CN111366627B - Covalent organic framework porous structure of capillary tip and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a covalent organic framework porous structure of a capillary tip, a preparation method and application thereof. The structure can be used for preparing a gas sensor. The preparation method is simple, the size is micro-nano, the advantages of high response speed, good reproducibility, high sensitivity, good selectivity and stability and the like are achieved, and the development direction and the potential application value of the combination of the double-channel capillary technology and the covalent organic framework COF porous material in the fields of nano devices, analysis sensing and the like are provided.
Description
Technical Field
The invention belongs to the technical field of nano pores and the field of electrochemical sensing, and particularly relates to a covalent organic framework COF porous structure based on a double-channel capillary tip, and a preparation method and application thereof.
Background
With the development of modernization, human survival and social activities are closely related to humidity, and the humidity sensor can well monitor the humidity in the environment, and has extremely important application in the aspects of food protection, industrial and agricultural production, environment detection and the like. In recent years, electronic humidity sensors have been developed rapidly, and conventional humidity sensors mostly employ humidity sensitive elements, mainly resistive and capacitive. When the environmental humidity is detected, the humidity sensitive element is easily polluted due to long-term exposure in the environment to be detected, so that the measurement precision and the long-term stability of the humidity sensitive element are influenced. Most of the existing humidity sensors have the self limitations of large size, long response recovery time, low sensitivity, difficulty in being applied to microenvironment humidity distribution imaging and the like.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a Covalent Organic Framework (COF) porous structure based on a two-channel capillary tip, and a preparation method and application thereof. The covalent organic framework has a stable porous structure and good chemical stability, is combined with a double-channel capillary technology with a substance transmission characteristic as a support, can be used as a novel micro-nano current type sensing probe, and provides a development direction and potential application value of the combination of the double-channel capillary technology and a covalent organic framework porous material in the fields of nano devices, analytical sensing, microcosmic humidity distribution imaging and the like. The sensor based on the structure is different from the traditional electronic sensing, can monitor the humidity value or other gas concentrations in the environment according to the real-time current change, and overcomes the problems of high manufacturing cost, poor pollution resistance, long response recovery time, low sensitivity and the like of the traditional electronic sensor.
The invention is mainly realized by the following technical scheme:
a covalent organic framework porous structure of a capillary tip, the porous structure comprised of a dual channel capillary and a covalent organic framework material overlaying the tip of the dual channel capillary.
Preferably, the covalent organic framework material covers the entire tip of the two-channel capillary.
Preferably, the covalent organic framework material has a structural unit (TAPB-PDA-R-COF) as shown in formula I, wherein R is hydrogen, alkyl or alkoxy, preferably, R is hydrogen, methoxy, ethoxy, butoxy, hexyloxy, heptyloxy or octyloxy;
formula I:
preferably, the double-channel capillary is made of glass or quartz.
Preferably, the cross-section of the two-channel capillary is circular or polygonal, preferably circular. A draft tube may be included in the capillary tube.
Preferably, the tip of the double-channel capillary is nano-scale, and the tail is macro-scale.
Preferably, the total length of the double-channel capillary tube is 1-15 cm, preferably 2-10 cm. The preparation of the capillary is prior art and the present invention is not particularly limited in this regard.
Preferably, the diameter of the tip of the double-channel capillary is 400nm to 1 μm, preferably 500nm to 600nm, and under the preferred condition, the covalent organic framework material prepared at the capillary tip can completely cover the whole capillary tip.
The invention also provides a preparation method of the covalent organic framework porous structure of the capillary tip, which comprises the following steps:
injecting a 1,3, 5-tri (4-aminophenyl) benzene (TAPB) solution into the double-channel capillary by taking the double-channel capillary as a support body, then immersing the double-channel capillary into a mixed solution containing a catalyst and a compound shown in a formula II, diffusing the 1,3, 5-tri (4-aminophenyl) benzene solution from the tip of the capillary, and reacting at the tip of the capillary to obtain the porous structure;
the catalyst is scandium trifluoromethanesulfonate (Sc (OTf)3)；
Formula II:
wherein R is hydrogen, alkyl or alkoxy, preferably, R is hydrogen, C1～8Alkyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy.
That is, the compound of formula II is preferably terephthalaldehyde (PDA), 2, 5-dimethylterephthalaldehyde (PDA-Me), 2, 5-diethylterephthalaldehyde (PDA-Et), 2, 5-dipropylterephthalaldehyde (PDA-Pr), 2, 5-dibutylterephthalaldehyde (PDA-Bu), 2, 5-dipentyldterephthalaldehyde (PDA-Pen), 2, 5-dihexylterephthalaldehyde (PDA-Hex), 2, 5-diheptylterephthalaldehyde (PDA-Hep), 2, 5-dioctylterephthalaldehyde (PDA-Oct), 2, 5-dimethoxyterephthalaldehyde (PDA-oMe), 2, 5-diethoxyphthalaldehyde (PDA-oEt), 2, 5-dipropoxyphthalaldehyde (PDA-oPr), 2, 5-dibutyloxy terephthalaldehyde (PDA-oBu), 2, 5-dipentyloxy terephthalaldehyde (PDA-oPen), 2, 5-dihexyl terephthalaldehyde (PDA-oHex), 2, 5-diheptyloxy terephthalaldehyde (PDA-oHep) or 2, 5-dioctyloxy terephthalaldehyde (PDA-oOct).
Preferably, the solvent containing the mixture of the catalyst and the compound of formula II is a polar organic solvent, preferably a mixture of one or more of 1, 4-dioxane, 1,3, 5-trimethylbenzene, o-dichlorobenzene, or n-butanol, most preferably a mixture of 1, 4-dioxane and 1,3, 5-trimethylbenzene in a volume ratio of 4: 1.
Preferably, the reaction time is 50-90 s. Most preferably the reaction time is 90 s. Under the preferable conditions, the size of the porous structure prepared by the reaction time of 90s is 2 +/-1 mu m, and the porous structure has more excellent response speed and sensitivity to gas.
The invention also provides a gas sensor based on the covalent organic framework porous structure of the capillary tip.
Further, the gas sensor includes: the double-channel capillary is filled with an organic salt solution or an inorganic salt solution, two channels of the double-channel capillary are respectively inserted with a metal wire immersed in the organic salt solution or the inorganic salt solution and respectively used as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with a constant voltage and connected with an ammeter.
Preferably, the organic salt solution is prepared by dissolving tetrabutylammonium perchlorate (TnBAPC), tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium iodide or tetrabutyl titanate in a high-polarity organic solvent with low vapor pressure.
Preferably, the high polarity low vapor pressure organic solvent is Dimethylformamide (DMF), Dimethylacetamide (DMA) or Dimethylsulfoxide (DMSO), most preferably Dimethylformamide (DMF).
Preferably, the inorganic salt solution is an aqueous solution of potassium chloride, sodium chloride, lithium chloride, potassium bromide or sodium bromide.
Preferably, the concentration of the organic salt solution is 5mM to 1M, preferably 50 mM.
Preferably, the concentration of the inorganic salt solution is 5mM to 1M, preferably 50 mM.
Preferably, the constant voltage is 0.8-2V, and preferably 1.2V.
When the organic salt solution is used, the gas sensor is a humidity sensor, and when the inorganic salt solution is used, the gas sensor is an ammonia gas sensor.
A covalent organic framework COF porous structure is prepared at the tip of the double-channel capillary tube, and the covalent organic framework COF porous structure can be used as a novel current type gas sensor. Specifically, a double-channel capillary with a nanoscale tip is used as a support, under the support of the support, a TAPB solution is diffused from the capillary tip to a mixed solution containing a catalyst and a compound of a formula II, and a COF porous structure with a micron size is synthesized at the capillary tip; organic salt solution or inorganic salt solution is injected into the capillary, constant voltage is applied, and the gas concentration in the environment can be monitored according to the change of real-time current.
The support body is a double-channel glass capillary tube, the preparation method of the glass capillary tube is simple, the operation is simple and easy to control, and the glass capillary tube can be used for researching the behavior of ionic current due to the double-channel property.
Humidity sensing detection principle: the mobility of the organic salt ion in the solvent determines the solution conductance. The solution conductance decreases with increasing water molecule content in the organic solvent. Under the condition of high RH, more water molecules are absorbed by the organic solvent through the COF nano-channel, so that the mobility of organic salt ions in the organic solvent is reduced, the conductance is reduced, and the ion current is reduced; under the condition of low RH, the organic solvent absorbs less water molecules, and the reduction of the ionic current is not obvious.
The ammonia gas sensing detection principle: the ammonia gas passing through the COF nanochannels interacts with the solvent water, increasing the number of free mobile ions in the inorganic salt solution, resulting in an increase in ionic current.
The invention creatively realizes the preparation of a covalent organic framework COF porous structure at the tip of the double-channel capillary tube, and can be used as a novel current type gas sensor, in particular to a humidity sensor or an ammonia gas sensor. The preparation method has the advantages of simplicity, low cost, high response speed, good reproducibility, high sensitivity and good selectivity to gas. And the rear end of the capillary tube is in a macroscopic size, so that the capillary tube can be conveniently combined with various mechanical and electronic devices, and other selective and specific gas sensors or nano devices can be developed through the functional modification of a covalent organic framework COF porous structure, so that the potential application value is very high.
Drawings
FIG. 1 is a schematic flow diagram of the covalent organic framework porous structure for making capillary tips according to the present invention.
Fig. 2 is an electron micrograph of the covalent organic framework porous structure of the capillary tip.
FIG. 3 is a schematic diagram of a humidity sensor electrochemical sensing device.
FIG. 4 is a dynamic current response curve of a humidity sensor for different humidity levels.
Fig. 5 is a graph measuring the linearity of a humidity sensor.
Fig. 6 is a graph of response speed of a humidity sensor.
Fig. 7 is a graph measuring the repeatability of a humidity sensor.
Fig. 8 is a response curve of the ammonia gas sensor prepared in example 2.
FIG. 9 is a response curve of the humidity sensor prepared in example 3.
Detailed Description
The following description of the embodiments of the present invention is provided for further illustration with reference to the following examples and drawings, but should not be construed as limiting the present invention:
example 1
The humidity sensor prepared by the invention comprises the following steps:
(1) preparing a double-channel capillary tube: the instrument used was a P-2000 pin puller from SUTTER, USA, and the Theta double channel glass capillary was a BOROSILIGATE GLASS WITH FILAMENT, O.D from SUTTER: 1.5mm, I.D: 1.0mm and a total length of 10 cm. Setting parameters as LINE 1: HEAT 650, FIL 5, VEL 25, DEL 140, PUL 40; LINE 2: HEAT-700, FIL-4, VEL-20, DEL-128, PUL-40.
The capillary tip prepared under the above conditions with this size capillary had a diameter of about 550nm and a length of 5 cm.
(2) Preparation of TAPB solution and PDA/Sc (OTf)3Mixing liquid: mixing the solid powders TAPB and PDA/Sc (OTf)3Respectively dissolving the components in 1, 4-dioxane/1, 3, 5-trimethylbenzene organic solvent with the volume ratio of 4: 1.
(3) Preparation of the covalent organic framework porous Structure of the capillary tip TAPB-PDA-COF: as shown in FIG. 1, the TAPB solution was injected into the tip of a two-channel capillary and the tip was then dipped into a solution containing PDA/Sc (OTf)3The mixture of (3) was reacted at room temperature for 90 seconds. Due to diffusion, TAPB comes into contact with the PDA solution at the tip of the capillary, in the presence of the catalyst Sc (OTf)3Under the action of the covalent bond, a hexagonal lamellar structure is formed through covalent bond connection, and through the continuous bond, a porous covalent organic framework structure covering the pipe orifice is finally formed at the tip of the capillary, and the size diameter is 1-2 mu m, as shown in figure 2.
(4) Preparing a humidity sensor based on a covalent organic framework porous structure with a capillary tip: injecting organic salt solution (50mM tetrabutylammonium perchlorate/dimethylformamide) as electrolyte solution into capillary tube with covalent organic frame porous structure at prepared capillary tube tip, respectively inserting Ag/AgCl electrodes into two channels of capillary tube filled with electrolyte solution, respectively, exposing the same glass capillary tube in different humidity environments by electrochemical sensing device shown in figure 3, applying constant voltage +1.2V, recording current-time curve with environment humidity change by potentiostat, and sealing with saturated salt solution lithium chloride (LiCl) and magnesium chloride (MgCl) in container2) Sodium bromide (NaBr), potassium bromide (KBr) and potassium sulfate (K)2SO4) Relative humidity environments of 11%, 33%, 56%, 75% and 98% RH are respectively provided, and as a result, as shown in FIG. 4, as the relative humidity% RH of the environment is reduced, the real-time response current is sharply increased, the measurement range can reach 11-98% RH, the magnitude of the current can be maximally different by 12 times, and the humidity sensor has good selectivity and high sensitivity to humidity.
And (3) carrying out linearity test on the prepared humidity sensor: the response currents corresponding to different% RH in step (4) are linearly fitted, and the result is shown in FIG. 5, where the degree of linear fit R is20.99729, the response current has a good linear dependence on relative humidity.
For prepared humidity sensingThe response speed test is carried out by the device: the response/recovery time is the time required for the sensor to reach 90% of the total current change in both adsorption (98% RH) and desorption (11% RH), and the results are shown in fig. 6, where the response time from 11% RH to 98% RH is 9s, while only 1.2s is required from 98% RH to 11% RH, compared to other GO, MoS based sensors2And SnO2The nano humidity sensor made of the same material has high response speed.
(7) And (3) carrying out repeatability test on the prepared humidity sensor: the same glass capillary was continuously switched between the highest 98% RH and the lowest 11% RH 13 times, and the current-time curve at constant potential was recorded, and as a result, as shown in fig. 7, the response curve (98% RH) showed good reversibility, corresponding to current values that were nearly constant, while the recovery curve (11% RH) showed slight variations in current values, and the 98% RH and 11% RH response curves corresponded to standard deviations of 7% and 18%, respectively, and, overall, the humidity sensor had good stability and reproducibility.
Example 2
The ammonia gas sensor prepared by the invention comprises the following steps:
(1) a quartz two-channel capillary was prepared, the diameter of the capillary tip being 500nm and the length of the capillary being 2 cm.
(2) Preparation of TAPB solution and PDA/Sc (OTf)3Mixing liquid: mixing the solid powders TAPB and PDA/Sc (OTf)3Respectively dissolving the components in 1, 4-dioxane/1, 3, 5-trimethylbenzene organic solvent with the volume ratio of 4: 1.
(3) Preparation of the covalent organic framework porous Structure of the capillary tip TAPB-PDA-COF: injecting TAPB solution into the tip of a two-channel capillary, and immersing the tip into a solution containing PDA/Sc (OTf)3The mixture of (3) was reacted at room temperature for 50 seconds. TAPB is contacted with the PDA solution at the tip of the capillary in the presence of a catalyst Sc (OTf)3Under the action of the covalent bond connection, a hexagonal lamellar structure is formed, and finally, a porous covalent organic framework structure covering the pipe orifice is formed at the tip of the capillary, and the size diameter is 1-2 mu m.
(4) Preparing an ammonia gas sensor based on a capillary tip covalent organic framework porous structure: injecting 50mM potassium chloride aqueous solution into the capillary with the covalent organic framework porous structure at the tip of the prepared capillary as electrolyte solution, respectively inserting Ag/AgCl electrodes into two channels of the capillary filled with the electrolyte solution, applying constant voltage +0.8V by adopting an electrochemical sensing device similar to that shown in figure 3, and recording a response curve when the capillary is switched back and forth in an ammonia gas and air environment by a potentiostat. The results are shown in FIG. 8, which shows selectivity to ammonia and better reproducibility and stability.
Example 3
The humidity sensor prepared by the invention comprises the following steps:
(1) a glass double-channel capillary tube was prepared, the diameter of the capillary tip being 600nm and the length of the capillary tube being 10 cm.
(2) Preparation of TAPB solution and PDA-oMe/Sc (OTf)3Mixing liquid: mixing the solid powders TAPB and PDA-oMe/Sc (OTf)3Respectively dissolved in o-dichlorobenzene/n-butanol with the volume ratio of 4: 1.
(3) Preparation of the capillary tip covalent organic framework porous structure TAPB-PDA-oMe-COF: injecting TAPB solution into the tip of a two-channel capillary, and immersing the tip into a solution containing PDA-oMe/Sc (OTf)3The mixture of (3) was reacted at room temperature for 70 seconds. TAPB is contacted with PDA-oMe solution at the tip of a capillary in the presence of a catalyst Sc (OTf)3Under the action of the covalent bond connection, a hexagonal lamellar structure is formed, and finally, a porous covalent organic framework structure covering the pipe orifice is formed at the tip of the capillary, and the size diameter is 1-2 mu m.
(4) Preparing a humidity sensor based on a covalent organic framework porous structure with a capillary tip: injecting an organic salt solution (5mM tetrabutylammonium bromide/dimethyl sulfoxide) serving as an electrolyte solution into the capillary with the covalent organic framework porous structure at the tip of the prepared capillary, respectively inserting Ag/AgCl electrodes into two channels of the capillary filled with the electrolyte solution, applying a constant voltage +2V by adopting an electrochemical sensing device similar to that shown in figure 3, and recording a response curve when switching back and forth in an environment of 98% RH and 11% RH by using a potentiostat. The results are shown in FIG. 9, which shows selectivity to humidity and better reproducibility and stability.
Example 4
This example 4 differs from example 3 only in that the total length of the capillary used was 15cm, the diameter of the capillary tip was 1 μ M, the covalent organic framework material was prepared using TAPB and PDA-oBu as starting materials, and the electrolyte used for the sensor was 1M solution of tetrabutylammonium fluoride in dimethylacetamide.
Example 5
This example 5 differs from example 3 only in that the total length of the capillary used was 1cm, the diameter of the capillary tip was 400nm, TAPB and 2, 5-diethylterephthalaldehyde were used as starting materials to prepare the covalent organic framework material, and the sensor used a 10mM solution of tetrabutyl titanate in dimethylformamide as the electrolyte.
Claims (18)
1. A covalent organic framework porous structure of a capillary tip, characterized in that the porous structure is composed of a two-channel capillary and a covalent organic framework material covering the tip of the two-channel capillary.
2. The capillary-tip covalent organic framework porous structure of claim 1, characterized in that the covalent organic framework material covers the entire dual-channel capillary tip.
3. The capillary tip covalent organic framework porous structure of claim 1, characterized in that the covalent organic framework material has structural units according to formula I, wherein R is hydrogen, alkyl or alkoxy;
formula I:
4. the capillary-tipped covalent organic framework porous structure of claim 3, characterized in that R is hydrogen, methoxy, ethoxy, butoxy, hexyloxy, heptyloxy or octyloxy.
5. The covalent organic framework porous structure of capillary tip of claim 1, characterized in that the diameter of the tip of the two-channel capillary is 400nm to 1 μ ι η.
6. The covalent organic framework porous structure of capillary tip of claim 1, characterized in that the diameter of the tip of the two-channel capillary is 500-600 nm.
7. A method for preparing a covalent organic framework porous structure of a capillary tip according to any of claims 1 to 6, comprising the steps of:
injecting a 1,3, 5-tris (4-aminophenyl) benzene solution into the double-channel capillary by taking the double-channel capillary as a support body, then immersing the double-channel capillary into a mixed solution containing a catalyst and a compound shown in a formula II, diffusing the 1,3, 5-tris (4-aminophenyl) benzene solution from the tip of the capillary, and reacting at the tip of the capillary to obtain the porous structure; the catalyst is scandium trifluoromethanesulfonate;
formula II:
wherein R is hydrogen, alkyl or alkoxy.
8. The process according to claim 7, wherein R is hydrogen or C1～8Alkyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy or octoxy.
9. The method according to claim 7, wherein the reaction time is 50 to 90 seconds.
10. The method of claim 7, wherein the reaction time is 90 s.
11. A gas sensor based on a covalent organic framework porous structure of a capillary tip according to any of claims 1 to 6, characterized in that the gas sensor comprises: the double-channel capillary is filled with an organic salt solution or an inorganic salt solution, two channels of the double-channel capillary are respectively inserted with a metal wire immersed in the organic salt solution or the inorganic salt solution and respectively used as a working electrode and a counter electrode, and the working electrode and the counter electrode are directly applied with a constant voltage and connected with an ammeter.
12. The gas sensor according to claim 11, wherein the organic salt solution is obtained by dissolving tetrabutylammonium perchlorate, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutylammonium iodide or tetrabutyl titanate in a high-polarity organic solvent with low vapor pressure;
the inorganic salt solution is an aqueous solution of potassium chloride, sodium chloride, lithium chloride, potassium bromide or sodium bromide.
13. The gas sensor according to claim 12, wherein the high polarity low vapor pressure organic solvent is dimethylformamide, dimethylacetamide, or dimethylsulfoxide.
14. The gas sensor according to claim 13, wherein the high polarity low vapor pressure organic solvent is dimethylformamide.
15. The gas sensor according to claim 11, wherein the concentration of the organic salt solution or the inorganic salt solution is 5mM to 1M.
16. The gas sensor according to claim 15, wherein the concentration of the organic salt solution or the inorganic salt solution is 50 mM.
17. The gas sensor according to claim 11, wherein the constant voltage is 0.8V to 2V.
18. The gas sensor according to claim 17, wherein the constant voltage is 1.2V.
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| In situ synthesis of the imine-based covalent organic framework LZU1 on the inner walls of capillaries for electrochromatographic separation of nonsteroidal drugs and amino acids;Kong, Deying et al.;《Microchimica Acta》;20170208;第184卷(第4期);全文 * |
| Scanning Electrochemical Cell Microscopy Investigation of Single ZIF-Derived Nanocomposite Particles as Electrocatalysts for Oxygen Evolution in Alkaline Media;Tarnev, Tsvetan et al.;《Angewandte Chemie International Edition》;20190726;第58卷(第40期);全文 * |
| Separation of small organic molecules using covalent organic frameworks-LZU1 as stationary phase by open-tubular capillary electrochromatography;Niu, Xiaoying et al.;《Journal of Chromatography A》;20160202;第1436卷;全文 * |
| Triazine-Based Two-Dimensional Organic Polymer for Selective NO2 Sensing with Excellent Performance;Yang, Kai et al.;《ACS Applied Materials & Interfaces》;20191231;第12卷(第3期);全文 * |
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