CN105372320B - Prepare the method and its application of nano pore - Google Patents
Prepare the method and its application of nano pore Download PDFInfo
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Abstract
The present invention relates to the method and its application for preparing nano pore, specifically using capillary as supporter, under the support of supporter, zinc ion aqueous solution diffuses in the aqueous solution containing 2- imidazole formaldehyde crosslinking agent from the tip of capillary, ZIF-90 structure is synthesized in capillary tip, to realize the nano pore preparation based on ZIF-90 structure.Nano pore structure preparation method of the invention is simple, and at low cost, pore size is small, structure-controllable, the micro-molecular gas characterization of adsorption for having both zeolite imidazole ester frame structure develops new opplication of the ZIF-90 in terms of nano pore, has potential application value in fields such as nano-device, sensings.
Description
Technical field
It is to be based on that there is zeolite in capillary tip synthesis the invention belongs to nano-pore technical field and materials science field
The imidazate frame ZIF-90 of structure prepares the method and its application of nano pore.
Background technique
As understanding of the mankind to vital movement is gradually goed deep into, Single Molecule Detection is increasingly taken seriously, nano-pore analysis
Technology is then presently the most young molecule detection, principle be analysis determinand when passing through nano-pore bring from
The detectable signals such as electron current change to achieve the purpose that detection.Therefore will be generated when aperture and determinand are closely sized to compared with
Big signal intensity, to realize the detection to individual molecule, ion.Nano-pore analytical technology testing conditions are mild, without pair
Detectable substance is pre-processed, the physico-chemical property of detection process not destructive test object.In recent years, the development of nano-pore analytical technology was fast
Speed, bioprotein alpha hemolysin, Si3N4Large quantities of materials such as film, pellumina are widely used in nano-pore analytical technology.
Currently, nano-pore technology embodies its exclusive glamour in numerous areas such as analysis of protein, DNA detections.
Zeolite imidazole ester frame structure (Zeolitic Imidazolate Framework, ZIF), which belongs to metal, machine frame
One kind of frame structure (Metal Organic Framework, MOF) material has the topological structure of similar zeolite, good heat
Stability, high-specific surface area porous structure so that it is widely used valence in numerous areas such as gas separation, storage, catalysis
Value.The MOF material of technology preparation at present mainly exists or in carrier surface in the form of crystal perhaps powder as membrane material
It is applied, lacks the supporter as nanochannel, it is difficult to generate nanochannel bring effect.ZIF-90 is ZIF
One kind of material has stable porous structure, and can synthesize in water phase.It is used for reference in nano pore technology,
In conjunction with the capillary technique at nanoscale tip as supporting, it is expected to the application field of abundant MOF class material, preparation has ion
It screens, the multifunctional sensing device of rectification characteristic and detection of gas.
Summary of the invention
The object of the present invention is to provide based on capillary tip synthesis have zeolite structured imidazate frame ZIF-90
The method for preparing nano pore.ZIF-90 material, which is overcome, with the nano pore that this method is prepared is not directly applicable nanometer
The problem of duct technology, develops the new opplication of ZIF-90 material.
The present invention mainly realizes by following technical solution:
Under the support of capillary supporter, zinc ion solution is diffused to from the tip of capillary containing 2- imidazole formaldehyde
In aqueous solution, to synthesize nano pore in capillary tip.
Specifically, this method is based on the zeolite imidazole ester frame structure ZIF- that can be prepared in a mild condition
90, zinc ion diffuses in the aqueous solution containing crosslinking agent 2- imidazole formaldehyde, and at tip, synthesis has the nanometer of sod topological structure
Duct.
Further, the nano pore of this method synthesis is mainly applied in terms of Ion transfer, gas sensing, therefore we
Method solvent is water.Further, it is the dissolution for promoting 2- imidazole formaldehyde, ultrapure water is added in 2- imidazole formaldehyde before synthesis
In, it is heated to reflux 30min at 80-90 DEG C and obtains clear 2- imidazole formaldehyde aqueous solution, insertion is equipped with zinc ion solution later
Capillary, zinc ion solution by capillary tip spread, its diffusion velocity is controlled under 55-65 DEG C of constant temperature, is conducive to
The generation of ZIF-90 frame structure is simultaneously gathered in capillary tip.This method preparation time 12-36h, but it is not limited in 12-36h,
Since capillary tip size slightly has difference, the diffusion velocity under the same terms is slightly different, under optimum condition, preparation time
1-10 μm of the nano pore size diameter of 12h preparation, size diameter can be stabilized at 1-200 μm.
In the present invention, the supporter be capillary glass tube, capillary glass tube preparation method is simple, preparation condition at
Ripe, easy to operate, controllability is preferable, is suitable for being used in aqueous environment.
Above-mentioned capillary form is circle, but is not limited to circle, can be rectangular, triangle etc.；It can be wrapped in capillary
Containing drainage tube, but it is not limited to the capillary that there must be flow tube.In addition, capillary is only nanoscale at tip, tail portion is macro
Size is seen, total length is several millimeters to more than ten centimetres.Capillary is prepared as the prior art, and the present invention does not limit this especially
It is fixed.
Nano pore prepared by the present invention is applied mainly as a kind of electrochemical device, therefore including its electrochemistry
Analytical procedure: for the wire of two same materials respectively as working electrode and to electrode, working electrode insertion is equipped with electrolyte
Capillary inside after use, and electrode is then inserted directly into External electrolytic liquid, its i-V is tested by linear sweep voltammetry
Curve.
Have well in fields such as electronic device, sensings using valence using the nano pore that capillary glass tube is prepared as supporter
Value.Using one: novel diode, nanotube is the single hole that tip is 100-200nm before the synthesis, passes through electrochemical measurement i-v
Curve only has more apparent rectifier phenomena in the lower situation of electrolyte concentration, after synthesizing completion, nanotube tip
It is less than the sub-nanometer duct of 1nm for aperture, since aperture is already close to ion size, tip taper pattern and with negative electricity
Capillary wall makes the migration difficulty differentiation of different directions inside and outside cation, and surveyed electrochemistry i-V signal will appear very
Apparent rectifying effect.Using two: pH response, as shown in the above description, the negative charge density of capillary glass tube wall can very great Cheng
The size of current passed through is influenced on degree, therefore under conditions of electrolyte inside is the highly basic, highly basic and weak base of various concentration
" on " current potential has different size of current-responsive, i.e. the structure may be implemented to respond in neutrality to the section pH of alkalinity.Using
Three: carbon dioxide sensing, zeolite imidazole ester frame (ZIF) structure have good adsorption effect, absorption two to carbon dioxide gas
After carbonoxide, the original cellular structure of ZIF structure can block and then influence the migration of ion, therefore the present invention is also used as two
The sensing of the micro-molecular gas such as carbonoxide.
From above-mentioned technical proposal and result it is found that the present invention is innovatively prepared for receiving based on zeolite imidazole ester frame
Rice channel design, develops application of the zeolite imidazole ester frame ZIF-90 in nanochannel technology.It is advantageous that raw material
Simply, inexpensively, be easy to get, mild condition, device architecture stablize, it is reusable.And capillary rear end is macro-size, it is convenient with
Various mechanical, electronic equipments combine, and potential application value is very big.
Detailed description of the invention
Fig. 1 is the method schematic diagram that the present invention prepares nano pore.
Fig. 2 is the structural schematic diagram of zeolite imidazole ester frame ZIF-90.
Fig. 3 is the electron microscope after the processing of nano-glass capillary.
Fig. 4 is the various sizes of nano pore photo prepared.
Fig. 5 is electrochemical testing device schematic diagram.
Fig. 6 be electrolyte be 0.01mol/L sodium hydroxide solution when i-V curve.
Fig. 7 is the i-V curve of various concentration sodium hydroxide solution.
Fig. 8 is the i-V curve of different electrolyte solutions.
Fig. 9 is CO absorption2Curent change under -0.3V afterwards.
Specific embodiment
Below with reference to embodiment and attached drawing explanation, the following further describes the technical solution of the present invention, but should not be construed as
Limitation of the present invention:
Embodiment 1
The method that the present invention prepares nano pore, includes the following steps:
(1) prepare capillary glass tube tip: instrument used is that SUTTER company P-2000 in the U.S. draws needle instrument, glass capillary
Pipe is BOROSILIGATE GLASS the WITH FILAMENT, O.D:1.0mm, I.D:0.58mm of SUTTER company, total length
For 10cm.Setting parameter be LINE 1:HEAT=350, FIL=3, VEL=30, DEL=200, PUL=Null LINE 2:
HEAT=340, FIL=2, VEL=27, DEL=160, PUL=250.
The capillary tip diameter prepared under the above conditions with the capillary of this specification is 100-200nm, such as Fig. 3 institute
Show.
(2) it prepares 2- imidazole formaldehyde aqueous solution: 2- imidazole formaldehyde being added to the water 80 DEG C is heated to reflux 30min and clarified
Bright yellow solution.
(3) nano pore is prepared: as shown in Figure 1, zinc ion solution is added to the tip of nano-glass capillary, then
Tip is immersed in 2- imidazole formaldehyde solution, constant temperature spreads 12h in 60 DEG C of metal baths.Due to diffusion, zinc ion with
The N atom of imidazole ring (Im) forms Zn-Im-Zn coordinate bond, and by such continuous conjunction, one is finally formed at the top of supporter
The zeolite imidazole ester frame structure of nozzle is wrapped up, size diameter is at 1-10 μm, as shown in Fig. 4 a, 4b.
Embodiment 2
2- imidazole formaldehyde is added to the water in (2) by the preparation at capillary glass tube tip with (1) the step of embodiment 1, step
90 DEG C are heated to reflux 30min and obtain clarification bright yellow solution.Constant temperature spreads 15h in 55 DEG C of metal baths in step (3).It prepares
Zeolite imidazole ester framework size diameter at 20-50 μm, as illustrated in fig. 4 c.
Embodiment 3
2- imidazole formaldehyde is added to the water in (2) by the preparation at capillary glass tube tip with (1) the step of embodiment 1, step
85 DEG C are heated to reflux 30min and obtain clarification bright yellow solution.Constant temperature spreads 36h in 65 DEG C of metal baths in step (3).It prepares
Zeolite imidazole ester framework size diameter at 100-200 μm, as shown in figure 4d.
Embodiment 4
The present embodiment has carried out electro-chemical test to the nano pore prepared in embodiment 1, and Fig. 5 is the dress of electro-chemical test
Set schematic diagram.1 is platinum filament as electrode, and 2 be electrolyte solution, and 3 be the cellular structure of receiving prepared.With 0.01mol/L hydroxide
Sodium is electrolyte, and linear sweep voltammetry scanning, take-off potential+0.8V, termination current potential -0.8V sweep fast 0.01V/s, as a result such as
Shown in Fig. 6, since tube wall is negatively charged, cationic migration is occupied an leading position, and cation migrates from inside to outside under positive potential, due to
Tip aperture is smaller, and a large amount of cations are gathered in tapered end, generates inverse potential, therefore electric current very little, produces good rectification
Effect.
Embodiment 5
The present embodiment is the application of the nano pore for preparing in embodiment 1 in pH response, and device is same as Example 4,
0.001 is changed to by the concentration of electrolyte sodium hydroxide to same capillary glass tube, 0.005,0.01mol/L scan its i-V curve,
As a result as shown in fig. 7, there is apparent rectifying effect, but the electric current under negative potential increases as concentration increases.Equally
, electrolyte is changed into the sodium bicarbonate, sodium chloride, ammonium chloride of 0.01mol/L, as a result such as Fig. 8, with pH decline and chlorine from
The introducing of son, the migration of anion also play a role in electric current, and rectifying effect weakens.
Embodiment 6
The present embodiment is the application of the nano pore for preparing in embodiment 1 in carbon dioxide sensing, device and embodiment 4
It is identical, to avoid electrolyte to CO2Influence, select the sodium bicarbonate solution of 0.1mol/L as electrolyte reduce CO2Hydrolysis,
The cellular structure of receiving of preparation is placed in CO after previously-scanned i-V curve230min is handled in atmosphere, is carried out continuously later more
Secondary i-V multiple scanning, electric current very little always under positive potential, what only the open-circuit current under negative potential was subject to is affected, as a result
As shown in figure 9, be reference with the electric current under -0.3V potential, it, originally should be under " on " state after finding carbon dioxide treatment
Open-circuit current be reduced rapidly, illustrate that entire channel tends to fully closed conjunction state, until absorption with gas in the solution after 2h
Desorption, channel part reopen, and have weak current and slight rectifying effect to occur.
Claims (9)
1. a kind of method for preparing nano pore, which is characterized in that there is zeolite structured imidazate in capillary tip synthesis
Frame ZIF-90 is directly based upon ZIF-90 structure and prepares nano-pore device；
Described method includes following steps:
(1) capillary tip is prepared；The capillary tip diameter is 100-200nm；
(2) it prepares 2- imidazole formaldehyde aqueous solution: 2- imidazole formaldehyde being added to the water 80-90 DEG C and is heated to reflux to obtain clear solution；
(3) it prepares nano pore: using capillary as supporter, zinc solution being added and is inserted into capillary in step (2)
Clear solution in, zinc solution from capillary tip prepared by step (1) constant temperature spread, capillary tip synthesize nanometer
Duct.
2. preparing the method for nano pore according to claim 1, which is characterized in that capillary tip in the step (1)
Needle instrument is drawn to prepare using U.S. SUTTER company P-2000.
3. preparing the method for nano pore according to claim 1, which is characterized in that the step (3) is permanent at 55-65 DEG C
Temperature carries out, and the reaction time is in 12-36h.
4. according to claim 1 or 3 methods for preparing nano pore, which is characterized in that the step (3) is permanent at 60 DEG C
Temperature carries out, reaction time 12h.
5. preparing the method for nano pore according to claim 1, which is characterized in that the capillary in the step (3) is
Capillary glass tube.
6. preparing the method for nano pore according to claim 1, which is characterized in that capillary tip in the step (1)
Needle instrument is drawn to prepare using capillary glass tube and U.S. SUTTER company P-2000, the capillary tip diameter prepared is 100-
200nm；2- imidazole formaldehyde is added to the water 80 DEG C in the step (2) to be heated to reflux；The step (3) at 60 DEG C constant temperature into
Row, reaction time 12h.
7. according to claim 1-3, the nano pore of any one of 5, the 6 method preparations for preparing nano pore.
8. application of the nano pore according to claim 7 in chemical analysis and bioanalysis.
9. application of the nano pore according to claim 8 in chemical analysis and bioanalysis, which is characterized in that described
Nano pore is for ion screening, rectification and detection of gas.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841157B (en) * | 2016-12-23 | 2019-12-17 | 南京大学 | method for preparing nano porous structure based on aqueous phase nanoparticle self-assembly and application thereof |
| CN107356580B (en) * | 2017-06-27 | 2020-04-03 | 南京大学 | Nano single hole based on monodisperse nanosheet layer and preparation method and application thereof |
| CN108247036B (en) * | 2018-01-15 | 2019-09-13 | 南京大学 | A kind of metal nano porous structure and its preparation method and application |
| CN111366627B (en) * | 2020-03-23 | 2021-02-26 | 南京大学 | Covalent organic framework porous structure of capillary tip and preparation method and application thereof |
| CN111487307B (en) * | 2020-05-07 | 2023-02-10 | 温州大学 | Method for detecting protein based on borosilicate glass nano-pore channel modified by metal organic framework material |
| CN112525880A (en) * | 2020-11-16 | 2021-03-19 | 南京大学 | Small-aperture nanopore device and preparation method and application thereof |
| CN115594857A (en) * | 2022-10-20 | 2023-01-13 | 华东理工大学（Cn） | MOFs nanoparticle interface dynamic growth method and MOFs nanoparticles |
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