CN107561201B - Silicon-based micro gas chromatographic column with high separation efficiency and preparation method thereof - Google Patents
Silicon-based micro gas chromatographic column with high separation efficiency and preparation method thereof Download PDFInfo
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Abstract
The invention provides a silicon-based micro gas chromatographic column with high separation efficiency and a preparation method thereof, wherein the preparation method comprises the following steps: 1) manufacturing a micro channel and a micro-fluidic port on a silicon substrate; 2) manufacturing a mask layer to protect a bonding surface on the silicon substrate; 3) constructing nano mesoporous silicon oxide in the micro channel; 4) bonding a packaging cover plate on the bonding surface of the silicon substrate; 5) and forming a corresponding modified material on the surface of the nano mesoporous silica based on the components needing to be separated. The nano mesoporous silica has larger specific surface area and pore volume, and has better thermal stability and mechanical strength, so the nano mesoporous silica is constructed in the silicon-based micro gas chromatographic column, and the separation efficiency of the chromatographic column can be greatly improved; the surface of the nano mesoporous silica has high-density silicon hydroxyl (Si-OH), and monomolecular layers with different separation functions can be further constructed on the surface of the nano mesoporous silica according to different separation objects, so that the required separation effect is realized.
Description
Technical Field
The invention relates to a silicon-based micro gas chromatographic column with high separation efficiency and a preparation method thereof, belonging to the field of micro-electromechanical systems, in particular to a silicon-based micro gas chromatographic column with high separation efficiency based on a mesoporous silica nano construction technology and a preparation method thereof.
Background
The main function of a gas chromatography column is to separate mixed sample gases to be analyzed, and the gas chromatography column is a core component of a gas chromatograph. Traditional gas chromatographic columns include capillary columns, packed columns and the like, and because the volume is large, a special column incubator is required for heating the traditional gas chromatographic columns, the power consumption of the traditional gas chromatographic columns reaches thousands of watts, and therefore the miniaturization of the gas chromatographic columns is of great importance in order to realize the miniaturization of gas chromatographs.
Since the end of the last 70 th century, attempts have been made to fabricate micro-chromatographic column chips on silicon wafers by etching/etching. In order to improve the separation efficiency of the silicon-based micro-chromatographic column, researchers carry out optimization design on the geometric structure of the silicon-based micro-chromatographic column and make important progress. The arrangement of the chromatographic columns on a silicon wafer as in A.D. radadai et al (A.D. radadai, A.Salehi-Khojin, R.I. Masel, M.A. Shannon. the effect of a micro-chromatography column on the performance of micro-chromatography columns for chip scales gas analyzers, Sensors and Actuators B150 (2010):456 & 464) shows that serpentine arrangements are preferred over serpentine arrangements; columns cross-sections are divided into circles and rectangles, high aspect ratio rectangular columns are preferred by researchers, Joshua j.while et al prepared high aspect ratio hollow rectangular columns with cross-sectional dimensions of 30 μm 675 μm in a paper (Joshua j.while, Cory s.fix, John m.anderson and et al.high-speed-two-dimensional gas chromatography using micro-machined GC columns combined with nano-electrical machinery sensors, Transducers 2009, 21-25.); mohammad amine Zarrian-Jahromi et al in the paper (Mohammad amine Zarrian-Jahromi, Mehdi Ashraf-Kharassani, Larry T. Taylor, and MasoudAgah. design, Modeling, and Fabrication of MEMS-based Multicaliforry Gas chromatography Columns, Journal of MEMS, vol.18, No.1,2009:28-37.) proposed a so-called multi-column structure, and Syed Ali et al in the same year in the paper (Syed Ali, Mehdi Ashraf-Kharani, Larry T. Taylor, Masdada. MEMS-based set-packed column chromatography Columns, arrays of 141,2009. A. micro-column structures are easily arranged in a fixed phase column array, micro-column arrays, and column arrays of 315. A. have the characteristic that the column structures are easily arranged in a fixed phase column array.
In summary, in the research of the silicon-based micro-gas chromatography column, the current progress made by researchers mainly focuses on the structural optimization design, and the space for improving the separation efficiency based on the structural optimization design is about to face the limit. The separation efficiency of the silicon-based micro gas chromatographic column is related to the fixed phase manufactured on the inner surface of the chromatographic column besides the geometrical structure parameters. Based on the above, the invention provides a silicon-based micro gas chromatography column with high separation efficiency based on mesoporous silica nano construction technology and a preparation method thereof.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a silicon-based micro gas chromatography column with high separation efficiency and a preparation method thereof, which are used for solving the problem that the separation efficiency of the silicon-based micro gas chromatography column in the prior art is difficult to further improve.
In order to achieve the above objects and other related objects, the present invention provides a method for improving the separation efficiency of a silica-based micro gas chromatography column based on a mesoporous silica nano-construction technology. Because the mesoporous silica has high specific surface area, the mesoporous silica is uniformly coated on the inner surface of the silicon-based micro gas chromatographic column by a pulling method (or other methods), so that the inner surface area of the micro gas chromatographic column is greatly increased, and the high-efficiency separation of various gas components can be realized by utilizing the high-density silicon hydroxyl on the surface of the mesoporous silica; on the other hand, according to different separation components, dense monomolecular layers with different structures can be modified on the surfaces of the mesoporous silicon oxide by utilizing high-density silicon hydroxyl on the surfaces of the mesoporous silicon oxide, the monomolecular layers have better chemical stability, and the separation of different complex gas components can be realized based on the interaction between the monomolecular layers and the components to be detected.
Accordingly, the present invention provides a method for preparing a silica-based micro gas chromatography column with high separation efficiency, the method comprising the steps of: and manufacturing a micro channel on a silicon substrate, and constructing nano mesoporous silicon oxide in the micro channel.
As a preferable scheme of the preparation method of the silicon-based micro gas chromatography column with high separation efficiency, the microchannel is further provided with a plurality of channel units or/and micro-column arrays, and the nano mesoporous silica is simultaneously constructed on the surfaces of the plurality of channel units or/and micro-column arrays.
Preferably, a non-aqueous synthesis method of solvent volatilization induced self-assembly is adopted to construct the nano mesoporous silicon oxide in the micro channel.
Preferably, the construction of the nano mesoporous silica comprises the following steps: step a), preparing a reaction solution of the nano mesoporous silica by adopting ethanol, TEOS, hydrochloric acid and CTAB powder; b), manufacturing a mask layer to protect a bonding surface on the silicon substrate, immersing the silicon substrate with the mask layer into a reaction solution of the nano mesoporous silicon oxide, and pulling out the silicon substrate by adopting a pulling method; and step c), drying the silicon substrate, removing the mask layer, and then roasting to form the nano mesoporous silicon oxide in the microchannel.
As a preferable embodiment of the preparation method of the silicon-based micro gas chromatography column with high separation efficiency of the present invention, the preparation method comprises the steps of: step 1), manufacturing a micro channel and a micro-fluidic port on a silicon substrate; step 2), manufacturing a mask layer to protect a bonding surface on the silicon substrate; step 3), constructing nano mesoporous silicon oxide in the micro channel, and removing the mask layer before roasting; and 4), bonding a packaging cover plate on the bonding surface of the silicon substrate.
Preferably, the method further comprises the steps of: scribing to obtain a silicon-based micro gas chromatographic column chip, and installing a capillary tube at the micro-fluidic port.
Preferably, the package cover plate comprises a glass substrate with two polished sides, and is bonded on the bonding surface of the silicon substrate by adopting an anodic bonding method, wherein the bonding temperature is 200-450 ℃, and the bonding voltage is 600-1400V.
As a preferable scheme of the preparation method of the silicon-based micro gas chromatographic column with high separation efficiency, the method also comprises the following steps: and forming a corresponding modified material on the surface of the nano mesoporous silica based on the components needing to be separated.
Preferably, the modifying reagent is octadecyltrichlorosilane, octadecyldimethylchlorosilane or octadecyltrimethoxysilane.
Preferably, the modification step of the octadecyltrichlorosilane comprises: step 1), preparing a mixed solution of toluene and octadecyltrichlorosilane, and injecting the mixed solution into the microchannel for reaction; and 2), cleaning the microchannel by using alcohol after reaction, and completely removing the alcohol in the microchannel in a vacuum or low-pressure environment.
The invention also provides a silicon-based micro gas chromatographic column with high separation efficiency, which comprises: a silicon substrate; a micro channel formed in the silicon substrate; the micro-fluidic ports are formed at two ends of the micro channel; and nano mesoporous silicon oxide constructed in the micro channel.
As a preferable embodiment of the silicon-based micro gas chromatography column with high separation efficiency of the present invention, the silicon-based micro gas chromatography column further comprises: corresponding modified materials are formed on the surface of the nano mesoporous silica based on components needing to be separated.
As a preferred scheme of the silicon-based micro gas chromatographic column with high separation efficiency, the modifying reagent is octadecyltrichlorosilane, octadecyldimethylchlorosilane or octadecyltrimethoxysilane.
As a preferable embodiment of the silicon-based micro gas chromatography column with high separation efficiency of the present invention, the micro channel further comprises a plurality of channel units or and/or micro column arrays, and the nano mesoporous silica is simultaneously constructed on the surfaces of the plurality of channel units or and/or micro column arrays.
As a preferable embodiment of the silicon-based micro gas chromatography column with high separation efficiency of the present invention, the present invention further comprises a sealing cover plate bonded to the surface of the silicon substrate.
Preferably, the package cover plate is a glass substrate with two polished sides, and is bonded on the bonding surface of the silicon substrate by an anodic bonding method.
As described above, the silica-based micro gas chromatography column with high separation efficiency and the preparation method thereof of the present invention have the following beneficial effects:
1) the nano mesoporous silicon oxide has larger specific surface area (about 400-1200 m)2In g) and a larger pore volume (about 1.0 cm)3About/g) and has better thermal stability and mechanical strength, the invention constructs the silica-based micro gas chromatographic column in the silica-based micro gas chromatographic column, and can greatly improve the separation efficiency of the chromatographic column;
2) the surface of the nano mesoporous silica has high-density silicon hydroxyl (Si-OH), and the invention can further construct monomolecular layers with different separation functions on the surface of the nano mesoporous silica according to different separation objects, thereby realizing the required separation effect.
Drawings
Fig. 1 to 5 show the structural schematic diagrams presented in each step of the preparation method of the silicon-based micro gas chromatographic column with high separation efficiency.
FIG. 6 is a scanning electron microscope image of a silicon substrate with a micro-channel and a micro-fluidic port etched/etched according to the present invention, wherein the micro-channel further comprises a series of micro-pillar arrays arranged according to a certain rule.
FIG. 7 shows a scanning electron microscope image of the nano-mesoporous silica at the bottom of the microchannel according to the present invention.
FIG. 8 shows a scanning electron microscope image of the inventive side wall nano-mesoporous silica.
Fig. 9 is a process diagram of modifying a monomolecular layer on a surface of a nano mesoporous silica by using OTS as a modifying reagent in example 2 of the present invention.
Fig. 10 is a process diagram of modifying a monolayer on a surface of a nano-mesoporous silica by using octadecyldimethylchlorosilane as a modifying reagent in embodiment 2 of the present invention.
Fig. 11 is a process diagram of modifying a monolayer on a surface of a mesoporous nano-silica by using octadecyltrimethoxysilane as a modifying agent in example 2 of the present invention.
Fig. 12 is a graph showing the separation effect of the nano-sized mesoporous silica-based micro-gas chromatography column chip on carbon disulfide and n-alkanes of C5-C10 constructed in the microchannel in example 1 of the present invention.
Fig. 13 is a schematic view showing the separation effect of carbon disulfide, chloroform, and acetone after a monomolecular layer is modified on the surface of the mesoporous nano-silica by using OTS as a modifying agent in embodiment 2 of the present invention.
Description of the element reference numerals
1 silicon substrate
2 micro channel
21 microcolumn
22 micro-channel wall
23 microfluidic port
3 mask layer
4 nanometer mesoporous silica
5 glass substrate
6 decorative material
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 13. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Example 1
As shown in fig. 1 to 8 and 12, the present embodiment provides a method for preparing a silicon-based micro gas chromatography column with high separation efficiency, the method comprising the steps of:
step 1), manufacturing a micro channel 2 and a micro-fluidic port 23 on a silicon substrate 1, wherein the micro channel 2 is also internally provided with a plurality of channel units or/and micro columns 21 array;
step 2), manufacturing a mask film layer 3 to protect a bonding surface on the silicon substrate 1;
step 3), constructing nano mesoporous silicon oxide 4 in the micro channel 2, and removing the mask layer 3 before roasting, wherein the nano mesoporous silicon oxide 4 is simultaneously constructed on the surfaces of the plurality of channel units or/and micro columns 21 arrays;
as an example, a non-aqueous synthesis method of solvent volatilization induced self-assembly is adopted to construct the nano mesoporous silica 4 in the microchannel 2, and the construction of the nano mesoporous silica 4 comprises the following steps:
step a), preparing a reaction solution of the nano mesoporous silica 4 by adopting ethanol, TEOS, hydrochloric acid and CTAB powder;
step b), manufacturing a mask, protecting a bonding surface on the silicon substrate 1 by using a mask layer 3, immersing the silicon substrate 1 with the mask layer 3 into a reaction solution of the nano mesoporous silicon oxide 4, and pulling out the silicon substrate 1 by using a pulling method;
and step c), drying the silicon substrate 1, removing the mask layer 3, and then roasting to form the nano mesoporous silicon oxide 4 in the microchannel 2.
Step 4), after removing the mask layer 3, bonding a packaging cover plate on the bonding surface of the silicon substrate 1, wherein the packaging cover plate comprises a glass substrate 5 with two polished surfaces, and is bonded on the bonding surface of the silicon substrate 1 by adopting an anodic bonding method, the bonding temperature is 200-;
and 5) scribing to obtain a silicon-based micro gas chromatographic column chip, and installing a capillary tube at the micro-fluidic port 23.
As shown in fig. 4, the present invention also provides a silica-based micro gas chromatography column with high separation efficiency, comprising: a silicon substrate 1; a micro channel 2 formed in the silicon substrate 1; microfluidic ports 23 formed at both ends of the microchannel 2; and nano mesoporous silica 4 constructed within the microchannel 2.
As an example, the microchannel 2 further has a plurality of channel units or and/or micropillar 21 arrays therein, and the nano mesoporous silica 4 is simultaneously constructed on the surfaces of the plurality of channel units or and/or micropillar 21 arrays.
As an example, the solar cell further comprises a packaging cover plate bonded on the surface of the silicon substrate 1, wherein the packaging cover plate is a glass substrate 5 with two polished sides and is bonded on the bonding surface of the silicon substrate 1 by an anodic bonding method.
As shown in fig. 1 to 8 and 12, in a specific implementation process, the method for preparing the silicon-based micro gas chromatography column with high separation efficiency includes the steps of:
as shown in fig. 1 and fig. 6, step S1 is performed to etch/etch a microchannel 2 and a microfluidic port 23 on a silicon substrate 1, where the interior of the microchannel may further include a series of channel units with narrower widths or an array of micropillars 21 arranged according to a certain rule;
as shown in fig. 2, step S2 is performed to fabricate a mask layer 3 to protect the bonding surface on the silicon substrate 1;
as shown in fig. 3, step S3 is performed, a layer of nano-mesoporous silica 4 is built inside the microchannel 2 by using a non-aqueous synthesis method of solvent Evaporation Induced Self-Assembly (EISA) or other methods; because the microchannel 2 is also provided with a plurality of channel units or and/or micro-column 21 arrays, the construction positions of the nano mesoporous silicon oxide 4 comprise: the bottom of the microchannel 2 and the side walls of the microchannel walls 22, the bottom and side walls of the channel unit or/and the entire outer surface of each microcolumn 21.
Specifically, step S3 includes:
step S3-1, adding 50mL of ethanol and 50mL of TEOS into a 500mL flask, then adding 4.14mL of water and 1ul of concentrated hydrochloric acid into the flask, and placing the flask into an oil bath kettle at 60 ℃ to stir for 30 min;
step S3-2, taking out the flask, adding 16.6ml of water, adding 76 mul of concentrated hydrochloric acid, and stirring at room temperature for 15 min;
step S3-3, placing the flask into an oil bath kettle at 50 ℃ and stirring for 15 min;
step S3-4, taking the flask out of the oil bath pan, adding 250ml of ethanol, and stirring at room temperature;
step S3-5, adding 8.36g of CTAB powder into the flask, stirring at room temperature until CTAB is completely dissolved, and continuing stirring for 1 h;
step S3-6, taking 20mL of the obtained solution, and adding 0-200mL of ethanol for dilution to prepare a reaction solution of the nano mesoporous silica 4;
step S3-7, a mask layer 3 is manufactured on the bonding surface of the silicon substrate 1 with the fabricated microchannel 2 and the fabricated microfluidic port 23 to protect the bonding surface; then, the silicon substrate 1 is immersed into the reaction solution of the nano mesoporous silicon oxide 4, and the silicon substrate 1 is pulled out at a constant speed by a pulling method;
step S3-8, placing the silicon substrate 1 in a drying tower for drying for three days, and removing the mask layer 3;
step S3-9, placing the silicon substrate 1 into a furnace for roasting, wherein the specific roasting conditions are as follows: the temperature of the calcining furnace is raised to 550 ℃ at the temperature rise rate of 1 ℃/min, the furnace temperature of 550 ℃ is kept for 360min, and then the furnace is naturally cooled. Electron micrographs of the nano-mesoporous silica 4 at the bottom of the microchannel 2 and on the side wall of the microcolumn 21 are shown in fig. 7 and 8, respectively;
as shown in fig. 4, step S4 is performed to anodically bond the surface of the silicon substrate 1 having the microchannel 2 and the double-polished glass substrate 5 at a bonding temperature of 200-;
and finally, carrying out step S5, scribing and packaging: scribing to obtain a silicon-based micro gas chromatographic column chip, installing a capillary tube at the microfluidic port 23, and sealing the port with glue.
The separation effect of the nano mesoporous silica 4 silicon-based micro gas chromatography column chip on carbon disulfide and normal paraffin of C5-C10 constructed in the microchannel 2 is shown in figure 12.
Example 2
The present embodiment provides a method for preparing a silica-based micro gas chromatography column with high separation efficiency, which includes the basic steps of embodiment 1, wherein, after step 5) is completed, a step of functionalization of nano mesoporous silica 4 is added. Step 6), forming a corresponding modification material 6 on the surface of the nano mesoporous silica 4 based on the components to be separated, as shown in fig. 5, in this embodiment, taking modification of Octadecyltrichlorosilane (OTS) on the surface of the nano mesoporous silica 4 as an example for explanation, including the steps of:
and 6-1), adding 10ml of toluene and 0.1ml of OTS into a small glass bottle with good sealing property, injecting the prepared OTS toluene solution into a silicon-based micro gas chromatographic column chip from one port by using an injector until the solution flows out from the other port, sealing two ends of the chromatographic column, and reacting for 30min at normal temperature. Monolayer modification process as shown in fig. 9;
and 6-2) injecting alcohol into the chromatographic column, cleaning for 30min, sealing one end of the chromatographic column, and putting the chromatographic column into a vacuum or low-pressure oven at 50 ℃ to completely extract the residual alcohol in the chromatographic column.
The separation effect of the nano mesoporous silica 4 on carbon disulfide, chloroform and acetone after the surface of the nano mesoporous silica 4 is modified with a monomolecular layer by using OTS as a modifying reagent is shown in fig. 13.
There are many alternative modifying agents, such as octadecyldimethylchlorosilane, octadecyltrimethoxysilane, and the like.
The process of using octadecyldimethylchlorosilane as a modification reagent to modify a monolayer on the surface of the nano mesoporous silica is shown in fig. 10.
The process of using octadecyltrimethoxysilane as a modifying reagent to modify a monolayer on the surface of the nano mesoporous silica is shown in fig. 11.
As described above, the silica-based micro gas chromatography column with high separation efficiency and the preparation method thereof of the present invention have the following beneficial effects:
1) the nano mesoporous silica 4 has a larger specific surface area (about 400-1200 m)2In g) and a larger pore volume (about 1.0 cm)3About/g) and has better thermal stability and mechanical strength, the invention constructs the silica-based micro gas chromatographic column in the silica-based micro gas chromatographic column, and can greatly improve the separation efficiency of the chromatographic column;
2) the surface of the nano mesoporous silicon oxide 4 has high-density silicon hydroxyl (Si-OH), and monomolecular layers with different separation functions can be further constructed on the surface of the nano mesoporous silicon oxide according to different separation objects, so that the required separation effect is realized.
Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (11)
1. A preparation method of a silicon-based micro gas chromatographic column with high separation efficiency is characterized by comprising the following steps:
manufacturing a micro channel on a silicon substrate, and constructing nano mesoporous silicon oxide in the micro channel; separating carbon disulfide and C6-C10 normal alkane based on the nano mesoporous silica;
the micro-channel is also internally provided with a plurality of channel units or/and micro-column arrays, and the nano mesoporous silicon oxide is simultaneously constructed on the surfaces of the plurality of channel units or/and micro-column arrays;
wherein, a non-aqueous synthesis method of solvent volatilization induced self-assembly is adopted to construct the nano mesoporous silicon oxide in the micro channel;
step a), preparing a reaction solution of the nano mesoporous silica by adopting ethanol, TEOS, hydrochloric acid and CTAB powder;
adding 50mL of ethanol and 50mL of TEOS into a 500mL flask, then adding 4.14mL of water and 1ul of concentrated hydrochloric acid into the flask, and putting the flask into an oil bath kettle at 60 ℃ to stir for 30 min;
taking out the flask, adding 16.6ml of water, adding 76 mu l of concentrated hydrochloric acid, and stirring at room temperature for 15 min;
placing the flask into an oil bath kettle at 50 ℃ and stirring for 15 min;
taking the flask out of the oil bath pan, adding 250ml of ethanol, and stirring at room temperature;
adding 8.36g of CTAB powder into the flask, stirring at room temperature until CTAB is completely dissolved, and continuing stirring for 1 h;
taking 20mL of the obtained solution, adding 0-200mL of ethanol for dilution, and preparing a reaction solution of the nano mesoporous silicon oxide;
b), manufacturing a mask layer to protect a bonding surface on the silicon substrate, immersing the silicon substrate with the mask layer into a reaction solution of the nano mesoporous silicon oxide, and pulling out the silicon substrate by adopting a pulling method;
step c), drying the silicon substrate, removing the mask layer, and then roasting to form nano mesoporous silicon oxide in the micro channel;
the specific process comprises the following steps:
manufacturing a mask layer on a bonding surface of a silicon substrate with a fabricated microchannel and a microfluidic port to protect the bonding surface; then, the silicon substrate is immersed into the reaction solution of the nano mesoporous silicon oxide, and the silicon substrate is pulled out at a constant speed by a pulling method;
drying the silicon substrate in a drying tower for three days, and removing the mask layer;
the silicon substrate is placed into a furnace for roasting, and the specific roasting conditions are as follows: the temperature of the calcining furnace is raised to 550 ℃ at the temperature rise rate of 1 ℃/min, the furnace temperature of 550 ℃ is kept for 360min, and then the furnace is naturally cooled.
2. The method for preparing a high separation efficiency silicon-based micro gas chromatography column according to claim 1, wherein the method comprises the steps of:
step 1), manufacturing a micro channel and a micro-fluidic port on a silicon substrate;
step 2), manufacturing a mask layer to protect a bonding surface on the silicon substrate;
step 3), constructing nano mesoporous silicon oxide in the micro channel, and removing the mask layer before roasting;
and 4), bonding a packaging cover plate on the bonding surface of the silicon substrate.
3. The method for preparing a high separation efficiency silicon-based micro gas chromatography column as claimed in claim 2, further comprising the steps of: scribing to obtain a silicon-based micro gas chromatographic column chip, and installing a capillary tube at the micro-fluidic port.
4. The method for preparing a silica-based micro gas chromatography column with high separation efficiency according to claim 3, wherein the method comprises the following steps: the packaging cover plate comprises a glass substrate with two polished surfaces, and is bonded on the bonding surface of the silicon substrate by adopting an anodic bonding method, wherein the bonding temperature is 200-450 ℃, and the bonding voltage is 600-1400V.
5. The method for preparing a high separation efficiency silicon-based micro gas chromatography column as claimed in claim 1, further comprising the steps of: forming a corresponding modification material on the surface of the nano mesoporous silica based on components to be separated, wherein the surface of the nano mesoporous silica has high-density silicon hydroxyl groups, monomolecular layers with different separation functions can be further constructed on the surface of the nano mesoporous silica according to different separation objects, and the desired separation effect is realized based on the monomolecular layers with different separation functions;
the modifying materials are selected from octadecyltrichlorosilane, octadecyldimethylchlorosilane and octadecyltrimethoxysilane, and the modifying process of each modifying material and the mesoporous silica respectively comprises the following steps:
6. the method for preparing a silicon-based micro gas chromatography column with high separation efficiency according to claim 5, wherein the modifying step of the octadecyl trichlorosilane comprises:
step 1), preparing a mixed solution of toluene and octadecyltrichlorosilane, and injecting the mixed solution into the microchannel for reaction;
and 2), cleaning the microchannel by using alcohol after reaction, and completely removing the alcohol in the microchannel in a vacuum or low-pressure environment.
7. A high separation efficiency silica-based micro gas chromatography column prepared by the preparation method according to any one of claims 1 to 6, comprising:
a silicon substrate;
a micro channel formed in the silicon substrate;
the micro-fluidic ports are formed at two ends of the micro channel;
the nano mesoporous silicon oxide is constructed in the micro channel.
8. The high separation efficiency silicon-based micro gas chromatography column of claim 7, wherein: further comprising: corresponding modified materials are formed on the surface of the nano mesoporous silica based on components needing to be separated.
9. The high separation efficiency silicon-based micro gas chromatography column of claim 8, wherein: the modifying material is selected from octadecyl trichlorosilane, octadecyl dimethylchlorosilane and octadecyl trimethoxysilane.
10. The high separation efficiency silicon-based micro gas chromatography column of claim 7, wherein: and the packaging cover plate is bonded on the surface of the silicon substrate.
11. The high separation efficiency silicon-based micro gas chromatography column of claim 10, wherein: the packaging cover plate is a glass substrate with two polished sides and is bonded on the bonding surface of the silicon substrate through an anodic bonding method.
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| CN113466393B (en) * | 2021-06-11 | 2022-07-12 | 西安交通大学 | Miniature gas chromatographic column capable of using air as carrier gas and its making method |
| CN114878734B (en) * | 2022-03-28 | 2023-12-01 | 中国科学院上海微系统与信息技术研究所 | Preparation method of micro chromatographic column based on layer-by-layer deposition mesoporous silica as stationary phase |
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| CN103776940A (en) * | 2012-10-19 | 2014-05-07 | 中国科学院电子学研究所 | Arrayed micro gas chromatographic column chip with super-large contact area |
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