CN115594857A - MOFs nanoparticle interface dynamic growth method and MOFs nanoparticles - Google Patents
MOFs nanoparticle interface dynamic growth method and MOFs nanoparticles Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 82
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000012010 growth Effects 0.000 title claims abstract description 40
- 239000002071 nanotube Substances 0.000 claims abstract description 83
- 239000011521 glass Substances 0.000 claims abstract description 75
- 239000012705 liquid precursor Substances 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 26
- 239000010949 copper Substances 0.000 claims abstract description 26
- 238000005370 electroosmosis Methods 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 32
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 32
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application discloses a MOFs nanoparticle interface dynamic growth method. The MOFs nano particle interface dynamic growth method comprises the following steps: obtaining a first liquid precursor raw material and a second liquid precursor raw material which can form a metal organic framework through coordination; placing the first liquid precursor feedstock within a glass nanotube; placing the second liquid precursor feedstock on a copper mesh; respectively arranging a working electrode and a reference electrode in the glass nano tube and on the copper mesh, and applying constant voltage to form a circuit loop so as to generate electroosmotic flow along the inner wall of the glass nano tube; the first liquid precursor feedstock and the second liquid precursor feedstock are mixed at the nano-interface to form the MOFs nanoparticles. The method and the device do not need to use any external mark, can realize the interface growth and movement of the MOFs nanoparticles only by utilizing the glass nanotubes to generate electroosmotic flow, and can control the precise synthesis of the MOFs nanoparticles by changing the electroosmotic flow.
Description
Technical Field
The invention relates to the technical field of nano material preparation and ultramicro electrochemical analysis, in particular to a dynamic growth method for an MOFs nano particle interface.
Background
In recent years, metal Organic Frameworks (MOFs) having a highly ordered three-dimensional porous crystal structure have received more and more attention, and compared with conventional porous materials (such as porous silicon and mesoporous molecular sieves), MOFs have advantages of high specific surface area, adjustable pore size, easy functionalization and the like. ZIF-8 is widely applied to the fields of gas adsorption and separation, reaction driving and monitoring, biosensing, medicine-carrying diagnosis and treatment and the like as classical MOFs. The synthesis of ZIF-8 focuses on hydrothermal method, solvothermal method, microwave-assisted method and xerogel method, and research shows that pulse laser deposition method and seed growth method can be used for synthesizing ZIF-8. However, the growth mechanism of ZIF-8 is not clear and accurate and detailed information of the early growth stage is difficult to obtain due to its rapid formation in solution.
Therefore, there is an urgent need to develop a simple and sensitive strategy for effectively analyzing the growth mechanism of Metal Organic Frameworks (MOFs) such as ZIF-8. The electrochemical method has higher space-time detection capability and good sensitivity, and is widely applied to micro/nano-scale sensing and detection. In particular, glass nanotubes have become an attractive nanoscale electrochemical sensor with a tip size that allows high resolution detection, facilitating measurement and monitoring of dynamic chemical reactions.
Disclosure of Invention
The invention aims to provide a MOFs (metal organic frameworks) nanoparticle interface dynamic growth method and MOFs nanoparticles, which can solve the technical problem that the interface growth of the MOFs nanoparticles cannot be realized to control the precise synthesis of the MOFs nanoparticles due to the difficulty in effectively obtaining the growth mechanism of the MOFs at present.
In order to achieve the above object, an embodiment of the present invention provides a method for interface dynamic growth of MOFs nanoparticles, which includes the steps of:
obtaining a first liquid precursor raw material and a second liquid precursor raw material capable of forming a metal organic framework by coordination;
placing the first liquid precursor feedstock within a glass nanotube;
placing the second liquid precursor feedstock on a copper mesh;
respectively arranging a working electrode and a reference electrode in the glass nano tube and on the copper mesh;
applying a constant voltage between the working electrode and the reference electrode to form a circuit loop, so that electroosmotic flow is generated along the inner wall of the glass nanotube; and
and adjusting the voltage in the glass nano tube to enable the first liquid precursor raw material to be positioned at the tip of the glass nano tube, controlling the tip of the glass nano tube to gradually approach the surface of the second liquid precursor raw material on the copper mesh, and mixing the first liquid precursor raw material and the second liquid precursor raw material at a nano interface to form the MOFs nano particles.
Further, in the step of obtaining a first liquid precursor raw material and a second liquid precursor raw material capable of forming a metal-organic framework by coordination, the first liquid precursor raw material comprises dimethyl imidazole 2MeIm, and the second liquid precursor raw material comprises zinc nitrate Zn (NO) 3 ) 2 The Metal Organic Frameworks (MOFs) nanoparticles comprise ZIF-8 nanoparticles, and the ZIF-8 nanoparticles are composed of zinc ions (Zn) 2+ ) Coordinated to dimethylimidazole (2 MeIm).
Further, before the step of placing the first liquid precursor raw material into the glass nanotube, the method further comprises:
glass nanotubes with sharp tips were drawn in two steps using a laser drawing machine.
Further, the step of drawing the glass nanotube having the pointed end by two steps using a laser drawing instrument includes:
selecting a laser drawing instrument as a P-2000 laser drawing instrument;
setting the first step parameters of the P-2000 laser drawing instrument as Heat 700, fil 4, vel 32, del 128 and pul 70; setting the parameters of the second step of the P-2000 laser drawing instrument as Heat 750, fil 4, vel 16, del 132 and pul 130; wherein Heat is the laser output power; fil is a shorthand for Filament, which is a laser scanning mode; vel is a shorthand for Velocity, to stop the heating rate; del is short for Delay, and is the time from the first heating stop to the second heating stop when a plurality of portions are drawn; pul is shorthand for Pull, a pulling force used to draw nanotubes;
the P-2000 laser drawing instrument was started to draw glass nanotubes with 100 ± 10nm tips by a two-step process.
Further, the step of respectively arranging the working electrode and the reference electrode in the glass nanotube and on the copper mesh comprises:
arranging the glass nano tube above a copper net;
placing an Ag/AgCl electrode in the glass nano tube to be used as a working electrode;
another Ag/AgCl electrode was attached to the copper grid as a reference electrode.
Further, in the step of forming a circuit loop by applying a constant voltage between the working electrode and the reference electrode, the constant voltage is in a range of-1000 mV to 1000mV.
Further, in the step of mixing the first liquid precursor raw material and the second liquid precursor raw material at the nanometer interface to form the MOFs nanoparticles, the method further includes:
and the electroosmotic flow is changed by adjusting the value of the constant voltage, so that the proportion of the first liquid precursor raw material and the second liquid precursor raw material for forming the MOFs nano-particles is controlled, and the appearance of the metal organic framework is controlled.
Further, after the step of applying a constant voltage between the working electrode and the reference electrode to form a circuit loop, the method further comprises the following steps:
recording an electrochemical signal in the glass nanotube by using a current amplifier;
and filtering the electrochemical signal recorded by the current amplifier by adopting a low-pass Bessel filter, and continuously recording the current signal so as to dynamically monitor the growth and the movement of the MOFs nano-particles.
Further, after the step of mixing the first liquid precursor raw material and the second liquid precursor raw material at the nanometer interface to form the MOFs nanoparticles, the method further comprises:
in situ scanning electron microscopy images were used to verify the formation of MOFs nanoparticles.
The application also provides MOFs nanoparticles prepared by the MOFs nanoparticle interface dynamic growth method.
The MOFs nanoparticle interface dynamic growth method and the MOFs nanoparticles provided by the invention have the beneficial effects that no external mark is needed, the interface growth and movement of the MOFs nanoparticles (such as ZIF-8) can be realized only by using the glass nanotubes (the tip size is about 100 nm) to generate electroosmotic flow, and the precise synthesis of the MOFs nanoparticles can be controlled by changing the electroosmotic flow.
Drawings
The technical solution and other advantages of the present application will be presented in the following detailed description of specific embodiments of the present application with reference to the accompanying drawings.
Fig. 1 is a flowchart of an interface dynamic growth method of MOFs nanoparticles provided in an embodiment of the present application.
Fig. 2 is a flowchart of a procedure of drawing a glass nanotube having a tip by two steps using a laser drawing apparatus according to an embodiment of the present application.
Fig. 3 is a flowchart of the steps of disposing a working electrode and a reference electrode in the glass nanotube and on the copper mesh, respectively, according to an embodiment of the present application.
FIG. 4 is a schematic view of electroosmotic flow-regulated dynamic growth of a ZIF-8 nanoparticle interface provided in an embodiment of the present application.
Fig. 5 is a flowchart of a method for interface dynamic growth of MOFs nanoparticles according to another embodiment of the present application.
Fig. 6 is a flowchart of a MOFs nanoparticle interfacial dynamic growth method according to yet another embodiment of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
As shown in fig. 1, an embodiment 1 of the present invention provides a method for interface dynamic growth of MOFs nanoparticles, which includes the steps of:
s1, obtaining a first liquid precursor raw material and a second liquid precursor raw material which can form a metal organic framework through coordination;
s2, using a laser drawing instrument to draw the glass nano tube with the tip through two steps;
s3, placing the first liquid precursor raw material in a glass nano tube;
s4, placing the second liquid precursor raw material on a copper net;
s5, respectively arranging a working electrode and a reference electrode in the glass nano tube and on the copper mesh;
s6, applying constant voltage between the working electrode and the reference electrode to form a circuit loop so as to generate electroosmotic flow along the inner wall of the glass nano tube; and
s7, adjusting the voltage in the glass nano tube to enable the first liquid precursor raw material to be located at the tip of the glass nano tube, controlling the tip of the glass nano tube to gradually approach the surface of the second liquid precursor raw material on the copper mesh, and mixing the first liquid precursor raw material and the second liquid precursor raw material at a nano interface to form the MOFs nano particles.
Wherein step S2 is not required if the glass nanotubes are present.
In this embodiment, the step S1 of obtaining a first liquid precursor raw material and a second liquid precursor raw material capable of forming a metal-organic framework by coordination includes a first liquid precursor raw material and a second liquid precursor raw material, the first liquid precursor raw material includes dimethylimidazole 2MeIm, and the second liquid precursor raw material includes zinc nitrate Zn (NO) 3 ) 2 The Metal Organic Frameworks (MOFs) nanoparticles comprise ZIF-8 nanoparticles, and the ZIF-8 nanoparticles are composed of zinc ions (Zn) 2+ ) Coordinated to dimethylimidazole (2 MeIm).
Two precursors for synthesizing ZIF-8 in the present invention were placed inside the glass nanotubes (inside: dimethylimidazole) and outside the glass nanotubes (outside: zinc nitrate), respectively. By applying constant voltage on the working electrode in the glass nano tube, electroosmotic flow is generated along the inner wall, and the ZIF-8 nano particles are induced to be formed by mixing at a nano interface at the tip of the glass nano tube.
As shown in fig. 2, in the present embodiment, the step S2 of drawing the glass nanotube having a sharp end by two steps using a laser drawing machine includes:
s21, selecting a laser drawing instrument as a P-2000 laser drawing instrument;
s22, setting the first step parameters of the P-2000 laser drawing instrument as Heat 700, fil 4, vel 32, del 128 and pul 70; setting the parameters of the second step of the P-2000 laser drawing instrument as Heat 750, fil 4, vel 16, del 132 and pul 130; wherein Heat is the laser output power; fil is a shorthand for Filament, which is a laser scanning mode; vel is shorthand for Velocity, stopping the heating rate; del is short for Delay, and is the time from the first heating stop to the second heating stop when a plurality of portions are drawn; pul is shorthand for Pull, a pulling force used to draw nanotubes;
and S23, starting the P-2000 laser drawing instrument to draw the glass nanotube with the tip of 100 +/-10 nm by a two-step method.
It is noted that the P-2000 laser drawing machine draws glass nanotubes having a tip size of about 100 nm. Wherein, the parameters of the glass nano tube can be adjusted, and the required size of the glass nano tube is drawn. In a P-2000 laser drawing instrument, heat (0-999) laser output power can increase or decrease the aperture of the nanotube every 10 units of change, fill (0-15) laser scanning mode can increase or decrease the aperture of the nanotube every 1 unit of change, vel (0-255) stops heating speed, generally between 45-60, del (0-255) draws for a plurality of times, first stops heating to second heating, del =128, hard drawing is performed while the laser is turned off, pull (0-255) is the pulling force used for drawing the nanotube, and the aperture of the nanotube can increase or decrease every 5 units of change; all parameters need to be adjusted according to experience, all parameters are not necessarily fixedly used, and generally, each parameter used for working is kept consistent; the size of the tip of the glass nanotube used in the method is controlled to be about 100nm, and synthesis of ZIF-8 nanoparticles of a nanometer interface is realized.
As shown in fig. 3, in this embodiment, the step S5 of providing the working electrode and the reference electrode in the glass nanotube and on the copper mesh, respectively, includes:
s51, arranging the glass nano tube above a copper net;
s52, placing an Ag/AgCl electrode in the glass nano tube to serve as a working electrode;
and S53, connecting another Ag/AgCl electrode to the copper net to serve as a reference electrode.
In this example, in the step of forming a circuit loop by applying a constant voltage between the working electrode and the reference electrode, the constant voltage is in the range of-1000 mV to 1000mV. In the embodiment, the formed electric signals and the appearance of the electron microscope are observed by adopting constant voltages of +/-200 mV, +/-400 mV, +/-600 mV, +/-800 mV, +/-1000 mV.
In this embodiment, in the step of mixing the first liquid precursor raw material and the second liquid precursor raw material at the nano interface to form the MOFs nanoparticles, the method further includes: and the electroosmotic flow is changed by adjusting the value of the constant voltage, so that the proportion of the first liquid precursor raw material and the second liquid precursor raw material for forming the MOFs nano-particles is controlled, and the appearance of the metal organic framework is controlled.
The embodiment dynamically monitors the growth and the movement of the ZIF-8 nano particles by utilizing a high-resolution electrochemical system, and distinguishes the formation and the movement of the ZIF-8 nano particles by identifying electrochemical signals. In situ scanning electron microscopy images were used to characterize the successful formation of ZIF-8 nanoparticles.
FIG. 4 is a graphical representation of the dynamic growth of the interface of the ZIF-8 nanoparticles for electroosmotic flow modulation in this example. (i) ZIF-8 precursor (2 MeIm and Zn (NO) 3 ) 2 ) Respectively added into the glass nano tube and out of the glass nano tube. (ii) electroosmotic flow induces the inner solution to contact the outer droplet. Electroosmotic flow is the flow of fluid caused by the application of a voltage across porous media, microchannels, and other fluid conduits. In the embodiment, electroosmotic flow driving force is utilized to drive the solution to the outsideAnd (4) moving. (iii) The growth and movement of the ZIF-8 nanoparticles were observed from the current trace.
The advantages of this embodiment are: (1) The aperture of the glass nano tube is about 100nm, so that the glass nano tube is allowed to be monitored at a nano-sized liquid-liquid interface; (2) The formation and the movement of the ZIF-8 nanoparticles can be precisely controlled by electroosmotic flow generated by the voltage applied to the working electrode; (3) The proportion of the precursor is easily controlled by changing electroosmotic flow, so that the shape of the ZIF-8 is controlled, a new method is provided for carrying out accurate chemical reaction on an interface, and a powerful tool is provided for researching the interface behavior of the ZIF-8.
Example 2
As shown in fig. 5, embodiment 2 of the present application includes all the technical features of embodiment 1, and the difference is that embodiment 2 further includes, after the step S6 of applying a constant voltage between the working electrode and the reference electrode to form a circuit loop:
s8, recording an electrochemical signal in the glass nano tube by using a current amplifier;
and S9, filtering the electrochemical signal recorded by the current amplifier by adopting a low-pass Bessel filter, and continuously recording the current signal so as to dynamically monitor the growth and the movement of the MOFs nanoparticles.
It is understood that fig. 5 only shows a part of the sequence of steps, and step S7 is in parallel with steps S8 and S9.
When the device is used, the formed electric signals and the appearance of the electron microscope are observed by adopting constant voltages of +/-200 mV, +/-400 mV, +/-600 mV, +/-800 mV and +/-1000 mV.
(1) Constructing an electrochemical dynamic analysis platform: one Ag/AgCl electrode is arranged in the glass nano tube to be used as a working electrode, and the other Ag/AgCl electrode is soaked in zinc nitrate liquid drops to be used as a reference electrode. And a constant voltage is applied between the working electrode and the reference electrode, and the working electrode and the reference electrode form a circuit loop together. The glass nanotubes were fixed on a support and the electrochemical signals were recorded using a current amplifier. And filtering the electrochemical signal recorded by the current amplifier by using a low-pass Bessel filter with the sampling frequency of 5kHz to 100 kHz. And controlling the glass nano tube to move along the X, Y and Z directions until the tip of the glass nano tube is close to the position of the zinc nitrate liquid drop on the copper mesh, and the tip of the glass nano tube is just collided with the zinc nitrate liquid drop on the copper mesh or enters the liquid drop. The current signal is recorded continuously throughout the process.
(2) Controllable dynamic growth and monitoring of ZIF-8 nanoparticles at liquid-liquid interface: first, 10 μ L of a dimethylimidazole solution was added to the back end of the glass nanotubes (opposite of the nanotube tip, like the tip and the back of the needle). Then, two Ag/AgCl electrodes were inserted into the glass nanotubes and into the zinc nitrate droplets on the copper mesh, respectively. And an x-y-z micro-manipulation system is adopted to adjust the tip of the glass nano tube to be gradually close to the surface of the liquid drop, so that the dynamic mixing of the two solutions at the nano interface is realized.
Example 3
As shown in fig. 6, embodiment 3 of the present application includes all the technical features of embodiment 1 or embodiment 2, and the difference is that, in embodiment 3, after the step S7 of mixing the first liquid precursor raw material and the second liquid precursor raw material at the nano interface to form the MOFs nanoparticles, the method further includes:
and S10, verifying the formation of the MOFs nanoparticles by using an in-situ scanning electron microscope image.
It is understood that fig. 6 only shows a part of the sequence of steps, which includes steps S8 and S9 of embodiment 2, and step S7 is in parallel relationship with steps S8 and S9. Step S10 may be provided after steps S8, S9.
In the embodiment, the ZIF-8 nano particles are respectively generated in the glass nano tube and on the copper mesh by applying forward voltage and reverse voltage, the glass nano tube and the copper mesh used after the experiment can be directly characterized under a field emission scanning electron microscope, and the generated particles are determined to be ZIF-8.
The application also provides the MOFs nanoparticles, which are prepared by the MOFs nanoparticle interface dynamic growth method.
The invention has the beneficial effects that the MOFs nanoparticle interface dynamic growth method and the MOFs nanoparticles are provided, any external mark is not needed, the interface growth and the movement of the MOFs nanoparticles (such as ZIF-8) can be realized only by using the glass nanotubes (the tip size is about 100 nm) to generate electroosmotic flow, and the precise synthesis of the MOFs nanoparticles can be controlled by changing the electroosmotic flow.
The invention has the advantages that: (1) The aperture of the glass nano tube is about 100nm, so that the glass nano tube is allowed to be monitored at a nano-sized liquid-liquid interface; (2) Electroosmotic flow generated by voltage applied to the working electrode can accurately control the formation and movement of the ZIF-8 nanoparticles; (3) The proportion of the precursor is easily controlled by changing electroosmotic flow, so that the morphology of the ZIF-8 is controlled, a novel method is provided for carrying out accurate chemical reaction on an interface, and a powerful tool is provided for researching the interface behavior of the ZIF-8.
The above embodiments of the present application are described in detail, and specific examples are applied in the present application to explain the principles and implementations of the present application, and the description of the above embodiments is only used to help understand the technical solutions and core ideas of the present application; those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure as defined by the appended claims.
Claims (10)
1. A MOFs nanoparticle interface dynamic growth method is characterized by comprising the following steps:
obtaining a first liquid precursor raw material and a second liquid precursor raw material which can form a metal organic framework through coordination;
placing the first liquid precursor feedstock within a glass nanotube;
placing the second liquid precursor feedstock on a copper mesh;
respectively arranging a working electrode and a reference electrode in the glass nano tube and on the copper mesh;
applying a constant voltage between the working electrode and the reference electrode to form a circuit loop, so that electroosmotic flow is generated along the inner wall of the glass nanotube; and adjusting the voltage in the glass nano tube to enable the first liquid precursor raw material to be positioned at the tip of the glass nano tube, controlling the tip of the glass nano tube to gradually approach the surface of the second liquid precursor raw material on the copper mesh, and mixing the first liquid precursor raw material and the second liquid precursor raw material at a nano interface to form the MOFs nano particles.
2. The MOFs nanoparticle interfacial dynamic growth method according to claim 1, wherein in said step of obtaining a first liquid precursor raw material and a second liquid precursor raw material capable of forming a metal-organic framework by coordination, said first liquid precursor raw material comprises dimethylimidazole, said second liquid precursor raw material comprises zinc nitrate, said metal-organic framework nanoparticles comprise ZIF-8 nanoparticles, and said ZIF-8 nanoparticles are formed by coordination of zinc ions and dimethylimidazole.
3. The MOFs nanoparticle interfacial dynamic growth method according to claim 2, further comprising, before the step of placing the first liquid precursor raw material into a glass nanotube:
glass nanotubes with sharp tips were drawn in two steps using a laser drawing machine.
4. The MOFs nanoparticle interfacial dynamic growth method according to claim 3, wherein the step of drawing the glass nanotubes with sharp ends by two steps using a laser drawing instrument comprises:
selecting a laser drawing instrument as a P-2000 laser drawing instrument;
setting the first step parameters of the P-2000 laser drawing instrument as Heat 700, fil 4, vel 32, del 128, pul 70; setting the parameters of the second step of the P-2000 laser drawing instrument as Heat 750, fil 4, vel 16, del 132 and pul 130; wherein Heat is the laser output power; fil is a short writing of Filament, and is in a laser scanning mode; vel is shorthand for Velocity, stopping the heating rate; del is short for Delay, and is the time from the first heating stop to the second heating stop when a plurality of portions are drawn; pul is shorthand for Pull, a pulling force used to draw nanotubes;
starting the P-2000 laser drawing instrument to draw the glass nano tube with the tip of 100 +/-10 nm by a two-step method.
5. The MOFs nanoparticle interfacial dynamic growth method of claim 2, wherein the step of disposing a working electrode and a reference electrode inside the glass nanotube and on the copper mesh, respectively, comprises:
disposing the glass nanotubes over the copper mesh;
placing an Ag/AgCl electrode in the glass nano tube to be used as a working electrode;
another Ag/AgCl electrode was attached to the copper grid as a reference electrode.
6. The MOFs nanoparticle interfacial dynamic growth method according to claim 2, wherein in the step of forming a circuit loop by applying a constant voltage between the working electrode and the reference electrode, the constant voltage is in a range of-1000 mV to 1000mV.
7. The MOFs nanoparticle interfacial dynamic growth method according to claim 6, wherein said step of mixing said first liquid precursor material and said second liquid precursor material at a nano interface to form MOFs nanoparticles further comprises:
and the electroosmotic flow is changed by adjusting the value of the constant voltage, so that the proportion of the first liquid precursor raw material and the second liquid precursor raw material for forming the MOFs nano-particles is controlled, and the appearance of the metal organic framework is controlled.
8. The MOFs nanoparticle interfacial dynamic growth method according to claim 2, further comprising, after the step of forming a circuit loop by applying a constant voltage between the working electrode and the reference electrode:
recording an electrochemical signal in the glass nanotube by using a current amplifier;
and filtering the electrochemical signal recorded by the current amplifier by adopting a low-pass Bessel filter, and continuously recording the current signal so as to dynamically monitor the growth and the movement of the MOFs nano-particles.
9. The method of claim 8, wherein after the step of mixing the first liquid precursor material and the second liquid precursor material at the nano interface to form the MOFs nanoparticles, the method further comprises:
in situ scanning electron microscopy images were used to verify the formation of MOFs nanoparticles.
10. MOFs nanoparticles, prepared by the MOFs nanoparticle interfacial dynamic growth method according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
| CN105372320A (en) * | 2015-10-29 | 2016-03-02 | 南京大学 | 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 |
| CN107151331A (en) * | 2017-06-05 | 2017-09-12 | 北京化工大学 | A kind of method of the quick preparation structure controllable metal organic framework compounds of electrochemical method |
| CN109709175A (en) * | 2019-02-25 | 2019-05-03 | 广东海洋大学 | A kind of lead ion detection method based on nanochannel electrochemical sensor |
| CN112014429A (en) * | 2019-05-30 | 2020-12-01 | 华东理工大学 | Cell membrane vibration detection method based on ultramicro electroosmotic flow regulation |
-
2022
- 2022-10-20 CN CN202211285885.5A patent/CN115594857A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
| CN105372320A (en) * | 2015-10-29 | 2016-03-02 | 南京大学 | 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 |
| CN107151331A (en) * | 2017-06-05 | 2017-09-12 | 北京化工大学 | A kind of method of the quick preparation structure controllable metal organic framework compounds of electrochemical method |
| CN109709175A (en) * | 2019-02-25 | 2019-05-03 | 广东海洋大学 | A kind of lead ion detection method based on nanochannel electrochemical sensor |
| CN112014429A (en) * | 2019-05-30 | 2020-12-01 | 华东理工大学 | Cell membrane vibration detection method based on ultramicro electroosmotic flow regulation |
Non-Patent Citations (2)
| Title |
|---|
| DE ZHAO等: "Highly sensitive microfluidic detection of carcinoembryonic antigen via a synergetic fluorescence enhancement strategy based on the micro/ nanostructure optimization of ZnO nanorod arrays and in situ ZIF-8 coating", 《CHEMICAL ENGINEERING JOURNAL》, pages 1 - 10 * |
| 李旭飞等: "沸石咪唑酯骨架材料ＺＩＦ－９０的合成及应用研究进展", 《化工新型材料》, pages 10 - 16 * |
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