CN1584544A - Method for forming nano gas layer on pyrolytic graphite surface based on alcohol-water substitution - Google Patents
Method for forming nano gas layer on pyrolytic graphite surface based on alcohol-water substitution Download PDFInfo
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- CN1584544A CN1584544A CN 200410025036 CN200410025036A CN1584544A CN 1584544 A CN1584544 A CN 1584544A CN 200410025036 CN200410025036 CN 200410025036 CN 200410025036 A CN200410025036 A CN 200410025036A CN 1584544 A CN1584544 A CN 1584544A
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Abstract
A method for forming nanoairlayer includes applying hydrophobic, flat and high-order pyrolytic graphite as base, injecting water first and then alcohol, forming nanoairlayer or nanoairbubble on boundary of base and water by utilizing alternative course of water and alcohol, keeping liquid temperature as above 5 degree C and below 85 degree C.
Description
Technical field
The present invention relates to a kind of method that forms nanometer gas-bearing formation (or bubble) at hydrophobic surface of replacing based on pure water, specifically, be a kind of process of utilizing the alcohol (comprising methyl alcohol, ethanol, n-propanol, isopropyl alcohol and the tert-butyl alcohol) that can dissolve each other with water and water to replace in high order pyrolytic graphite (HOPG) substrate can form nanometer gas-bearing formation (or bubble) on the interface of substrate and water method, belong to nanometer gas-bearing formation (or bubble) the formation technical field of solid-liquid interface in the physical chemistry.
Background technology
No matter in the fundamental research field or in application branch of learning, the nanometer gas-bearing formation (or bubble) of solid-liquid interface all is a problem that receives much attention.According to classical thermodynamics, the volume of bubble is more little, and pressure inside is just big more, and the big bubble that must cause of pressure breaks.In theory, nano bubble can not stable existence in the water under the room temperature.But have several seminar to observe directly the nano bubble of solid-liquid interface with atomic force microscope (AFM) in recent years, this existence for nano bubble provides evidence.In theory, the someone proposes at solid-liquid interface gas a kind of mode is also arranged in addition: the nanometer gas-bearing formation except this mode enrichment with nano bubble.Experimental result also has some signs to show the existence of nanometer gas-bearing formation.Because nanometer gas-bearing formation (or bubble) size is little very easily destroyed again, be difficult to arrive with optical means and contact instrument visual inspection.The advantage of atomic force microscope is can be in imaging under the solution state, and obtains nano level resolution.Therefore especially the pattern of rapping of AFM is very suitable for the research of soft sample, is the powerful measure of surveying solid-liquid interface nanometer gas-bearing formation (or bubble) at present.
Nanoscale gas has caused the very big concern of physical chemistry, Surface Science, colloidal chemistry and other subject after solid-liquid interface is suggested to the viewpoint of the mode enrichment of gas-bearing formation or bubble.Gas is relevant with effect with a lot of phenomenons in the enrichment of solid-liquid interface (especially hydrophobic surface), as the interaction between colloidal particle and solid surface, moistened surface, surface adhesion, liquid to the viscous effect of motion solid, biomolecule in the gathering of solid-liquid interface, the flotation and the sedimentation of micelle, even all there is confidential relation the aspects such as stability of protein structure.In addition, gas may provide a kind of valid approach for the storage of gas being enriched with of solid-liquid interface.Want system, in depth study the fundamental property of nanometer gas-bearing formation (or bubble), and use this important interfacial property in practice, must set up a kind of easy, repeatable strong method earlier and form nanometer gas-bearing formation/bubble.Except that this group, nano bubble (J.W.G., Yyrrell and P.Attard, Phys.Rev.Lett.2001 directly study at water-immersed hydrophobic surface in other seminar at present; 87, P176104.N.Ishida, M.Sakamoto, M.Miyara and K.Higashitani, Langmuir 2000; 16, P5681.NR study2004; On Au surface 2004 La).The inhomogeneity that on this surface, has physics or chemical property, the adsorbed gas in air easily of this heterogeneity surface.And the surface is minimum even nano level inhomogeneity all might have influence on the enriched form of interfacial gases and the character that is had thereof by the utmost point significantly, even can't form the nanometer gas-bearing formation at all.Biao Mian inhomogeneity also can be brought a great adverse effect in addition, causes the illusion in the AFM research exactly.So on these surfaces, can not realize systematic study, more impossiblely in practice the gas enrichment process is applied to the nanometer gas-bearing formation (or bubble) of solid-liquid interface.
HOPG is made up of highly purified carbon simple substance, and its surface has certain hydrophobicity, can repeatedly dissociate also can reach atomically flating.The unevenness that the HOPG surface does not have the chemical modification surface to be had, and have relative chemical inertness, be a kind of AFM imaging substrate commonly used.But because the contact angle on HOPG surface, is difficult to the directly a large amount of gas formation gas-bearing formation (or bubble) of enrichment from water usually less than 90 degree.Therefore, set up that a kind of the method for controllably a large amount of enriched gas all is significant for the theoretical research of nanometer gas-bearing formation (or bubble) and the practical application of this critical nature of solid-liquid interface enriched gas on the HOPG surface.
This group adopts pure water to replace formation nano bubble (S.T.Lou, Z.Q.Ouyang, Y.Zhang, X.J.Li, J.Hu, M.Q.Li and F.J.Yang, J.Vac.Sci.Technol.B, 2000 early stage; 18, P2573.S.T.Lou, J.X.Gao, X.D.Xiao, G.L.Li, Y.Zhang, M.Q.Li, J.L.Sun, J.Hu, Chin.Phys.2001,10 (Suppl) P1009.S.T.Lou, J.X.Gao, X.D.Xiao, X.J.Li, G.L.Li, Y.Zhang, M.Q.Li, J.L.Sun, X.H.Li and J.Hu, Mater.Charact.2002; 48, P211), do not recognize the material impact of some parameter conditions (for example the purity of fluid temperature and water etc.) to the gas enrichment process, therefore can't form the nanometer gas-bearing formation, also just can't obtain the true form of gas at HOPG/ water termination enriched gas.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method that forms nanometer gas-bearing formation (or bubble) at hydrophobic even curface is provided.This method not only is suitable for atomic force microscope AFM nanometer gas-bearing formation (or bubble) being observed, and is easy and simple to handle, can not introduce pollution, and have fine reappearance, can be used as the basis of nanometer gas-bearing formation (bubble) being goed deep into systematic study and application.
For realizing such purpose, it is substrate that the present invention adopts HOPG hydrophobic, atomically flating, injects earlier the alcohol water that reinjects, and utilizes the replacement process of alcohol and water, forms nanometer gas-bearing formation (or bubble) on the interface of substrate and water.
The present invention specifically comprises the steps:
(1) preparation of instrument
Atomic force microscope is that (Digital Instruments Inc.), is equipped with O circle and liquid bath in NanoScope IIIa SPM system." E " scanner head; Elasticity coefficient is the NP-S needle point of 0.58N/m or 0.32N/m.Needle point water, ethanol and acetone before use cleans.The temperature of liquid is all more than 5 ℃, below 85 ℃.
(2) preparation of substrate
The present invention adopt new explanation from hydrophobic smooth HOPG surface as substrate.The HOPG that with size is 12mm * 12mm is bonded at it on iron plate of AFM imaging special use with double faced adhesive tape, with transparent adhesive tape the one deck of leaving away is separated on the HOPG surface equably, is put into the AFM head.The liquid bath that installs needle point, O circle and rising pipe is put in the HOPG substrate of AFM head, fixes.
(3) form nanometer gas-bearing formation (or bubble)
Water inlet pipe by connecing liquid bath injects liquid bath gently with the absolute ethyl alcohol (top grade is pure) of syringe about with 2ml, clips the inlet tube and outlet tube of liquid bath, convergence needle point, imaging.Determine that the HOPG surface does not have obvious particle in ethanol, can't distinguish the nanometer gas-bearing formation (or bubble) of possible pollution and formation after preventing.
After imaging is finished, lift needle point.Take off water inlet pipe, suck ultrapure water (Milli Q).When on liquid bath, injecting water pipe, open rising pipe gently.Ultrapure water about 5ml is injected liquid bath gently, discharge ethanol wherein.Do not form the nanometer gas-bearing formation if only will form nano bubble, can replace ultrapure water, replace with ethanol with 5% ethanolic solution.
(4) observation of nanometer gas-bearing formation (or bubble)
Drive nearly needle point, rap driving frequency (drive amplitude) 7-12KHz of pattern, driving amplitude (drive amplitude) 250-500mV is about sweep speed (scan rate) 2Hz.When selecting the set point (setpoint) of AFM imaging, do the force curve on HOPG surface earlier.The value of set point should be lower than the position that force curve begins to descend slightly.
The substrate that the present invention adopts can be other and the bigger surface of contact angle of water that comprises HOPG, comprises through reaching and does not pass through the surface of chemistry or physical modification.
The alcohols that the present invention selects for use is except that ethanol, and these also can be replaced methyl alcohol, n-propanol, isopropyl alcohol and the tert-butyl alcohol by water by identical method with the alcohols that water dissolves each other, and forms nanometer gas-bearing formation (or bubble) on the HOPG surface.What the present invention was used is the alcohol and water of handling without the degassing.
The present invention is in the replacement process that has utilized alcohol and water, can form nanometer gas-bearing formation (or bubble) at hydrophobic, even curface.Method is easy and simple to handle, can not introduce pollution, and have fine reappearance, be suitable for the observation of AFM nanometer gas-bearing formation (or bubble), be nanometer gas-bearing formation (or bubble) deeply, the basis of systematic study, also be the basis that solid-liquid interface gas enrichment process is used in practice.
Embodiment
Below by specific embodiment method of the present invention is further described.
Embodiment 1: the enriched form of solid-liquid interface gas
Atomic force microscope is that (Digital Instruments Inc.), is equipped with O circle and liquid bath in NanoScope IIIa SPM system." E " scanner head; Elasticity coefficient is the NP-S needle point of 0.58N/m.Needle point cleans with ethanol and acetone before use.Water is the Millipore ultrapure water, and ethanol is that top grade is pure, purchases in Chinese chemical reagent main office.
HOPG with a 12mm * 12mm is bonded on the iron plate with double faced adhesive tape, throws off the one deck on HOPG surface with transparent adhesive tape, is put into the AFM head.Adjust head position, make needle point apart from the about 40um in HOPG surface, the liquid bath that installs needle point, O circle and rising pipe is put in the HOPG substrate of AFM head, fixes.
Water inlet pipe by liquid bath injects liquid bath with syringe gently with 2ml ethanol, clips the inlet tube and outlet tube of liquid bath, convergence needle point, imaging.Do not observe tangible larger particles.Lift needle point 5-10 micron, take off water inlet pipe, suck ultrapure water.When on liquid bath, injecting water pipe, open rising pipe gently.Ultrapure water about 5ml is injected liquid bath gently, discharge ethanol wherein.Drive nearly needle point, rap driving frequency (drive amplitude) 7.2KHz of pattern, driving amplitude (drive amplitude) 280mV, sweep speed (scanrate) 2Hz determines setpoint according to force curve.Earlier than large-area scanning, as a token of find image space in the ethanol with atomic steps.That the result can observe is that the HOPG surface has that some are large-area, the top is more smooth, height is at the nanometer gas-bearing formation of several nanometers and circle, higher nano bubble.
Carry out above-mentioned replacement process with water respectively with methyl alcohol, n-propanol, isopropyl alcohol or the tert-butyl alcohol, the result also can observe nanometer gas-bearing formation and nano bubble.This shows through pure water replaces and can have two kinds at the enriched form that the HOPG/ water termination is observed nanoscale gas: nanometer gas-bearing formation and nano bubble.
Embodiment 2: temperature is to forming the influence of nanometer gas-bearing formation (or bubble)
Atomic force microscope is that (Digital Instruments Inc.), is equipped with O circle and liquid bath in NanoScope IIIa SPM system." E " scanner head; Elasticity coefficient is the NP-S needle point of 0.58N/m.Needle point cleans with ethanol and acetone before use.Water is the Millipore ultrapure water, and ethanol is that top grade is pure, purchases in Chinese chemical reagent main office.HOPG with a 12mm * 12mm is bonded on the iron plate with double faced adhesive tape, throws off the one deck on HOPG surface with transparent adhesive tape, is put into the AFM head.Adjust head position, make needle point apart from the about 40um in HOPG surface, the liquid bath that installs needle point, O circle and rising pipe is put in the HOPG substrate of AFM head, fixes.
Water inlet pipe by liquid bath will be incubated in 25 ℃ 2ml ethanol with syringe and inject liquid bath gently, clip the inlet tube and outlet tube of liquid bath, convergence needle point, imaging.Do not observe tangible larger particles.Lift needle point 5-10 micron, take off water inlet pipe, suction is incubated in 25 ℃ ultrapure water.When on liquid bath, injecting water pipe, open rising pipe gently.Ultrapure water about 5ml is injected liquid bath gently, discharge ethanol wherein.Drive nearly needle point, imaging can be observed the nanometer gas-bearing formation and the nano bubble on HOPG surface.Statistical unit area nanometer gas-bearing formation is in the area coverage of substrate and the quantity of nano bubble.
As a comparison, by above-mentioned same quadrat method, with being lower than and being higher than 25 ℃ second alcohol and water replacement, the AFM imaging still can be observed nanometer gas-bearing formation (or bubble) respectively.The area coverage of statistics number of bubbles and gas-bearing formation, result can determine the second alcohol and water of different temperatures is replaced the how much also different of formation nanometer gas-bearing formation (or bubble), and the liquid of higher temperature can more help the formation of nanometer gas-bearing formation (or bubble).
Contrast of the result's that will experimentize respectively in two researchs original position and statistics, this is impossible immerse with the surface that the method for enriched gas realizes in the water.Alcohol and water is replaced and can be formed nanometer gas-bearing formation (or bubble) on hydrophobic, smooth HOPG surface, and it is repeatable preferably to make experimental result have.Contrast, statistical experiment result, such two researchs have all obtained clear and definite result.
Claims (4)
1, a kind of based on the method for pure water replacement at high order pyrolytic graphite surface formation nanometer gas-bearing formation, it is characterized in that comprising:
1) hydrophobic smooth high order pyrolytic graphite HOPG surface is adopted in substrate, the HOPG of 12mm * 12mm is bonded on the iron plate of atomic force microscope imaging special use, again its surperficial one deck is thrown off gently, be put into the atomic force microscope head, the liquid bath that installs needle point, O circle and rising pipe is put in the substrate fixes;
2) with syringe absolute ethyl alcohol is injected liquid bath gently by the water inlet pipe that connects liquid bath, clip the inlet tube and outlet tube of liquid bath, the convergence needle point, after imaging is finished, lift needle point, take off water inlet pipe, suck ultrapure water, when on liquid bath, injecting water pipe, open rising pipe gently, ultrapure water is injected liquid bath gently, discharge ethanol wherein, form nanometer gas-bearing formation or bubble on the interface of substrate and water, wherein the temperature of liquid is more than 5 ℃, below 85 ℃;
3) drive nearly needle point, rap the driving frequency 7-12KHz of pattern, driving amplitude 250-500mV, sweep speed 2Hz carries out the observation of nanometer gas-bearing formation or bubble.
2, as claimed in claim 1 based on the method for pure water replacement at high order pyrolytic graphite surface formation nanometer gas-bearing formation, it is characterized in that ethanolic solution replacement ultrapure water with 5%, replace with ethanol.
3, as claim 1 or 2 replace the method that forms the nanometer gas-bearing formation on high order pyrolytic graphite surface based on pure water, it is characterized in that the ethanol that adopts can use methyl alcohol, n-propanol, isopropyl alcohol or tert-butyl alcohol replacement, also can be the aqueous solution of above-mentioned alcohol.
4, as claimed in claim 1 based on the method for pure water replacement at high order pyrolytic graphite surface formation nanometer gas-bearing formation, it is characterized in that substrate surface can be process or not pass through chemistry or physical modification.
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| CN 200410025036 CN1246681C (en) | 2004-06-10 | 2004-06-10 | Method for forming nano gas layer on pyrolytic graphite surface based on alcohol-water substitution |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071151A1 (en) * | 2005-12-21 | 2007-06-28 | Shanghai Institute Of Applied Physics, Chinese Academy Of Sciences | A method for storing gas |
| CN1987414B (en) * | 2005-12-21 | 2011-04-20 | 中国科学院上海应用物理研究所 | Method for growing nano grade air bubbles and its observation and control device and method |
| CN104446645A (en) * | 2014-11-13 | 2015-03-25 | 昆明理工大学 | Amphiphilic ruthenium complex monomolecular film directionally modified HOPG (highly oriented pyrolytic graphite) substrate and preparation method thereof |
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2004
- 2004-06-10 CN CN 200410025036 patent/CN1246681C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071151A1 (en) * | 2005-12-21 | 2007-06-28 | Shanghai Institute Of Applied Physics, Chinese Academy Of Sciences | A method for storing gas |
| US20080317664A1 (en) * | 2005-12-21 | 2008-12-25 | Shanghai Institute Of Applied Physics, Chinese Academy Of Sciences | Method for Gas Storage |
| CN1987414B (en) * | 2005-12-21 | 2011-04-20 | 中国科学院上海应用物理研究所 | Method for growing nano grade air bubbles and its observation and control device and method |
| CN1986894B (en) * | 2005-12-21 | 2011-06-15 | 中国科学院上海应用物理研究所 | Integrated hydrogen producing and storing process and apparatus |
| CN104446645A (en) * | 2014-11-13 | 2015-03-25 | 昆明理工大学 | Amphiphilic ruthenium complex monomolecular film directionally modified HOPG (highly oriented pyrolytic graphite) substrate and preparation method thereof |
| CN104446645B (en) * | 2014-11-13 | 2016-02-24 | 昆明理工大学 | HOPG substrate of amphipathic ruthenium complex monomolecular film directed modification and preparation method thereof |
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