CN103895278B - There is porous graphene composite of micropore support and preparation method thereof - Google Patents
There is porous graphene composite of micropore support and preparation method thereof Download PDFInfo
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- CN103895278B CN103895278B CN201410145541.3A CN201410145541A CN103895278B CN 103895278 B CN103895278 B CN 103895278B CN 201410145541 A CN201410145541 A CN 201410145541A CN 103895278 B CN103895278 B CN 103895278B
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Abstract
The invention discloses a kind of graphite nanometer hole preparation method that there is micropore and support, belong to HIB application and processing film field.There is the porous graphene composite that micropore supports, include and be provided with single-layer graphene on polymer thin film, Graphene is provided with nanoscale hole and overlaps with the bellmouth on polymer thin film and communicate.The present invention adopts high-energy heavy ion irradiation Graphene/thin polymer film composite construction, utilizes the irradiation damage effect of heavy ion, Graphene is formed the hole of a few nanometer of diameter, produces the damage field of column in thin polymer film simultaneously.Then by the method for chemical etching, polymer is formed taper nano-pore by irradiation zone etching, because the position of the bellmouth on the position in Graphene hole and polymer overlaps and communicates, therefore can obtain the grapheme nano-pore that there is micropore and support, grapheme nano-pore is with a wide range of applications in ion rectification, ion filter and screening and biomolecule detection.
Description
Technical field
The present invention relates to high-energy heavy ion is instrument, carries out irradiation to Graphene/polymer complex structure, prepares the grapheme nano-pore having micropore and support, belongs to Application of Nuclear Technology field.
Background technology
Graphene is by the former molecular nano material with two-dimensional structure of monolayer carbon, because it has good conduction, heat conductivility and high mechanical strength, can be used for preparing semiconductor transistor, be with a wide range of applications.The performance excellent just because of it and potential application foreground, the finder of single-layer graphene is awarded Nobel Prize in physics in 2010.
Along with the continuous reinforcement be familiar with single-layer graphene and deeply, people prepare the nano-pore with different pore size on single-layer graphene by multiple method, achieve the detection of the molecules such as Small molecular, organic polymer, protein, even may be used for DNA sequencing.Technology of preparing at present about Graphene hole has had patent and relevant report, bombard to obtain grapheme nano-pore to Graphene as utilized the high-power electron beam of transmission electron microscope, its minimum-value aperture is determined by Electron Beam spot size, and difficulty of processing is very large, require higher to operating personnel; In addition, because sample for use in transmitted electron microscope frame size is only 3mm, this Graphene sample also determined selected by it must be less than 3mm, significantly limit its application.Meanwhile, also have researcher by the defect of Graphene itself, the way etched by acid solution is etched with acquisition graphite nanometer hole to defect.Although the preparation method of grapheme nano-pore can prepare the Graphene with nano aperture at present, but utilize the pertusate Graphene of band to carry out Small molecular detection, also need the support of a support and fixing Graphene, otherwise only lean on single-layer graphene itself to be to bear the pressure from the aqueous solution.Have special requirement for the support supporting Graphene hole, it must have aperture, and Graphene must make the aperture on support overlap with the nano aperture of Graphene when shifting to support, otherwise support itself will the nano-pore blocking on Graphene.In addition, the small aperture on support can not be too large, otherwise can not play good supporting role.Grapheme nano-pore is wanted really to detect for Small molecular, very high to the substrate requirements for supporting Graphene, usually needs just to complete and realize by means of modern micro fabrication.
Summary of the invention
The object of the invention is to, for avoiding the deficiencies in the prior art, provide a kind of grapheme nano-pore preparation method having micropore and support, the grapheme nano-pore prepared by the inventive method can be directly used in Small molecular and detect and filter.
For achieving the above object, the technical scheme that the present invention takes is: a kind of porous graphene composite having micropore and support, its main feature is to include and is provided with single-layer graphene on polymer thin film, Graphene is provided with nanoscale hole and overlaps with the bellmouth on polymer thin film and communicate.
The described porous graphene composite with micropore support, described polymer thin film is polycarbonate or polyethylene, and thickness is 2 ~ 30 μm.
Have a preparation method for the porous graphene composite that micropore supports, its main feature is that step includes:
(1) single-layer graphene is transferred on polymer thin film;
(2) composite of the heavy ion utilizing heavy ion avcceleration to accelerate to step (1) carries out irradiation, and heavy ion energy is 1 ~ 100MeV/u, and irradiation dose is for being greater than 1 ion/sample;
(3) composite of step (2) is put into etching bath and carry out one side etching, insert etching solution in polymer thin film side, insert prevention liquid at Graphene opposite side, in the one side chemical etching of polymer thin film side to obtain bellmouth.
Described heavy ion is any ion from C to U.
The described preparation method with the porous graphene composite that micropore supports, also include the one side chemical etching described in step (3), etch temperature is 0 DEG C ~ 95 DEG C, and etching solution is aqueous slkali: pH value range 8 ~ 15; Prevention liquid is acid solution, and pH value range is-1 ~ 6.
General principle of the present invention:
1, when the high-energy heavy ion that accelerates of accelerator is through Graphene, due to the Coulomb interactions of heavy ion and mono-layer graphite atom, the disappearance of graphene carbon atom can be caused and on Graphene, form nano aperture;
2, simultaneously, owing to selecting ion energy high, not only can pass single-layer graphene, most importantly can reach the polymer thin film of tens microns through thickness and form cylindrical damage field;
3, in polymer thin film, because the damage field of heavy ion irradiation formation carries out easily via the method for chemical etching the hole etching formation tens nanometer, the damage field and the grapheme nano-pore that form hole are caused by same heavy ion bombardment, polymer thin film hole and Graphene hole location are overlapped, thus ensures that the hole on thin polymer film has supporting role to grapheme nano-pore.
Beneficial effect of the present invention:
1. the Graphene hole that the method is prepared has the micropore supporting construction corresponded, and directly can carry out Small molecular and ion filter with it;
2. can prepare large-area sample, the sample that area is 5cm × 5cm can be prepared;
3. on product, hole density is adjustable, can regulate the number in hole on sample, from single hole/sample to 10 conveniently by adjustment irradiate ion number
9individual/cm
2hole density is adjustable arbitrarily;
The method adopts high-energy heavy ion irradiation Graphene/thin polymer film composite construction, utilize the irradiation damage effect of heavy ion, Graphene is formed the hole of a few nanometer of diameter, in thin polymer film, produce the damage field of column simultaneously, then by the method for chemical etching, polymer is formed taper nano-pore by irradiation zone etching.Because the position of the bellmouth on the position in Graphene hole and polymer overlaps and communicates, the grapheme nano-pore that there is micropore and support therefore can be obtained.Due to the supporting role of polymer micro, Graphene and nano-pore thereof are with a wide range of applications in ion rectification, ion filter, screening and biomolecule detection.
accompanying drawing illustrates:
Fig. 1 is the structural representation of graphene composite material;
Fig. 2 is bellmouth etching schematic diagram;
Fig. 3 is polymer thin film bellmouth scanning electron microscope diagram;
The grapheme nano-pore transmission electron microscope figure of Fig. 4 to be aperture be 8nm.
Detailed description of the invention
Below in conjunction with accompanying drawing shownschematically preferred example be described in further detail:
Embodiment 1: see Fig. 1, Fig. 2, a kind of porous graphene composite having micropore and support, includes and be provided with single-layer graphene 1 on polymer thin film 2, Graphene 1 is provided with nanoscale hole 1-1 and overlaps with the bellmouth 2-1 on polymer thin film 2 and communicate;
The described area being provided with single-layer graphene 1 on polymer thin film 2 is 5mm × 5mm;
Described polymer thin film 2 is polycarbonate, and thickness is 10 μm.
Embodiment 2: see Fig. 1, a kind of porous graphene composite having micropore and support, the described area being provided with single-layer graphene 1 on polymer thin film 2 is 10mm × 10mm.Described polymer thin film 2 is polyethylene film, and thickness is 20 μm;
All the other structures are identical with embodiment 1.
Embodiment 3: see Fig. 1, a kind of porous graphene composite having micropore and support, the described area being provided with single-layer graphene 1 on polymer thin film 2 is 20mm × 20mm.Described polymer thin film 2 is polycarbonate membrane, and thickness is 30 μm;
All the other structures are identical with embodiment 1.
Embodiment 4: see Fig. 1, Fig. 2, a kind of preparation method with the graphene composite material that micropore supports, its main feature is that step includes:
(1) the large area single-layer graphene prepared by CVD is transferred to polycarbonate, and thickness is 10 μm;
(2) composite of the Bi ion pair step (1) utilizing heavy ion avcceleration to accelerate carries out irradiation, and heavy ion energy is 20MeV/u, and irradiation dose is 10
6individual/cm
2, heavy ion can pass this composite construction, and single-layer graphene forms nano aperture, produces damage in the thin polymer film simultaneously below graphite nanometer hole.In irradiation process, need monitoring heavy ion fluence simultaneously, the heavy ion number of unit are internal irradiation is controlled.By heavy ion irradiation, nano pore can be formed on Graphene;
(3) composite of step (2) is put into etching bath and carry out one side etching, insert etching solution in polymer thin film side, insert prevention liquid in Graphene side, in the one side chemical etching of polymer thin film side to obtain bellmouth; In etching, for obtaining less opening in Graphene side, stop etching when bellmouth etching conducting.Utilizing the method for chemical etching to etch irradiated Graphene/polymer complex structure, just forming corresponding Micro-v oid in the thin polymer film below graphite nanometer hole, for supporting the nano aperture of graphenic surface;
The described preparation method with the graphene composite material that micropore supports, also includes in step 3) described in one side chemical etching, etch temperature is 20 DEG C, and to etch solution used be the NaOH solution pH value of 1M/L is 14; Stop liquid to be the hydrochloric acid of 0.05M/L, pH value is 1.3.
Embodiment 5: see Fig. 1, Fig. 2, a kind of preparation method with the graphene composite material that micropore supports, its main feature is that step includes:
(1) the large area single-layer graphene prepared by CVD is transferred to polyethylene, and thickness is on 20 μm;
(2) composite of the Kr ion pair step (1) utilizing heavy ion avcceleration to accelerate carries out irradiation, and heavy ion energy is 25MeV/u, and irradiation dose is 10
7individual ion/cm
2;
(3) composite of step (2) is put into etching bath and carry out one side etching, insert etching solution in polymer thin film side, insert prevention liquid in Graphene side, in the one side chemical etching of polymer thin film side to obtain bellmouth; In etching, for obtaining less opening in Graphene side, stop etching when bellmouth etching conducting;
In step 3) described in one side chemical etching, etch temperature is 50 DEG C, etches solution used to be: the KOH solution of 3M/L, and pH value is 14.48; Stop liquid to be 0.1M/L hydrochloric acid, pH value is 1.
Embodiment 6: see Fig. 1, Fig. 2, a kind of preparation method with the graphene composite material that micropore supports, its main feature is that step includes:
(1) the large area single-layer graphene prepared by CVD is transferred on polycarbonate, and thickness is 30 μm;
(2) composite of the Xe heavy ion utilizing heavy ion avcceleration to accelerate to step (1) carries out irradiation, and heavy ion energy is 20MeV/u, and irradiation dose is 10
8individual/cm
2, Graphene forms nano aperture;
(3) composite of step (2) is put into etching bath and carry out one side etching, insert etching solution in polymer thin film side, insert prevention liquid in Graphene side, in the one side chemical etching of polymer thin film side to obtain bellmouth; In etching, for obtaining less opening in Graphene side, stop etching when bellmouth etching conducting;
In step 3) described in one side chemical etching, etch temperature is 20 DEG C, etches the NaOH solution that solution used is 8M/L, and pH value is 14.9; Stop liquid to be the hydrochloric acid of 0.1M/L, pH value is 1.
Embodiment 7: see Fig. 1, Fig. 2, a kind of preparation method with the graphene composite material that micropore supports, its main feature is that step includes:
1) single-layer graphene with photoresist (PMMA) prepared by chemical vapour deposition technique (CVD) is cleaned 5 times in deionized water, then the Graphene with PMMA be transferred to 20 μm of thick mylars (PET film) and place 1 hour in 80 DEG C of air ambients; Afterwards Graphene/PET is put into acetone soln cleaning 30 minutes, then put into ethanolic solution cleaning 20 minutes, finally put into washed with de-ionized water, take out after 10 minutes and dry up;
2) utilize energy for 8MeV/L's
209bi
31+ion pair Graphene/PET film carries out irradiation, and irradiation dose is 10
6individual/cm
2;
3) Fig. 2 shown device is utilized to etch irradiated Graphene/PET composite construction, the NaOH solution (pH=14) of 1M/L is put into as etching solution in PET side, the HCl solution (pH=0.7) of 0.2M/L is put into as stoping liquid in Graphene side, solution temperature is room temperature, and etching period is 1 hour;
Fig. 3 is the PET bellmouth stereoscan photograph of preparation, and can see that polymer osculum opening diameter is 56nm, the large mouth opening diameter of polymer is about 1 μm.Fig. 4 is the grapheme nano-pore transmission electron microscope photo that diameter is about 8nm.The graphene nano bore dia obtained under this condition is at 8nm, and in PET film, bellmouth osculum diameter is 56nm, and large mouth opening diameter is 1000nm.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. there is the porous graphene composite that micropore supports, it is characterized in that including be provided with single-layer graphene on polymer thin film, Graphene is provided with nanoscale hole and overlaps with the bellmouth on polymer thin film and communicate.
2. have the porous graphene composite that micropore supports as claimed in claim 1, it is characterized in that described polymer thin film is polycarbonate or polyethylene, thickness is 2 ~ 30 μm.
3. there is the porous graphene composite material and preparation method thereof that micropore supports, it is characterized in that step includes:
(1) single-layer graphene is transferred on polymer thin film;
(2) composite of the heavy ion utilizing heavy ion avcceleration to accelerate to step (1) carries out irradiation, and select the energy range of heavy ion to be 1-100MeV/u, irradiation dose is greater than 1 ion/sample;
(3) composite of step (2) is put into etching bath and carry out one side etching, insert etching solution in polymer thin film side, insert prevention liquid at Graphene opposite side, in the one side chemical etching of polymer thin film side to obtain bellmouth.
4. there is porous graphene composite material and preparation method thereof that micropore supports as claimed in claim 3, characterized by further comprising
In the one side chemical etching described in step (3), etch temperature is 0 DEG C ~ 95 DEG C, and etching solution is aqueous slkali, pH value range 8 ~ 15; Prevention liquid is acid solution, and pH value range is-1 ~ 6.
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| JP2018529612A (en) * | 2015-08-05 | 2018-10-11 | ロッキード・マーチン・コーポレーション | Perforated sheet of graphene material |
| CN106570297A (en) * | 2016-11-15 | 2017-04-19 | 南京理工大学 | Ion rectification research method of tapered nanopore with pH-adjustable electrolyte layer |
| CN111068520A (en) * | 2020-02-14 | 2020-04-28 | 惠州市科近离子膜材料研究院 | Submicron aperture composite membrane based on heavy ion microporous membrane and preparation method and application thereof |
| CN112892240A (en) * | 2021-01-15 | 2021-06-04 | 湖南二零八先进科技有限公司 | Metal-supported graphene separation membrane and preparation method thereof |
| CN113387388B (en) * | 2021-06-15 | 2023-03-07 | 中国科学院近代物理研究所 | Nano porous tungsten trioxide material and preparation method thereof |
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| GB201214565D0 (en) * | 2012-08-15 | 2012-09-26 | Univ Manchester | Membrane |
| CN102989330A (en) * | 2012-12-20 | 2013-03-27 | 浙江工商大学 | Hybrid graphene/aromatic polyamide reverse osmosis membrane and preparation method thereof |
| CN103611431B (en) * | 2013-11-11 | 2015-10-28 | 南京工业大学 | Preparation method of graphene membrane supported by porous ceramic |
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