Method for hydrophobizing inner wall of glass probe
By hydrophobizing the inner wall of the glass probe with modified components such as silane or Teflon, the problem of easy clogging of the probe in the aqueous solution is solved, the smooth flow of the probe sampling channel in an environment where liquid exists, and the gas-phase species are promoted collection and analysis.
Patent Information
- Application Number
- CN202310996752.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-08-08
- Publication Date
- 2025-02-18
AI Technical Summary
The hydrophilic properties of glass probes lead to prone to clogging in aqueous solutions, limiting their application in environments where liquids exist.
Modified components such as silane or Teflon are used to hydrophobize the inner wall of the glass probe, and the solution is introduced through capillary effect and the excess solution is removed with high-pressure gas, thereby achieving selective treatment of single-channel and multi-channel probes.
It effectively avoids interference with the sampling channel by aqueous solution, ensures the unblocking of the sampling channel of the probe in an environment where there is liquid, and promotes the collection and analysis of gas-phase species at the micro-nano scale.
Smart Images
Figure CN119461878A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a method for hydrophobizing the inner wall of a glass probe. Background Art
[0002] In the study of gas-liquid-solid interface reactions, the collection and rapid analysis of gaseous or volatile products and intermediates are very important for clarifying the relationship between structure-performance-products and understanding the reaction mechanism and kinetic characteristics. Especially for materials with heterogeneous surface conformations and activities, we need to develop micro-area sampling tools to obtain information about products near each reaction area while reacting. The tip size (micrometer / nanometer scale) of the hollow probe drawn from a glass tube is flexible and controllable, low-cost, and can be used for micro-area product sampling and analysis. However, the hydrophilicity of the glass probe itself makes the sampling channel easy to clog in aqueous solutions, which greatly limits its application as a sampling probe in environments with liquids. Summary of the invention
[0003] The present invention provides a method for hydrophobizing the inner wall of a single-channel and multi-channel glass probe. The treatment process is simpler and less time-consuming than traditional methods, so that the probe is not affected by the aqueous solution environment, and the collection and analysis of gas-phase species at the micro-nano scale can be achieved. In particular, for a multi-channel probe, the present method is used to achieve hydrophobic treatment of the inner wall of a specific channel while maintaining the original state of other channels, so that the reactions and sampling processes in different channels of the probe do not interfere with each other after treatment. A method for hydrophobizing the inner wall of a glass probe, the probe comprising a single-channel probe and a multi-channel probe; comprising the following steps:
[0004] Step 1: For a single-channel probe, dip its tip below the surface of the solution containing the modified component, and a small amount of solution enters the probe by capillary effect ( Figure 2 a), and modify the inner wall;
[0005] For the multi-channel probe, it is divided into an electrolyte channel and a sampling channel. Before dipping into the solution, the top of the sampling channel needs to be sealed with parafilm or hot melt adhesive. The top of the multi-channel probe is connected to a high-pressure gas (0.1-1.5 MPa, such as Figure 3 As shown), after the tip of the multi-channel probe is immersed below the liquid surface of the solution containing the modifying component, the gas flow in the electrolyte channel is maintained to prevent the solution containing the modifying component from entering, while a small amount of solution enters the sampling channel to modify its inner wall;
[0006] Step 2: remove the probe from the solution and place it in the air for 1 to 10 minutes to complete the inner wall modification;
[0007] For a single-channel probe, connect it to a high-pressure gas processing unit and use high-pressure gas to blow excess solution out of the probe.
[0008] For the multi-channel probe, the sealing material at the top of the sampling channel is first removed, and the top of the multi-channel probe is then connected to high-pressure gas to remove excess solution inside;
[0009] Step 3: Then immerse the probe tip in anhydrous ethanol to remove the modification components at the probe opening and outer wall (to prevent the high-pressure gas from entering the probe again after it is removed). Turn off the high-pressure gas and keep the probe in ethanol for 10 to 60 seconds. The ethanol enters the probe through the capillary effect, and then the high-pressure gas is used to blow the ethanol out to further remove the excess modification solution. The treated probe is dried in the air for later use. Figure 2 b).
[0010] Furthermore, in the above technical solution, the solution of the modifying component in step one or step two is selected from C8-C16 fluorine-containing silane and Teflon solution.
[0011] Furthermore, in the above technical solution, the diameter of the probe tip is tens to hundreds of nanometers or micrometers.
[0012] Furthermore, in the above technical solution, the probe is drawn by a laser or resistance wire heating capillary drawing instrument.
[0013] Furthermore, in the above technical solution, the pressure of the high-pressure gas is 0.1-1.5 MPa.
[0014] Furthermore, the high-pressure gas is discharged through a high-pressure gas processing unit. The high-pressure gas processing unit adopted in the above method is a gas path joint structure, including an adapter body arranged in the middle; the outer sides of the upper and lower parts of the adapter body are respectively provided with ferrule nuts; at least two groups of rubber rings are provided at the contact point between the upper ferrule nut and the top of the upper part of the adapter body; a heat shrink tube is passed through the inside of the rubber ring, and the upper part of the heat shrink tube extends out of the ferrule nut on the upper part of the adapter body.
[0015] Furthermore, in the above technical solution, the inner diameter of the upper part of the adapter body is smaller than the inner diameter of the lower part of the adapter body.
[0016] Beneficial Effects
[0017] 1. Use silane, Teflon and other modifying components to achieve hydrophobic treatment of the inner wall of the micro-nano probe, especially to achieve selective treatment of some channels in the multi-channel probe, avoid the interference of aqueous solution on the sampling channel, and promote the development of coupled characterization methods of scanning probe microscopy and product analysis technology.
[0018] 2. When treating the inner wall of the probe, the solution is introduced from the bottom by means of capillary effect to prevent excessive solution from entering the probe. At the same time, the steps of modification-high-pressure gas purging-cleaning are combined to minimize the impact of the inner wall treatment on the sampling path.
[0019] 3. The high-pressure gas processing unit uses a common stainless steel gas line connector, and the probe is firmly fixed by a heat shrink tube and a rubber ring inside, so that it can be pressurized to >1.2MPa and the residual liquid in the probe can be quickly removed. It can effectively replace the use of commercial Omnifit plastic connectors, not only reducing the wear of the probe tip on the clamp (the glass probe does not directly contact the rubber ring and the inner wall of the clamp) and the aging and deformation of the plastic nut caused by repeated use, but also preventing plastic (commonly polytetrafluoroethylene) debris from entering the probe and causing channel blockage. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 The steps of treating the inner wall of the single-channel (a) and multi-channel (b) probe channels to be hydrophobic;
[0021] Figure 2 Optical photos of the dual-channel probe at different stages of the hydrophobic treatment process. Among them: a. Probe dipped in the modification solution, b. Probe after high-pressure gas purging, c. Probe after adding electrolyte to the reaction side (the inset shows the liquid level), d. Probe used for interface reaction testing (the left side is the solution channel, and the right side is the blank sampling channel);
[0022] Figure 3 Schematic diagram of high-pressure gas processing unit. 1. 1 / 16 ferrule nut, 2. 1 / 16 to 1 / 8 connector body, 3. 1 / 8 ferrule nut, 4. Glass probe, 5. Rubber tube, 6. Rubber O-ring, 7. Front ferrule, 8. Rear ferrule, 9. Stainless steel tube;
[0023] Figure 4 Mass spectrometric signal when the tip of a dual-channel probe with one side filled with electrolyte and the other side blank is exposed to CO2 gas (mass-to-charge ratio m / z = 44);
[0024] Figure 5 a is an optical photograph of a probe treated with hydrophobicity using dichlorodimethylsilane diluted with toluene (1% by volume) after contacting with a platinum-plated sample; Figure 5 b is an optical photograph of the dual-channel probe processed by the method and apparatus described in Example 1 of the present invention after contacting with a platinum-coated silicon wafer sample. DETAILED DESCRIPTION
[0025] The high-pressure gas in the following embodiments is generated by a high-pressure gas processing unit, which is a gas path joint structure, including an adapter body arranged in the middle; the outer sides of the upper and lower parts of the adapter body are respectively provided with ferrule nuts; at least two sets of rubber rings are provided at the contact between the upper ferrule nut and the top of the upper part of the adapter body; a heat shrink tube is passed through the rubber ring, and the upper part of the heat shrink tube extends out of the ferrule nut on the upper part of the adapter body. The inner diameter of the upper part of the adapter body is smaller than the inner diameter of the lower part of the adapter body.
[0026] For specific structure, see Figure 3 The high-pressure gas processing unit is a gas line joint structure, including a 1 / 16 to 1 / 8 joint body arranged in the middle; the outer sides of the upper and lower parts of the 1 / 16 to 1 / 8 joint body are respectively provided with a 1 / 16 ferrule nut and a 1 / 8 ferrule nut; at least two sets of rubber O-rings are provided at the top contact between the 1 / 16 ferrule nut and the upper part of the 1 / 16 to 1 / 8 joint body; a heat shrink tube, i.e., a rubber tube, is provided inside the rubber O-ring, and the upper part of the heat shrink tube extends out of the 1 / 16 ferrule nut at the upper part of the 1 / 16 to 1 / 8 joint body. The inner diameter of the upper part of the 1 / 16 to 1 / 8 joint body is smaller than the inner diameter of the lower part of the 1 / 16 to 1 / 8 joint body. The front ferrule and the rear ferrule for fixing the stainless steel pipe are provided at the bottom contact between the 1 / 8 ferrule nut and the lower part of the 1 / 16 to 1 / 8 joint body; the high-pressure gas enters the high-pressure gas processing unit through the stainless steel.
[0027] Example 1
[0028] A method for hydrophobizing the inner wall of a glass probe, wherein the probe includes a single-channel probe and a multi-channel probe; the method comprises the following steps:
[0029] 1. Set parameters on a laser or resistance wire heating capillary puller to pull the probe, making a probe with a tip diameter of tens to hundreds of nanometers or microns.
[0030] 2. The processing steps of the probe are as follows Figure 1 As shown. For a single-channel probe, dip its bottom end into the pure solution of trichloro(1H,1H,2H,2H-tridecafluorooctyl)silane below the liquid surface, and a small amount of solution enters the probe by capillary effect ( Figure 2 a) and modify the inner wall. For multi-channel probes, before dipping into the solution, the top of the sampling channel needs to be sealed with hot melt adhesive and connected to a high-pressure gas processing unit (0.1-1.5 MPa, such as Figure 3 As shown), after being immersed in the solution, the gas flow in the electrolyte channel is maintained to prevent the solution containing the modified components from entering, while a small amount of solution enters the sampling channel to modify its inner wall.
[0031] 3. Remove the probe from the solution and let it stand in the air for 5 minutes to complete the modification of the inner wall. For a single-channel probe, connect it to a high-pressure gas processing unit and use high-pressure gas to blow out excess solution from the inside of the probe. For a multi-channel probe, first remove the sealing material on the top, and then connect high-pressure gas to remove excess solution inside. Then immerse it in anhydrous ethanol to remove trichloro(1H,1H,2H,2H-tridecafluorooctyl)silane from the opening and outer wall of the probe (to avoid it entering the probe again after the high-pressure gas is removed). Turn off the high-pressure gas and keep the probe in ethanol for 10 to 60 seconds. The ethanol enters the probe through the capillary effect, and then the ethanol is blown out by high-pressure gas to further remove excess modification solution. The treated probe is dried in the air for use ( Figure 2 b).
[0032] 4. Place the dried single-channel probe directly into the solution to collect and analyze the gas products in the reaction. Alternatively, add 0.1M perchloric acid electrolyte to the unmodified channel of the multi-channel probe as a reaction channel, fix the probe on the piezoelectric ceramic, and precisely control its movement toward the surface of the platinum-coated silicon wafer sample ( Figure 2 cd). When the probe is near the sample surface, the tip is exposed to CO2 gas, and the sampling channel collects the species and transports them to the mass spectrometer connected to the tip. The CO2 (mass-to-charge ratio = 44) obtained by analysis is shown in the following figure. Figure 4 This indicates that a stable gas-liquid interface is formed between the two channels at the tip of the probe, and the sampling channel can be kept unobstructed even in the presence of a solution, thereby achieving the sampling function.
[0033] Example 2
[0034] A method for hydrophobizing the inner wall of a glass probe, wherein the probe includes a single-channel probe and a multi-channel probe; the method comprises the following steps:
[0035] Step 1: For a single-channel probe, dip its tip into the liquid surface of trichloro(1H,1H,2H,2H-tridecafluorooctyl)silane solution. A small amount of solution enters the probe by capillary effect ( Figure 2 a), and modify the inner wall;
[0036] For the multi-channel probe, the electrolyte channel and the sampling channel; before dipping into the solution, the top of the sampling channel needs to be sealed with parafilm or hot melt adhesive. The top of the multi-channel probe is connected to a high-pressure gas processing unit (0.1-1.5 MPa, such as Figure 3 As shown), the tip of the multi-channel probe is immersed below the liquid surface of the trichloro(1H,1H,2H,2H-tridecafluorooctyl)silane solution to maintain the gas flow in the electrolyte channel to prevent the solution containing the modified component from entering, while a small amount of solution enters the sampling channel to modify its inner wall;
[0037] Step 2: remove the probe from the solution and place it in the air for 5 minutes to complete the inner wall modification;
[0038] For a single-channel probe, connect it to a high-pressure gas processing unit and use high-pressure gas to blow excess solution out of the probe.
[0039] For the multi-channel probe, the sealing material at the top of the sampling channel is first removed, and the top of the multi-channel probe is then connected to high-pressure gas to remove excess solution inside;
[0040] Step 3: Then immerse the probe tip in anhydrous ethanol to remove trichloro(1H,1H,2H,2H-tridecafluorooctyl)silane from the probe opening and outer wall (to prevent it from entering the probe again after the high-pressure gas is removed). Turn off the high-pressure gas and keep the probe in ethanol for about 10 to 60 seconds. The ethanol enters the probe through the capillary effect, and then the high-pressure gas is used to blow the ethanol out to further remove the excess modification solution. The treated probe is dried in the air for later use ( Figure 2 b).
[0041] The solution of the modification component in step 1 or step 2 is selected from a silane solution.
[0042] The diameter of the probe tip is tens to hundreds of nanometers or micrometers.
[0043] The probe is drawn by a laser or resistance wire heating capillary puller.
[0044] The pressure of the high-pressure gas is 0.1-1.5 MPa.
[0045] Comparative Example 1
[0046] Figure 5 The probe in a is made of borosilicate glass. The glass probe is hydrophobized using a pure solution of short-chain silane dichlorodimethylsilane or dichlorodimethylsilane diluted in toluene (1% by volume). After the probe comes into contact with the platinum-plated sample, 0.1 M perchloric acid electrolyte gradually fills the sampling channel from the bottom of the probe (e.g. Figure 5 As shown by the arrow in a). However, the dual-channel probe processed by the method and device described in Example 1 of the present invention always keeps the sampling channel unobstructed during the contact and reaction process with the platinum-coated silicon wafer sample ( Figure 5 b).
[0047] Comparative Example 2
[0048] For borosilicate glass probes that have not been hydrophobized, the 0.1M perchloric acid electrolyte will quickly enter the probe during the injection stage or when the probe reaches the surface of the platinum-plated sample, causing blockage in the sampling channel.
[0049] There is no related design or report on the use of a micro-nano scale dual-channel probe to add electrolyte on one side and keep the other side blank to collect and analyze gas species. However, the method and device described in the present invention can realize micro-nano scale electrochemical testing and gas species collection and analysis (taking CO2 as an example, such as Figure 4 shown).
Claims
1. A method for hydrophobizing the inner wall of a glass probe, characterized in that: The probe includes a single-channel probe and a multi-channel probe; comprising the following steps: Step 1: For a single-channel probe, dip its tip into a solution containing a modification component below the liquid surface. A small amount of solution enters the probe by capillary effect and modifies the inner wall. The multi-channel probe is divided into an electrolyte channel and a sampling channel; before dipping into the solution, the top of the sampling channel needs to be sealed with parafilm or hot melt adhesive, and the top of the multi-channel probe is connected to high-pressure gas. After the tip of the multi-channel probe is immersed below the liquid surface of the solution containing the modifying component, the gas flow in the electrolyte channel is maintained to prevent the solution containing the modifying component from entering, and a small amount of solution enters the sampling channel to modify its inner wall; Step 2: remove the probe from the solution and place it in the air for 1 to 10 minutes to complete the inner wall modification; For single-channel probes, high-pressure gas is used to blow excess solution out of the probe interior; For the multi-channel probe, the sealing material at the top of the sampling channel is first removed, and the top of the multi-channel probe is then connected to high-pressure gas to remove excess solution inside; Step 3: Immerse the tip of the probe in anhydrous ethanol to remove the modified components at the probe opening and outer wall; turn off the high-pressure gas and keep the probe in ethanol for 10 to 60 seconds. The ethanol enters the interior of the probe through the capillary effect, and then the ethanol is blown out by the high-pressure gas to further remove excess modification solution; the treated probe is dried in the air for later use.
2. The method according to claim 1, characterized in that: In the step 1 or step 2, the modification component is selected from C8-C16 fluorine-containing silane and Teflon solution.
3. The method according to claim 1, characterized in that: The diameter of the probe tip is tens to hundreds of nanometers or micrometers.
4. The method according to claim 1, characterized in that: The probe is drawn by a laser or resistance wire heating capillary puller.
5. The method according to claim 1, characterized in that: The pressure of the high-pressure gas is 0.1-1.5 MPa.
6. The method according to claim 1, characterized in that: The high-pressure gas is discharged through a high-pressure gas processing unit, which is a gas path joint structure, including an adapter body arranged in the middle; the outer sides of the upper and lower parts of the adapter body are respectively provided with ferrule nuts; at least two groups of rubber rings are provided at the contact point between the upper ferrule nut and the top of the upper part of the adapter body; a heat shrink tube is passed through the inside of the rubber ring, and the upper part of the heat shrink tube extends out of the ferrule nut on the upper part of the adapter body.
7. The method according to claim 6, characterized in that: The inner diameter of the upper part of the adapter body is smaller than the inner diameter of the lower part of the adapter body.