CN105372320A - Method for preparing nano porous channel based on imidazate framework ZIF-90 which is of zeolite structure and synthesized at tip end of capillary tube and application thereof - Google Patents
Method for preparing nano porous channel based on imidazate framework ZIF-90 which is of zeolite structure and synthesized at tip end of capillary tube and application thereof Download PDFInfo
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- CN105372320A CN105372320A CN201510716560.1A CN201510716560A CN105372320A CN 105372320 A CN105372320 A CN 105372320A CN 201510716560 A CN201510716560 A CN 201510716560A CN 105372320 A CN105372320 A CN 105372320A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- YAGCJGCCZIARMJ-UHFFFAOYSA-N N1C(=NC=C1)C=O.[Zn] Chemical compound N1C(=NC=C1)C=O.[Zn] YAGCJGCCZIARMJ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims description 45
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 2
- 238000011953 bioanalysis Methods 0.000 claims 2
- 229910052725 zinc Inorganic materials 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 15
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000008093 supporting effect Effects 0.000 abstract 3
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- -1 Zeolite imidazole ester Chemical class 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000002090 nanochannel Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 101710092462 Alpha-hemolysin Proteins 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a method for preparing a nano porous channel based on an imidazate framework ZIF-90 which is of a zeolite structure and synthesized at the tip end of a capillary tube. In particular, the capillary tube is used as a supporting body, a zinc ion aqueous solution is diffused into an aqueous solution containing a 2-imidazole aldehyde cross-linking agent from the tip end of the capillary tube under the supporting action of the supporting body, the ZIF-90 structure is synthesized at the tip end of the capillary tube, and therefore preparation of the nano porous channel based on the ZIF-90 structure is achieved. The nano porous channel is simple in structure and preparation method, low in cost, small in porous channel size and controllable in structure; the small molecule gas absorption characteristic of the zeolite imidazate framework structure is achieved at the same time, the new application of the ZIF-90 on the aspect of the nano porous channel is developed, and potential application value is achieved in the fields of nano devices, sensing and the like.
Description
Technical field
The invention belongs to nano-pore technical field and material science, be based on capillary tip and synthesize the method and the application thereof that there is zeolite structured imidazate framework ZIF-90 and prepare nano pore.
Background technology
Along with the mankind progressively go deep into the understanding of vital movement, Single Molecule Detection more and more comes into one's own, nano-pore analytical technology is then molecule detection the youngest at present, and its principle analyzes determinand in detectable signal changes such as the gas currents by bringing during nano-pore with the object reaching detection.Therefore when aperture and determinand size close to time will produce larger signal intensity, thus realize the detection to individual molecule, ion.Nano-pore analytical technology testing conditions is gentle, without the need to carrying out pre-service to detection thing, and the physico-chemical property of testing process not destructive test thing.In recent years, the development of nano-pore analytical technology was rapid, bioprotein alpha hemolysin, Si
3n
4large quantities of material such as film, pellumina is widely used in nano-pore analytical technology.At present, nano-pore technology embodies its exclusive glamour at numerous areas such as analysis of protein, DNA detections.
Zeolite imidazole ester framed structure (ZeoliticImidazolateFramework, ZIF) metal-organic framework (MetalOrganicFramework is belonged to, MOF) one of material, have the topological structure of similar zeolite, good thermal stability, the porous structure of high-specific surface area make it have a wide range of applications at numerous areas such as gas separaion, storage, catalysis.MOF material prepared by current technology mainly exists with the form of crystal or powder, or applies as membrane material at carrier surface, lacks the supporter that it can be used as nanochannel, is difficult to the effect that generation nanochannel brings.ZIF-90 is the one of ZIF material, has stable porous structure, and can synthesize in aqueous phase.Used for reference in nano pore technology, the capillary technique at combining nano yardstick tip, as support, is expected to the application enriching MOF class material, and preparation has the multifunctional sensing device of ion screening, rectification characteristic and detection of gas.
Summary of the invention
The object of this invention is to provide based on synthesizing the method that there is zeolite structured imidazate framework ZIF-90 and prepare nano pore at capillary tip.Overcome with the nano pore structure that the method is prepared the problem that ZIF-90 material can not directly apply to nano pore technology, develop the new opplication of ZIF-90 material.
The present invention realizes mainly through following technical scheme:
Under the support of kapillary supporter, zinc ion solution diffuses to the aqueous solution containing 2-imidazole formaldehyde from the tip of kapillary, thus at capillary tip synthesis of nano pore passage structure.
Specifically, this method is based on the zeolite imidazole ester framed structure ZIF-90 that can be prepared in a mild condition, and zinc ion diffuses in the aqueous solution containing crosslinking chemical 2-imidazole formaldehyde, has the nano pore structure of sod topological structure in tip synthesis.
Further, the nano pore structure of this method synthesis is mainly applied in Ion transfer, gas sensing, and therefore this method solvent is water.Further, for promoting the dissolving of 2-imidazole formaldehyde, before synthesis, 2-imidazole formaldehyde is added in ultrapure water, the 2-imidazole formaldehyde aqueous solution that hot reflux 30min obtains clarifying is added at 80-90 DEG C, insert the kapillary that zinc ion solution is housed afterwards, zinc ion solution is spread by capillary tip, controls its rate of propagation under 55-65 DEG C of constant temperature, is conducive to the generation of ZIF-90 framed structure and is gathered in capillary tip.This method preparation time 12-36h, but be not limited in 12-36h, due to capillary tip size slightly difference, rate of propagation under the same terms is slightly different, under optimum condition, nano pore structure size diameter 1-10 μm prepared by preparation time 12h, size diameter all can stable existence at 1-200 μm.
In the present invention, described supporter is glass capillary, and glass capillary preparation method is simple, and preparation condition is ripe, easily operates, and controllability is better, is suitable for being used in aqueous environment.
Above-mentioned capillary form is circular, but is not restricted to circle, can be square, triangle etc.; Can drainage tube be comprised in kapillary, but not be restricted to the kapillary that must have stream pipe.In addition, kapillary is only nanoscale at tip, and its afterbody is macro-size, and total length is several millimeters to tens centimetres.Kapillary be prepared as prior art, the present invention is not particularly limited this.
Nano pore structure prepared by the present invention is applied mainly as a kind of electrochemical device, therefore its electrochemical analysis step is comprised: the tinsel of two same materials is respectively as working electrode with to electrode, working electrode uses after inserting and the kapillary inside of electrolytic solution being housed, electrode is then directly inserted in External electrolytic liquid, tests its i-V curve by linear sweep voltammetry.
Be that nano pore structure prepared by supporter has good using value in the field such as electron device, sensing with glass capillary.Application one: Novel diode, nanotube is the most advanced and sophisticated single hole for 100-200nm before the synthesis, by electrochemical measurement i-v curve, comparatively significantly rectifier phenomena is only had when electrolyte concentration is lower, after synthesis completes, nanotube is most advanced and sophisticated is less than the sub-nano pore structure of 1nm for aperture, because aperture is close to ion size, tip taper pattern and make the migration difficulty differentiation of different directions inside and outside kation with the capillary wall of negative electricity, survey galvanochemistry i-V signal and there will be fairly obvious rectifying effect.Application two: pH response, as shown in the above description, the negative charge density of glass capillary wall can affect the size of current passed through to a great extent, therefore at the current-responsive that electrolyte inside is the highly basic of variable concentrations, " on " current potential has different size under the condition of highly basic and weak base, namely this structure can realize response in the pH interval of neutrality to alkalescence.Application three: carbon dioxide sensing, zeolite imidazole ester framework (ZIF) structure has good adsorption effect to carbon dioxide, after absorbing carbon dioxide, the original pore passage structure of ZIF structure can block and then affect the migration of ion, and therefore the present invention can also as the sensing of the micro-molecular gas such as carbon dioxide.
From technique scheme and result, the present invention has prepared the nanochannel structure based on zeolite imidazole ester framework innovatively, develops the application of zeolite imidazole ester framework ZIF-90 in nanochannel technology.It is advantageous that starting material are simple, cheap, be easy to get, mild condition, device architecture is stablized, reusable.And kapillary rear end is macro-size, be conveniently combined with various machinery, electronic equipment, potential using value is very large.
Accompanying drawing explanation
Fig. 1 is the method schematic diagram that the present invention prepares nano pore structure.
Fig. 2 is the structural representation of zeolite imidazole ester framework ZIF-90.
Fig. 3 is the Electronic Speculum figure after the processing of nano-glass kapillary.
Fig. 4 is the nano pore structure photo of the different size of preparation.
Fig. 5 is electrochemical testing device schematic diagram.
The i-V curve that Fig. 6 is electrolyte when being 0.01mol/L sodium hydroxide solution.
Fig. 7 is the i-V curve of variable concentrations sodium hydroxide solution.
Fig. 8 is the i-V curve of different electrolyte solution.
Fig. 9 is CO absorption
2curent change under-0.3V afterwards.
Embodiment
Illustrate below in conjunction with embodiment and accompanying drawing and technical scheme of the present invention be described further, but should not be construed as limitation of the present invention:
Embodiment 1
The present invention prepares the method for nano pore, comprises the steps:
(1) glass capillary tip is prepared: instrument used is that SUTTER company of U.S. P-2000 draws pin instrument, and glass capillary is the BOROSILIGATEGLASSWITHFILAMENT of SUTTER company, O.D:1.0mm, I.D:0.58mm, and total length is 10cm.Parameters is LINE1:HEAT=350, FIL=3, VEL=30, DEL=200, PUL=NullLINE2:HEAT=340, FIL=2, VEL=27, DEL=160, PUL=250.
The capillary tip diameter prepared under these conditions with the kapillary of this specification is 100-200nm, as shown in Figure 3.
(2) prepare 2-imidazole formaldehyde aqueous solution: 2-imidazole formaldehyde is added to the water 80 DEG C add hot reflux 30min obtain clarify bright yellow solution.
(3) prepare nano pore: as shown in Figure 1, zinc ion solution is joined the tip of nano-glass kapillary, then tip is immersed in 2-imidazole formaldehyde solution, constant temperature diffusion 12h in 60 DEG C of metal baths.Due to diffusion, the atom N of zinc ion and imidazole ring (Im) forms Zn-Im-Zn coordination bond, through so continuous conjunction, finally forms the zeolite imidazole ester framed structure of a parcel mouth of pipe at supporter top, size diameter at 1-10 μm, as shown in Fig. 4 a, 4b.
Embodiment 2
2-imidazole formaldehyde, with the step (1) of embodiment 1, is added to the water 90 DEG C and adds hot reflux 30min and obtain clarifying bright yellow solution by the preparation at glass capillary tip in step (2).In step (3), in 55 DEG C of metal baths, constant temperature spreads 15h.The zeolite imidazole ester framework size diameter prepared at 20-50 μm, as illustrated in fig. 4 c.
Embodiment 3
2-imidazole formaldehyde, with the step (1) of embodiment 1, is added to the water 85 DEG C and adds hot reflux 30min and obtain clarifying bright yellow solution by the preparation at glass capillary tip in step (2).In step (3), in 65 DEG C of metal baths, constant temperature spreads 36h.The zeolite imidazole ester framework size diameter prepared at 100-200 μm, as shown in figure 4d.
Embodiment 4
The nano pore of the present embodiment to preparation in embodiment 1 has carried out electro-chemical test, and Fig. 5 is the device schematic diagram of electro-chemical test.1 be platinum filament as electrode, 2 is electrolyte solutions, 3 be preparation receive pore passage structure.With 0.01mol/L NaOH for electrolyte, linear sweep voltammetry scans, take-off potential+0.8V, stop current potential-0.8V, sweep fast 0.01V/s, result as shown in Figure 6, because tube wall is electronegative, cationic migration is occupied an leading position, and under positive potential, kation moves from inside to outside, because most advanced and sophisticated aperture is less, a large amount of kation gathers at tapering point, produce inverse electromotive force, therefore electric current is very little, creates good rectifying effect.
Embodiment 5
The present embodiment is the application of nano pore in pH response of preparation in embodiment 1, device is identical with embodiment 4, the concentration of electrolyte NaOH changes into by 0.001 to same glass capillary, 0.005,0.01mol/L scans its i-V curve, result as shown in Figure 7, all have rectifying effect clearly, but the electric current under negative potential increases along with concentration and increases.Same, electrolyte is changed into the sodium bicarbonate of 0.01mol/L, sodium chloride, ammonium chloride, result is as Fig. 8, and along with the decline of pH and the introducing of chlorion, the migration of negative ion also plays a role in electric current, and rectifying effect weakens.
Embodiment 6
The present embodiment is the application of nano pore in carbon dioxide sensing of preparation in embodiment 1, and device is identical with embodiment 4, for avoiding electrolyte to CO
2impact, select the sodium bicarbonate solution of 0.1mol/L to reduce CO as electrolyte
2hydrolysis, is placed in CO by the pore passage structure of receiving of preparation after scanning i-V curve in advance
230min is processed in atmosphere, carry out repeatedly i-V multiple scanning continuously afterwards, under positive potential, electric current is always very little, the impact only having the open-circuit current under negative potential to be subject to is larger, result as shown in Figure 9, with the electric current under-0.3V electromotive force for reference, after finding carbon dioxide treatment, the open-circuit current that originally should be under " on " state reduces rapidly, illustrate that whole passage is tending towards complete closure state, until along with gas absorption desorption in the solution after 2h, channel part reopens, weak current and slight rectifying effect is had to occur.
Claims (10)
1. prepare a method for nano pore, it is characterized in that, in capillary tip synthesis, there is zeolite structured imidazate framework ZIF-90, directly prepare nano-pore device based on ZIF-90 structure.
2. prepare the method for nano pore according to claim 1, it is characterized in that, comprise the steps:
(1) capillary tip is prepared;
(2) 2-imidazole formaldehyde aqueous solution is prepared: 2-imidazole formaldehyde is added to the water 80-90 DEG C and adds hot reflux and obtain settled solution;
(3) prepare nano pore: be supporter with kapillary, be added in kapillary by zinc solution in the settled solution be inserted in (2), zinc solution is constant temperature diffusion from capillary tip prepared by (1), at capillary tip synthesis of nano pore passage structure.
3. prepare the method for nano pore according to claim 2, it is characterized in that, in described step (1), capillary tip uses SUTTER company of U.S. P-2000 to draw pin instrument to prepare, and the capillary tip diameter prepared is 100-200nm.
4. prepare the method for nano pore according to claim 2, it is characterized in that, described step (3) constant temperature at 55-65 DEG C carries out, and the reaction time is at 12-36h.
5. according to claim 2 or 4, prepare the method for nano pore, it is characterized in that, described step (3) constant temperature at 60 DEG C carries out, reaction time 12h.
6. prepare the method for nano pore according to claim 2, it is characterized in that, the kapillary supporter in described step (3) is glass capillary.
7. prepare the method for nano pore according to claim 2, it is characterized in that, in described step (1), capillary tip uses glass capillary and SUTTER company of U.S. P-2000 to draw pin instrument to prepare, and the capillary tip diameter prepared is 100-200nm; In described step (2), 2-imidazole formaldehyde is added to the water 80 DEG C and adds hot reflux; Described step (3) constant temperature at 60 DEG C carries out, reaction time 12h.
8. according to claim 1-4, nano pore structure prepared by the method preparing nano pore structure described in 6,7 any one.
9. the application of nano pore structure according to claim 8 in chemical analysis and bioanalysis.
10. the application of nano pore structure according to claim 9 in chemical analysis and bioanalysis, is characterized in that, described nano pore structure is used for ion screening, rectification and detection of gas.
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| CN107356580A (en) * | 2017-06-27 | 2017-11-17 | 南京大学 | A kind of nanometer single hole based on dispersed nano lamella and its preparation method and application |
| CN108247036A (en) * | 2018-01-15 | 2018-07-06 | 南京大学 | A kind of metal nano porous structure and its preparation method and application |
| CN111366627A (en) * | 2020-03-23 | 2020-07-03 | 南京大学 | Covalent organic framework porous structure of capillary tip and preparation method and application thereof |
| CN111487307A (en) * | 2020-05-07 | 2020-08-04 | 温州大学 | Method for detecting protein based on borosilicate glass nanopores modified by metal organic framework material |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106841157A (en) * | 2016-12-23 | 2017-06-13 | 南京大学 | A kind of method and its application that nano-porous structure is prepared based on water phase nano-particles self assemble |
| 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 |
| CN107356580A (en) * | 2017-06-27 | 2017-11-17 | 南京大学 | A kind of nanometer single hole based on dispersed nano lamella and its preparation method and application |
| 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 |
| CN108247036A (en) * | 2018-01-15 | 2018-07-06 | 南京大学 | A kind of metal nano porous structure and its preparation method and application |
| 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 |
| CN111366627A (en) * | 2020-03-23 | 2020-07-03 | 南京大学 | Covalent organic framework porous structure of capillary tip and preparation method and application thereof |
| 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 |
| CN111487307A (en) * | 2020-05-07 | 2020-08-04 | 温州大学 | Method for detecting protein based on borosilicate glass nanopores modified by metal organic framework material |
| 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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