, as fibre diameter is relatively thick (micro- from several microns to tensRice) and synthetic aperture it is larger, filter particulate efficiency it is relatively low, film heaviness etc..Currently, having developed number of ways to prepareNano fibrous membrane is used for separate fine particles, including mutually separates, templated synthesis, corona treatment and fusion method.But in these sidesIn method, most of there are still filter efficiency is low and the high problem of energy consumption.Thus developing one kind can simply prepare and high efficiency filterThe filter membrane of various pollutants, and be applied to most important in production and living.The technology simple and powerful as one kind,Tunica fibrosa is prepared under nanometer and submicron-scale, electrostatic spinning has been obtained for more and more paying close attention to.
But existing filter membrane function is more single in the market, is only capable of filtering some large particles, is not able to satisfy high efficiency filterDemand.
Summary of the invention
The purpose of the present invention is a kind of improvement to common macromolecular filtering film, imitate the filter membrane with higher filteringRate does not increase complicated preparation process.
Technology of the invention is as follows:
A kind of nanofiber filter membrane of functionalization graphene intercalation, it is characterised in that: the filter membrane contains high molecular nanometer fibrePeacekeeping functionalization graphene layer, the functionalization graphene layer insert in inside high polymer nanometer fiber, mutually overlapping between the two.
It is using electrostatic that functionalization graphene layer of the present invention, which is inserted in inside high polymer nanometer fiber and mutually overlapped,The synchronous realization of spinning technique.
Preferably, the functionalization graphene layer be by graphene oxide, redox graphene, hydroxylating graphene andOne or more of carboxylated graphene material is formed.
Preferably, the high polymer nanometer fiber be by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone,The nanofiber that one or more of bisphenol-a polysulfone, polystyrene and nylon material is formed.
The preparation method of the nanofiber filter membrane of a kind of functionalization graphene intercalation provided by the invention, it is characterised in that shouldMethod includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization grapheneDrive liquid and high molecular material precursor liquid；
2) electrospinning device is used, macromolecule precursor liquid and functionalization graphene precursor liquid are respectively placed in syringeIt is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6-1.0mm/min makes functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, can make functionalization grapheneLayer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Preferably, the mass-volume concentration of the functionalization graphene precursor liquid is 0.01-0.5g/mL, high molecular materialThe mass-volume concentration of precursor liquid is 0.5-2g/10mL.
Preferably, the organic solvent is using n,N-Dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxideOne or more of mixing.
The present invention has the following advantages that and high-lighting technical effect: the present invention is in conventional nano fiber membrane preparation processIn, insertions function graphite alkene layer, so that the functional group abundant using functionalization graphene surface greatly improves fine grainedThe strainability of object can effectively adsorb NH3、CO、NO2Equal polluted gas, and smog, pollen, PM in energy high efficiency filter air2.5Etc. tiny particles contents.Preparation method simple process simultaneously, can one-pass molding, preparation efficiency is high, effectively reduces production cost.
Detailed description of the invention
Fig. 1 is the schematic diagram of preparation method of the present invention.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
Fig. 1 is the schematic diagram of preparation method of the present invention, which includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization grapheneDrive liquid and high molecular material precursor liquid；The mass-volume concentration of functionalization graphene precursor liquid is preferably 0.01-0.5g/mL, highThe mass-volume concentration of molecular material precursor liquid is preferably 0.5-2g/10mL；The organic solvent uses volatile N, N-The mixing of one or more of dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide；The functionalization graphene layerIt is by one or more of graphene oxide, redox graphene, hydroxylating graphene and carboxylated graphene material shapeAt；The high polymer nanometer fiber is gathered by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, bisphenol A-typeThe nanofiber that one of sulfone, polystyrene and nylon Hu different materials are formed.
2) electrospinning device is used, macromolecule precursor liquid 1 and functionalization graphene precursor liquid 2 are respectively placed in syringeIt is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6-1.0mm/min making functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, functionalization graphene can be madeLayer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.The NanowireDimension filter membrane contains functionalization graphene layer 4 and high polymer nanometer fiber 3, and functionalization graphene layer inserts in high polymer nanometer fiberPortion, it is mutually overlapping between the two；It is to adopt that the functionalization graphene layer, which is inserted in inside high polymer nanometer fiber and mutually overlapped,With the synchronous realization of electrostatic spinning process.
Embodiment 1:
Step A, graphene oxide, eccentric cleaning drying are prepared using improved Hummer method.
Step B, 10mg graphene oxide and polyacrylonitrile n,N-Dimethylformamide dispersion liquid are prepared respectively, and it is poly- to weigh 1g10mLN is added in acrylonitrile, and in dinethylformamide, stirring makes precursor liquid be uniformly dispersed, and weighs 10mg graphene oxide and addsEnter in 10mL n,N-Dimethylformamide, stirring ultrasound keeps its evenly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connectsDevice 20.5cm, voltage 10kV, fltting speed 0.8mm/min are received, 10mg graphene oxide is inserted into polyacrylonitrile fibre, is formedThe nanofiber filter membrane of graphene oxide insertion.
Embodiment 2:
Step A, redox graphene, eccentric cleaning freeze-drying are prepared.
Step B, 15mg redox graphene and bisphenol-a polysulfone ethylene glycol dispersion liquid are prepared, 1.5g bisphenol A-type is weighedPolysulfones is added in 10mL ethylene glycol, and stirring makes precursor liquid be uniformly dispersed, then weigh 15mg redox graphene, and 10mL is addedIn ethylene glycol, stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connectsDevice 18cm, voltage 15kV, fltting speed 1mm/min are received, 15mg redox graphene is inserted into bisphenol-a polysulfone fiber,Form the nanofiber filter membrane of redox graphene intercalation.
Embodiment 3:
Step A, hydroxylating graphene, eccentric cleaning drying are prepared.
Step B, 5mg hydroxylating graphene and polyvinylpyrrolidone N-Methyl pyrrolidone dispersion liquid are prepared, 2g is weighedPolyvinyl alcohol is added in 10mL N-Methyl pyrrolidone, and stirring makes precursor liquid be uniformly dispersed, then weigh 5mg hydroxyl graphiteAlkene is added in 10mL N-Methyl pyrrolidone, and stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connectsDevice 20cm, voltage 8kV, fltting speed 0.6mm/min are received, by the polyvinyl pyrrolidone fibers of 5mg hydroxylating graphene intercalationIn, form the nanofiber filter membrane of hydroxylating graphene intercalation.