CN102812355A - Method for manufacturing thin layer chromatography plates - Google Patents

Method for manufacturing thin layer chromatography plates Download PDF

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Publication number
CN102812355A
CN102812355A CN2011800108326A CN201180010832A CN102812355A CN 102812355 A CN102812355 A CN 102812355A CN 2011800108326 A CN2011800108326 A CN 2011800108326A CN 201180010832 A CN201180010832 A CN 201180010832A CN 102812355 A CN102812355 A CN 102812355A
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stationary phase
coating
cnt
catalyst layer
tlc plate
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M·R·林福德
R·C·戴维斯
R·R·范佛里特
D·S·詹森
杨立
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Brigham Young University
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Brigham Young University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/90—Plate chromatography, e.g. thin layer or paper chromatography
    • G01N30/92—Construction of the plate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components

Abstract

A method for manufacturing a thin layer chromatography ("TLC") plate (100) is disclosed. The method includes forming a catalyst layer (104) disposed on a substrate that includes a first portion and at least a second portion, each of the first and at least a second portions exhibiting a selected non-linear configuration. The method also includes forming a layer of elongated nanostructures (e.g. carbon nanotubes), and at least partially coating the elongated nanostructures with a coating. The coating includes a stationary phase and/or precursor of a stationary phase for use in chromatography. The stationary phase is functionalized with hydroxyl groups by exposure to acidified water vapor or immersion in a concentrated acid liquid bath (e.g. HCI and methanol). At least a portion of the elongated nanostructures are removed after being coated.

Description

The method for preparing TLCP
The cross reference of related application
The application has required in the U.S. Provisional Application No.61/339 that is entitled as " method for preparing effective thin-layer chromatography carrier " of submission on February 26th, 2010,095 rights and interests, and the disclosure of this application is incorporated herein by reference at this in full.
Background technology
Chromatogram and SPE (" SPE ") are the isolation technics commonly used that in multiple analytical chemistry and biological chemical environment, adopts.Chromatogram and SPE are usually used in the various compositions in the interested sample or fraction separation, extraction and analysis.Chromatogram and SPE also can be used for preparation, purifying, the concentrated and cleaning of sample.
Chromatogram and SPE relate to the multiple technologies of coming the separate complex potpourri based on the differential segment of the stationary phase of being flowed through with entrained sample component of its mobile phase flows and sample by sample.Generally speaking, chromatogram and SPE relate to the use of stationary phase, and said stationary phase comprises in the tube of packing into, in the pillar or as thin layer setting adsorbent onboard.Thin-layer chromatography (" TLC ") uses the stationary phase of sprawling in the thin layer on carrier or backing material plate.Stationary phase commonly used comprises silica gel base absorbant material.
Moving phase is solvent based liquid usually, although gas chromatography adopts the gas flow phase usually.Depend on and hope the various components that extract and/or analyze in various characteristics and the sample of sample to be analyzed, the composition of liquid flow phase maybe be obviously different.For example the pH of liquid flow phase maybe be obviously different with solvent property.In addition, depend on the characteristic of the stationary phase that is adopted, the composition of liquid flow phase maybe be different.During given chromatogram or SPE program, often adopt several kinds of different mobile phase.
Typical TLC plate is through adsorbent (playing stationary phase) and a small amount of inert binder and water are mixed with.Can be with this potpourri as relatively than mucilage material drawout on carrier-pellet.Then, can be with plate drying and activation in baking oven of gained.Combine to be fixed on carrier-pellet or other base material through the stationary phase of bonding agent with gained.The existence of bonding agent possibly cause and the secondary interaction of moving phase and the decline of separation efficiency.
Summary of the invention
Embodiment of the present invention relate to the TLC plate, in chromatogram, use the method and the relevant preparation method of this TLC plate, wherein form a plurality of elongated stationary phase structures and this structure are fixed in base material not using under the independent adhesive case.Do not use any bonding agent can prevent that unwanted secondary from interacting and can improve separation efficiency.
In one embodiment, a kind of method that is used to prepare the TLC plate is disclosed.This method comprises the elongated nanostructured layers of formation and at least partly applies this elongated nanostructured with coating.This coating comprises stationary phase and/or the stationary phase precursor that is used for chromatogram.In one embodiment, can in well-oxygenated environment, burn elongated nanostructured subsequently, remove this elongated nanostructured thus through heating.In one embodiment, elongated nanostructured layers is included in first of growing in the first of catalyst layer and the second portion at least of on the second portion at least of catalyst layer, growing, and each part all demonstrates selected nonlinear organization.
In one embodiment, a kind of TLC plate is disclosed.Said TLC plate comprises base material and extends longitudinally a plurality of stationary phase structures away from base material.At least a portion of a plurality of stationary phase structures demonstrates elongated geometry and does not contain basically as the CNT (" CNT ") that forms the template of stationary phase structure above that.In one embodiment, a plurality of stationary phase structures with selected arranged in patterns on base material.A plurality of stationary phase structures first and at least second portion can be separately for example zigzag pattern or other selected non-linear pattern are arranged with non-linear pattern.This non-linear pattern offers the mechanical stability that the stationary phase structure increases, because single stationary phase structure is easy to each other part entanglement or contact at least, supporting is provided relative to each other.In addition, have been found that and use zigzag or other non-linear pattern to offset the trend that material is peeled off from base material during oxidation forms the stationary phase structure.
In one embodiment, a kind of method of implementing chromatogram is disclosed.This method comprises providing and comprises base material and extend longitudinally the TLC plate away from a plurality of stationary phase structures of base material.At least a portion of these a plurality of stationary phase structures demonstrates elongated geometry.This method also comprise with sample to be analyzed be applied over a plurality of stationary phase structures of this TLC plate and drag flow the mutual-assistance its flow through and be coated with a plurality of stationary phase structures of sample.The different component of sample can be used as moving phase separated and this sample and the interaction of TLC plate.
Any characteristic of disclosed embodiment unrestrictedly combination with one another is used.In addition, through considering following detailed description and accompanying drawing, for those those of ordinary skill of this area, it is obvious that the further feature of present disclosure and advantage will become.
Description of drawings
Fig. 1 is the schematic top plan view of the embodiment of TLC plate intermediate structure, and this intermediate structure comprises base material and be arranged on the catalyst layer on the base material that wherein catalyst layer demonstrates the zigzag pattern;
Fig. 2 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 1, but catalyst layer demonstrates alternative zigzag pattern;
Fig. 3 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 1, but catalyst layer demonstrates substantially parallel intermittent pattern;
Fig. 4 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 3, but catalyst layer demonstrates another kind of substantially parallel intermittent pattern;
Fig. 5 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 1, but catalyst layer demonstrates argyle design;
Fig. 6 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 5, but catalyst layer demonstrates another kind of argyle design;
Fig. 7 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 1, but catalyst layer demonstrates honeycomb-like pattern;
Fig. 8 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 7, but catalyst layer demonstrates another kind of honeycomb-like pattern;
Fig. 9 is the schematic top plan view of another embodiment that is similar to the TLC plate intermediate structure of Fig. 7, but catalyst layer demonstrates another kind of honeycomb-like pattern;
Figure 10 A is the sectional view of the TLC plate intermediate structure of Fig. 1;
Figure 10 B is the sectional view of TLC plate intermediate structure that has Figure 10 A of the CNT that on catalyst layer, grows;
Figure 10 C is the CNT sectional view of the TLC plate intermediate structure of Figure 10 B of the coated coating of part at least;
Figure 10 CC is the amplification plan view from above through one of coating CNT of Figure 10 C;
Figure 10 D is the sectional view of the TLC plate intermediate structure of Figure 10 C, thereby wherein CNT has been burnt and oxide covering formation stationary phase structure;
Figure 10 DD is the amplification plan view from above that is similar to Figure 10 CC, but CNT is burnt;
The serve as reasons schematic top plan view of the TLC plate that the TLC plate intermediate structure that is similar to Fig. 1 processes of Figure 11 A;
Figure 11 B is the amplification plan view from above of the TLC plate intermediate structure of Figure 11 A, and several stationary phase structures that are arranged on the high aspect ratio deposition on this TLC plate substrate have been shown among the figure;
The figure line that Figure 12 A and 12B provide described according to the present invention before the work embodiment oxidation with oxidation after the energy of TLC plate disperse x ray spectrum (" EDX ") spectrogram;
Figure 13 A-13D has provided scanning electron microscope (" the SEM ") image of the various non-linear catalyst layer pattern that on aluminum oxide base material, forms;
Figure 14 A-14P has provided the SEM image of TLC plate, CNT with different corresponding height and SiO that said TLC plate has the different catalyst layer thickness and on catalyst layer, forms 2Elongated nanostructured;
Figure 15 A-15N has provided the SEM image of elongated nanostructured of CNT and the oxidation of silicon infiltration;
Figure 16 A-16D has provided the SEM and other image of more various TLC plate separation efficiencies;
Figure 17 has provided the CNT structure of various silicon infiltrations and the image after this structure oxidation;
Figure 18 A has provided the SiO with zigzag structure of another kind of preparation 2The SEM image of the TLC plate of stationary phase structure;
Figure 18 B has provided the result who puts the TLC plate that CAMAG test mixing thing is arranged;
Figure 18 C has provided and has put the comparative result that is purchased the TLC plate that CAMAG test mixing thing is arranged;
Figure 19 is for permeating transmission electron microscope (" TEM ") and scanning transmission electron microscope (" STEM ") image and electron energy loss spectra (" the EELS ") related data with CNT heart yearn behind the formation silicon shell; With
Figure 20 is the SEM image of the TLC plate with zigzag structure of another kind of preparation.
Embodiment
I. foreword
Embodiment of the present invention relate to TLC plate and relevant preparation method and application.Disclosed TLC plate can be included in a plurality of elongated stationary phase structure that is fixed in base material under the situation of not using independent bonding agent, thereby the high pore texture that is suitable for the chromatogram purposes is provided.Do not use any bonding agent can prevent that unwanted secondary from interacting and can improve separation efficiency.
II. the embodiment and the firm and hard scheme of executing of TLC that prepare the method for TLC plate
In various embodiments, the TLC plate can prepare through following mode: on base material, form elongated nanostructured layers, then with the coating that comprises the stationary phase that is used for chromatogram and/or stationary phase precursor at least part apply this elongated nanostructured.Though in the description hereinafter with the instance of CNT as suitable elongated nanostructured; But also can adopt other elongated nanostructured, such as the semiconductor nanowires that is with or without porous coating, the metal nanometer line that is with or without porous coating, the combination of passing through the formed nano-pillar of nano print photoetching, aforementioned nanostructured or any other suitable nanostructured.
CNT is homeotropic alignment relative to each other usually, although adjacent CNT possibly occur some contacts and/or at least part tangle, this can offer the mechanical stability that whole C NT jungle increases.CNT applies less than the stationary phase of CNT spacing with thickness, and this obtains the porous medium that possibly separate through it by means of chromatogram.The CNT jungle uses as the framework that can apply and/or form stationary phase on it, obtains not containing usually any final structure that is used for stationary phase is incorporated into the bonding agent on the base material.
Said base material can comprise: bottom, be arranged on the back sheet on this bottom and be arranged on the catalyst layer of on base material, growing in order to catalysis CNT on the back sheet.In general, can catalyst layer be deposited on the back sheet through any appropriate technology.For example can use photoetching process to accomplish the setting of catalyst layer, for example shelter catalyst layer and etching and remove the catalyst layer zone of exposing to the open air through mask.This photoetching process can be used for preparing the catalyst layer with selected non-linear (for example zigzag) pattern.Also can use other patterning method, for example during catalyst deposit or printing with the planar mask of paraffin paper.In another embodiment, thus can apply catalyst layer applies whole base material basically.
Catalyst layer can be included in suitable growth conditions and (for example heat and be exposed to process gas such as H 2With carbonaceous gas such as C 2H 4) following any suitable material of catalysis CNT growth.Various transition metal possibly be suitable as catalyst layer.The metal that is fit to includes but not limited to the alloy of iron, nickel, copper, cobalt, aforementioned metal and their combination.
The back sheet of base material is that the structure of TLC plate provides supporting.For example back sheet provides catalyst layer can deposit supporting above that, and the work that also can play diffusion barrier prevents between catalyst layer and the bottom chemical reaction to take place in order to helping.The instance of back sheet material can include but not limited to silicon dioxide (for example fused quartz), aluminium oxide, low bulk high temperature borosilicate glass (for example Pyrex 7740 and/or Schott Borofloat glass), steel (for example stainless steel), silicon wafer, Ni-based material or any other high temp glass or other suitable material.Comprise in the embodiment of the material that is different from aluminium oxide at back sheet, can prepare the back sheet that is used for the CNT growth through on the back sheet of non--aluminium oxide, applying the skim aluminium oxide.The thickness of alumina layer can be about 5-100nm, more particularly for about 10-50nm be about 20-40nm (for example about 30nm) the most especially.
Catalyst layer (for example iron) can put on the back sheet.The thickness of catalyst layer can be about 0.1-15nm, more particularly about 0.5-8nm and even more particularly about 0.5-5nm (for example about 2-3nm).For example the thickness of catalyst layer can be about 0.5nm, about 1nm, about 2nm, about 3nm, about 4nm, about 5nm, about 6nm, about 7nm, about 8nm, about 9nm, about 10nm, about 11nm, about 12nm, about 13nm, about 14nm or about 15nm.Although described concrete catalyst layer thickness in the above, the inventor further find to change catalyst layer thickness effect in diameter, density and the height of the CNT that under the identical condition of others, grows some or each.Therefore, according to an embodiment, can change catalyst layer thickness one or more with in diameter, density or the height of the CNT that changes growth.
The non-linear pattern that catalyst layer can be selected or other pattern apply, and perhaps can put on the whole basically surface of back sheet.Fig. 1-9 shows the various embodiments of catalyst layer pattern.For example Fig. 1 and Figure 10 A show the TLC plate intermediate structure 100 that comprises base material 101; This base material 101 has the back sheet 102 that is arranged on the bottom 103 and is formed on the catalyst layer 104 on the back sheet 102 with non-linear zigzag pattern, and wherein dark line is represented the catalyzer of patterning.In some embodiments, can in some or whole zigzag part of catalyst layer 104, form periodically crack, to offer the TLC plate that forms the most at last average flow phase flow velocity more uniformly.Fig. 2 shows another embodiment of the zigzag pattern of catalyst layer 104, and wherein dark line is represented the catalyzer of patterning.Fig. 3 and Fig. 4 show the TLC plate intermediate structure 100 that comprises base material 101 according to another embodiment separately; This base material 101 has the back sheet 102 that is arranged on the bottom 103 and is formed in the catalyst layer 104 on the back sheet 102 with substantially parallel pattern, and wherein dark line is represented the catalyzer of patterning.Fig. 5 and Fig. 6 show the TLC plate intermediate structure 100 that comprises base material 101 according to different embodiments separately; This base material 101 has the back sheet 102 that is arranged on the bottom 103 and is formed at the catalyst layer 104 on the back sheet 102 with the argyle design of various repetitions, and wherein rhombus is represented catalyzer.Fig. 7-9 shows the TLC plate intermediate structure 100 that comprises base material 101 according to different embodiments separately, and this base material 101 has the back sheet 102 that is arranged on the bottom 103 and is formed at the catalyst layer 104 on the back sheet 102 with different honeycomb-like pattern.Fig. 1 and 2 and 5-9 show non-linear catalyst pattern separately, and the pattern of Fig. 3 and 4 shows the catalyst pattern of common linearity.
Can be with catalyst layer 104 patternings between the adjacent part of the catalyst layer 104 of patterning, to demonstrate any desired spacing.For example average bed interlamellar spacing " S " is shown in Fig. 1.In one embodiment, the average bed interlamellar spacing between the adjacent part of patterned catalyst layer 104 is about 1-50 μ m, more particularly for about 3-20 μ m be about 5-15 μ m (for example about 10 μ m) the most especially.It will be understood by those skilled in the art that catalyst layer 104 can form and has any desired pattern and/or spacing " S ".In another embodiment, catalyst layer 104 can form the whole basically back sheet 102 of covering, has no specific different pattern.In some embodiments, catalyst layer 104 is from inside interval, the edge of back sheet 102, thereby prevents that basically CNT from going up growth on the edge of.In some embodiments, spacing " S " can change on one or two direction, for example partly changes to zigzag from the zigzag part.
Along with on back sheet 102, forming catalyst layer 104; Can TLC plate intermediate structure 100 be placed on the suitable carrier (for example quartzy carrier) in the stove, and be heated to about 600-900 ℃, more particularly for about 650-850 ℃ with even more particularly be the interior temperature of about 700-800 ℃ of (for example about 750 ℃) scope.Before the CNT growth, catalyst layer 104 can be annealed in annealing process, wherein H 2Or other process gas flows through catalyst layer 104 (for example in fused quartz tube), and simultaneous temperature increases to the temperature that will occur the CNT growth at it down from environment temperature.H 2Flow can be about 300cm 3/ min or other suitable flow.
Introduce process gas (H for example 2, ammonia, N 2Or their combination) and carbonaceous gas (for example acetylene, ethene, ethanol, methane or their combination) and make them flow through catalyst layer 104.The carbon containing air-flow also can comprise inert gas (for example argon gas) with control CNT on catalyst layer 104 or the growth rate above it.The throughput ratio of process gas and carbonaceous gas (for example ethene) can be about 0.5: 1-1:1 more particularly is about 0.55: 1-0.85: 1 and even more particularly for about 0.6: 1-0.8: 1.
In case reach the CNT growing height of expectation; Just turn off process gas and carbonaceous gas stream; Along with stove partly is cooled to for example between about 100-300 ℃, more particularly for about 150-250 ℃ and even more particularly under the temperature of about 175-225 ℃ (for example about 200 ℃), can use inert gas (for example argon gas) to flow the purging furnace chamber.
In one embodiment, in order to obtain the aspect ratio of higher bottom width and CNT height, can adopt " beginning/stop " method.For example can turn off carbonaceous gas, thereby cause CNT on a plurality of directions, to grow at the CNT growing period.Such growth possibly be desired in some embodiments, because this can cause more the CNT of mechanically stable (for example adjacent CNT possibly be easier to contact with each other and/or part entanglement at least).
Figure 10 B is the sectional view of an embodiment that is similar to the structure of Fig. 1 and 10A, and wherein CNT 106 is growing above with it on the catalyst layer 104.Thereby CNT 106 growths are extended longitudinally away from base material 101.For example CNT basically quadrature (promptly vertical) extend in each surface of catalyst layer 104 and base material 101.As required, the CNT 106 of growth can be walls single wall or many.The CNT 106 of growth can have about 3-20nm, more particularly be the perhaps average length of about 20-200 μ m of the mean diameter of about 5-10nm (for example about 8.5nm) and about 10-2000 μ m, about 10-1000 μ m, about 10-500 μ m, about 20-400 μ m, about 20-200 μ m, about 100-300 μ m, about 10-100 μ m.The CNT 106 of growth can demonstrate about 10,000-2, and 000,000 average aspect ratio (being average length and the ratio of mean diameter), for example about 10,000-1,000,000 or about 100,000-750,000.
Can select the average length of CNT 106 growths based on specific chromatogram purposes.For example for ultra-thin-layer chromatography (" UTLC "); The average length of CNT 106 can be about 10-100 μ m; For high-performance thin-layer chromatography (" HPTLC "); The average length of CNT 106 can be about 100-300 μ m and for preparation liquid phase chromatography (" PLC "), the average length of CNT 106 can be about 500-2000 μ m.
The additional detail of relevant CNT 106 growths can be at the U.S. Patent application No.12/239 that is entitled as " the X-radiation window with CNT framework ", finds in 281 and 12/239,339.Above-mentioned two applications require U.S. Provisional Patent Application No.60/995,881 right of priority.U.S. Patent application No.12/239,281 and 12/239,339 and U.S. Provisional Patent Application No.60/995,881 all are incorporated herein by reference at this in full.
Although described CNT106 is evenly spaced, and CNT106 also can at least partly tangle to form vertical CNT106 wall each other.As previously mentioned, part entanglement and/or contact help to reduce, limit perhaps to prevent vertical CNT106 wall bending out-of-plane CNT106 at least each other.In addition; On each non-linear partial of catalyst layer 104, grow to form each wall of CNT106 with selected non-linear pattern (the for example pattern shown in Fig. 1) patterning and the each several part that makes CNT106 through making catalyst layer 104; Can further strengthen the rigidity of CNT106 wall, to reduce, to limit or prevent its crooked out-of-plane.
CNT is as the framework that awaits being permeated by material, and said material can increase the mechanical stability of total and be provided for the stationary phase of chromatographic applications.With reference to Figure 10 C, after growth, CNT 106 can use one or more bleeding agents (for example precursor gases) infiltration, so that coating 108 is deposited on the CNT 106.Coating 108 comprises stationary phase and/or stationary phase precursor.The instance that is used for the material of coating 108 includes but not limited to that elemental silicon is (for example by precursor SiH 4Gas aggradation), the combination of silicon dioxide, silicon nitride, element aluminum, aluminium oxide, element, zirconium, zirconia (for example zirconium dioxide), element titanium, titanium dioxide, agraphitic carbon, graphitic carbon and previous materials.Owing to can change the selectivity of the TLC plate of gained to the selection of coating 108, so can select to be used to prepare the coating 108 of any given TLC plate according to the desired use of TLC plate.
In one embodiment, can use chemical vapour deposition technique (for example low-pressure chemical vapor deposition (" LPCVD ")) or other suitable deposition process (for example ald (" ALD ")) to accomplish the infiltration of CNT 106.For example can with the intermediate structure of TLC plate shown in Figure 10 B place stove and be heated to about 500-650 ℃, more particularly for about 540-620 ℃ with even more particularly be the temperature of about 560-600 ℃ (for example about 580 ℃).During permeating, can osmotic pressure be maintained less than about 400 millitorrs.For example can osmotic pressure be maintained about 50-400 millitorr, more particularly for about 100-300 millitorr with even more particularly be about 150-250 millitorr (for example about 200 millitorrs).Under such temperature and pressure condition, make on CNT 106 and to form coating 108 (seeing Figure 10 C) thereby bleeding agent flows through CNT 106.Processing time can influence the deposition of coating material.For example the processing time of infiltration can be about 0.5-10 hour, more particularly for about 1-5 hour be about 1-4 hour (for example about 3 hours) the most especially.
The agraphitic carbon infiltration of CNT106 can use the carbon source that at high temperature flows through fused quartz tube to carry out.For example ethene can be for example at 170cm 3Under the flow of/min and at 200cm 3Argon gas under the flow of/min mixes and in about 900 ℃ temperature current downflow.Because the light absorption characteristic of agraphitic carbon, the detection that therefore separates the post analysis thing maybe needs back specimen preparation.This process can comprise the de-carbon of (for example using oxygen plasma) with oxidation-stabilized label labelled analyte with in high temperature oxygen ambient.For example developer can comprise the silane in gas phase or the solution, and it will put on the TLC plate.In well-oxygenated environment (for example stove, plasma or flame), carbon is burnt, stay SiO 2Pattern, this pattern will be presented at the migration that analyte where occurs.
Can permeate CNT106 and then if desired or hope then to carry out oxidation and form SiO with elemental silicon through LPCVD 2Be used for SiO 2Other deposition process comprise direct SiO 2LPCVD, ALD are perhaps through using SiH 4And O 2Or SiH 2Cl 2With N 2Other CVD method of O is perhaps through being used for the method for CNT infiltration to those skilled in the art with conspicuous other according to the disclosure.The inventor carries out the LPCVD infiltration of CNT, subsequent drying oxidation with elemental silicon.The silicon infiltration method is used SiH 4As the elemental silicon source.Depend on the thickness (penetration degree) of hope, silicon infiltration is through making SiH 4At about 20cm 3Carry out about 530 ℃ of temperature and about 160 millitorrs the about 1-3 of pressure current downflow hour under the flow of/min.Behind the siliceous deposits, in air, material put into stove and handle to about 500-1000 ℃ about 1-10 hour.This processing changes into silicon dioxide with elemental silicon, simultaneously also through making them be oxidized to CO and/or CO 2And remove CNT106, stay the elongated stationary phase structure of processing by silicon dioxide thus, and have no the CNT106 of obvious amount to fill.The degree that depends on oxidizing process, elongated stationary phase structure can be solid basically nano wire, and does not have CNT to be present in hollow central portion wherein.This process makes white and/or the transparent SiO that can be used for chromatogram 2Material.Between the CNT line and silicon infiltration on every side can be near fully (for example at least about 90%).
Can substitute the conformal coating infiltration CNT106 that uses ALD method apparatus that the chromatogram ability is arranged or can handle the selected material that obtains this ability subsequently.ALD can be used for using SiO 2Infiltration CNT.A kind of these class methods can be used SiCl under chosen temperature 4And water.With SiCl 4Introducing comprises the chamber of CNT106 and allows its reaction preset time.After finishing self-limited chemical absorbing/Physical Absorption process, water is introduced said chamber, this water and the SiCl that combines 4Reaction is to make SiO on CNT 106 2Conforma layer.Repeat this process up to realizing predetermined SiO 2Thickness.In other embodiments, can use the method infiltration CNT 106 of similar ALD.For example introduce SiCl 4, but before introducing water, can remove excessive SiCl fully through pumping 4, also can not exclusively remove.Conversely, introducing SiCl 4Before, excessive water can be removed fully, also can not exclusively remove.As suitable for real ALD method,, can deposit SiO sooner through not exclusively removing excess reagent 2For other ALD chemical method that can be used for permeating CNT 106, can expect this same policy of not exclusively removing material.Be also noted that the perfect conformal coating of the uniform thickness that possibly hope or not hope CNT 106.Can permeating method be designed to make the roughly coating of non-uniform thickness, to increase the surface area of carrier.
Figure 10 C is the sectional view of the intermediate structure of TLC plate shown in Figure 10 B, thereby wherein CNT 106 has been deposited on the coating 108 that forms the said periphery extension of periphery and edge that at least partly applies each CNT 106 on the CNT 106 with bleeding agent infiltration coating.At bleeding agent is under the situation of silicon precursor gas such as silane, and coating 108 can be a silicon.But as stated, can use other precursor gases, thereby coating 108 can be formed by aluminium or zirconium.Depend on selected bleeding agent, coating 108 can be only part or apply the whole array of CNT 106 basically at least, perhaps also can be coated in the center section of back sheet 102 and catalyst layer 104 between the CNT 106, the TLC plate that obtains combining.Coating 108 on each CNT 106 shown in Figure 10 C has formed each high-aspect-ratio structure that demonstrates elongated ring-type geometry (for example being hollow cylinder basically).CNT 106 plays the effect that is deposited upon its template on every side that is coated with that makes.In some embodiments, coating 108 can be porous or non--porous.The particular aspect ratio of the slim-lined construction of being processed by coating 108 depends on the combination of height, sedimentation time, technological temperature (the for example temperature of bleeding agent and CNT 106) or the aforementioned technological parameter of template CNT 106.Figure 10 CC is the amplification plan view from above of the single coating CNT 106 of Figure 10 C.Can be the average aspect ratio of a plurality of slim-lined constructions that limited of the coating 108 that applies each CNT 106 (being average length and the ratio of mean diameter) for about 10,000-2,000,000, for example about 10,000-1,000,000, perhaps about 100,000-750,000.The average radial thickness that applies the coating 108 of CNT 106 can be about 10-100nm, more particularly for about 20-80nm with even more particularly be about 25-40nm (for example about 30nm).The average length of the slim-lined construction that is limited coating 108 can be basic identical or similar with template CNT 106.
Figure 19 is illustrated in TEM and STEM and the EELS image with CNT behind the silicon coating formation silicon shell.Analysis result shows that not detecting carbon is diffused into the silicon coating from CNT each other.
In some situations, infiltration and optional oxidation that coating 108 is carried out in CNT 106 unordered growths subsequently possibly cause potential problem.During silicon is changed into the oxidizing process of silicon dioxide, because the adding of oxygen makes the volumetric expansion of material experience.Volumetric expansion causes material to peel off from backing, particularly during long oxidization time more completely.Even seem at first not occur peeling off, but owing to expand, therefore as the result of slight convex or contact, material can be easily wrinkling with peel off.Reducing, minimize or eliminate this material peels off, peels off or wrinkling a kind of mode is through with CNT growth catalyst patterning (for example zigzag or other non-linear) from backing; Like this total is inserted in the space, thereby allowed volumetric expansion during oxidation step.In addition, the patterning of stationary phase medium on the microcosmic scale can improve separation efficiency.The SEM image shows how the thickness that changes catalyst layer causes the CNT growth of differing heights.This SEM image is shown among Figure 14 A-14P.Figure 14 A-14P shows behind oxidation step the outward appearance of infiltration plate, and silicon changes into silicon dioxide and CNT 106 is removed in oxidation step.Note change color be changes in material sign (be that CNT is dark, SiO 2Bright).The SEM image of patterned media shows between the heat of oxidation volume expand (referring to Figure 15 A-15O) before the oxidation and after the oxidation.
Selected zigzag pattern can be included between the specific part of zigzag greater than 0 ° and less than any different angles of 180 °.For example the zigzag pattern shown in Fig. 1,2,11A-11B, the 18A and 20 can be included in the about 90 ° of angles between the adjacent part of zigzag and zigzag of pattern.
As stated, the average bed interlamellar spacing between the adjacent part of patterned catalyst layer 104 can be about 1-50 μ m, more particularly for about 3-20 μ m be about 5-15 μ m (for example about 10 μ m) the most especially.The spacing that causes being limited coating 108 between the slim-lined construction adjacent when CNT 106 side direction outwards and are against each other grown with bleeding agent infiltration and/or coating 108 growth around CNT 106 after CNT 106 growth is less.For example the average headway that is limited coating 108 between the adjacent elongated structure can be about 0.5-30 μ m, more particularly for about 2-10 μ m be about 4-8 μ m the most especially.This spacing causes having the body construction (being that spacing between the adjacent structure plays moving phase and the entrained sample of moving phase owing to the advance effect in hole of process of capillarity) of very high body porosity.When existing, the porosity of any single coating 108 (promptly and relative by the body porosity that spacing produced between the adjacent structure) also has contribution for the overall porosity of TLC plate.
In one embodiment, in case coating 108 has been deposited on the CNT 106, then can partly or remove CNT 106 basically fully.For example can with the TLC plate intermediate structure shown in Figure 10 C place stove and in the presence of oxidizing atmosphere (for example oxygen atmosphere) heating (for example arrive about 800-900 ℃; Perhaps about 850 ℃); Thereby remove (for example burning) all basically CNT 106, only remaining coating 108 and the catalyst layer 104 of TLC plate substrate 101 that is arranged on the back sheet 102.If coating 108 is not a stationary phase, then such oxidation step also can play through change into the effect of stationary phase with institute's coating deposited 108 oxidations and with coating 108.If for example coating 108 is silicon, aluminium or zirconium, then it can be oxidized into monox, aluminium oxide or zirconia.An embodiment of removing the method for CNT 106 can comprise the plasma oxidation coating 108 of utilizing oxygen.Be used at least part and remove other method of CNT 106 and can comprise dissolving CNT 106, perhaps remove through any method.
Figure 10 D is the sectional view of structure shown in Figure 10 C, and wherein CNT 106 has been removed and a plurality of elongated stationary phase structure 108' of the oxidized formation of coating 108.Figure 10 DD is the plan view from above that CNT 106 has been burnt back stationary phase structure 108'.Figure 10 D clearly show that the aspect ratio structure of total height of stationary phase structure 108'.Before oxidation, the size of a plurality of elongated stationary phase structure 108' can be basic identical or similar with the size of a plurality of slim-lined constructions that limited coating 108.Oxidizing process can be carried out at least about 5 hours, more particularly was at least about 10 hours and was at least about 24 hours the most especially.The inventor finds that the oxidation of increase has improved the separation efficiency that is realized by the stationary phase of oxidation.In some embodiments, only part to apply the coating 108 of each CNT 106 oxidized.In other embodiments, it is oxidized all to apply the coating 108 of each CNT 106 basically.
In Figure 10 D and 10DD, be described to hollow state although remove the elongated stationary phase structure 108' in back at CNT 106; But the degree that depends on oxidizing process; Elongated stationary phase structure 108' can be solid basically nano wire, and the space oxide that is wherein occupied by CNT 106 in advance consumes or fills.In the embodiment of coating 108 through ALD or the similar method of ALD (the for example ALD of monox deposition) deposition, the elongated cylinder that the elongated stationary phase structure of gained can be a hollow, vacancy is the position that CNT 106 is positioned in this.
Remove before the separation (for example interact and disturb) that CNT 106 can prevent CNT 106 Interference Flow phases during use TLC plate at use TLC plate through secondary.In addition, this causes white and/or transparent stationary phase; Making chromatogram result's evaluation thus is that black or brown are easier than stationary phase.Comprise in the embodiment of agraphitic carbon in coating 108; Can not remove CNT 106; Because coating 108 all contains carbon with CNT 106, eliminated basically thus by being present in the interactional possibility of secondary that the CNT 106 in the stationary phase is caused that forms during the infiltration.
In some embodiments, stationary phase structure 108' comprise white, canescence, transparent or or be generally the material of light color, thereby make use the moving phase compound that is separated during the TLC plate developing after on the surface of TLC plate it is thus clear that.Silicon and/or silicon dioxide provide the instance of the material of this color contrast.In some embodiments, can fluorescent material (for example ZnS) be attached in the TLC plate to make the TLC plate of fluorescence activity.This can accomplish on the top of chromosorb or on the several individual layers below the chromosorb through making thin film deposition.This can carry out in liquid phase or gas phase.ALD and other CVD or liquid phase process can be used for dead matter put among the chromosorb or on.For example can make fluorescent material at least part apply and/or be incorporated into stationary phase structure 108 ' in, can at least partly apply the center section of the back sheet 102 between the stationary phase structure 108', or this two.
After CNT 106 oxidations and removing, in some embodiments, can the TLC plate be exposed at least a acid so that stationary phase structure 108' is functionalized.The TLC plate that for example can in the presence of HCl, will so form places stove, thereby makes stationary phase structure 108' functionalized so that HCl steam places on the surface of stationary phase structure 108' hydroxyl.Through for example carrying out silanization with moieties, can other chemical functionality and selectivity be added among the stationary phase structure 108' with any suitable gas chemistry method.When stationary phase structure 108' comprises silicon dioxide (for example through silicon coating 108 is carried out oxidation), can pass through C 8Chain, C 18Chain, NH 2Or their incorporate to silicon dioxide so that silicon dioxide is functionalized.
In one embodiment, can behind the oxidation step and during being cooled to environment temperature stationary phase be exposed to water vapor from oxidizing temperature.The water vapor of acidifying can be used for surface hydroxylation.For example this can make solution vapor and stationary phase interaction carry out through the HCl solution top that the TLC plate is placed on boiling.The solution of boiling can comprise that methyl alcohol is to help moistened surface.Spendable other component comprises that other strong acid (for example nitric acid, HBr), organic acid (for example acetate, formic acid, trifluoroacetic acid) maybe can make other appropriate chemical article of surface hydroxylation.In one embodiment, can expose about 5 minutes, although can use the shorter or longer time.Can use multiple silane (for example monochlorosilane, dichlorosilane, trichlorosilane or their combination) will contain the surface silicon alkanisation of silanol.The example of suitable silane comprises alkyl silane (for example octadecyl trichlorosilane, octadecyl dimethylchlorosilane, perfluoroalkyl silane), amino silane, phenyl silane, cyanic acid silane, xenyl silane or their combination.These silane can be that simple function (for example comprises a Si-Cl group, a Si-OCH 3Group, a Si-OCH 2CH 3Group or a Si-OC (O) CH 3Group) or have the silane of a plurality of surface reaction functional group.Considered for example octadecyl diisopropyl chlorosilane of molecule, wherein isopropyl is given the hydrolytic stability that silicon dioxide TLC plate increases.
The water vapor that is exposed to acidifying can make the chromatographic performance of material improve.Figure 16 A-16D has proved the chromatogram ability of using this acid treatment how to influence material.The chemical substance of separating in the image among Figure 16 A-16D is rhodamine 6G, Sunset Yellow FCF and Sulforhodamine B.Rhodamine 6G is at utmost to be retained on the TLC plate.
As described, can after infiltration, remove CNT through wet or dry oxidation.At least with regard to dry oxidation, this method of removing CNT has reduced the lip-deep silanol of stationary phase structure 108' (" SiOH ") group.In order to increase the lip-deep silanol groups of stationary phase structure 108', can make the SiO of stationary phase structure 108' as stated 2Material stands the steam treatment of acidifying.In addition or alternatively, can be with the SiO of stationary phase structure 108' 2The HCl acidic liquid that material stands to concentrate is bathed preset time.For example can the TLC plate be immersed the selected time of acid solution.In one embodiment, acid solution can comprise HCl that 50:50vol./vol. concentrates and methyl alcohol and TLC plate and can be heated to reflux temperature therein several hours (for example 4-20 hour).Methyl alcohol in the acid solution can help moistened surface.Spendable other acid is included in those (for example nitric acid, HBr, acetate, formic acid, trifluoroacetic acid or their combinations) that other places are described.Be exposed to HCl steam or the water vapor (comprising above-mentioned acid or other suitable acid) of water vapor or acidifying is introduced oxidizing chamber; Simultaneously with material cooled or preset time at high temperature, can increase the number of hydroxyl on the silica surface of stationary phase structure 108'.
In one embodiment, can prepare the TLC plate that has enrichment region.This relates to the zone with low relatively residence time that setting wherein possibly put compound.This allow moving phase promptly carry analyte through this zone and then analyte will slow down when sorbent bed normally arriving.This can be through forming the pre-concentration district and/or carrying out with this zone of chemical substance selective functionalization that allows analyte to reduce the residence time with low-density stationary phase structure.
In some embodiments, before or after CNT 106 growths and/or applying CNT 106, base material 101 can be rule or the part cutting.Through line or cutting base material 101, can prepare less TLC plate through line/bigger TLC plate of line of cut division along base material 101.
Figure 11 A is the plan view from above of the embodiment of TLC plate 100'.Figure 11 B is the guide wire of alternative shape of TLC plate 100', comprising the stationary phase structure 108' between end 110 that is arranged on TLC plate 100' and the end 112.The TLC plate prepared according to the disclosed the inventive method of this paper provides stationary phase, wherein under the situation of not using any independent bonding agent (for example being generally calcium sulphate), stationary phase is attached on the base material of TLC plate.Because the secondary that bonding agent caused interacts, said bonding agent possibly influence the performance of TLC plate.Can form TLC plate more efficiently without any need for bonding agent, this secondary interacted minimize and/or prevent that this secondary from interacting.
The spacing of stationary phase structure 108' is shown in Figure 11 A and Figure 11 B, and this spacing generally is uniform.At the diverse location of TLC plate 100', the density of stationary phase structure 108' maybe difference (for example bigger or less) but in some embodiments.For example can be different from (for example being greater than or less than) density near end 112 in density near the stationary phase structure 108' of end 110.As substituting perhaps in addition, the density of stationary phase structure 108' changes with the position, and the composition of stationary phase structure 108' can change with the position.As non-limitative example, another part that the part of stationary phase structure 108' can comprise zirconia and stationary phase structure 108' can comprise silicon dioxide.
In addition, according to the prepared TLC plate of the inventive method disclosed herein stationary phase with extra high porosity is provided.High porosity and do not exist bonding agent can make that the efficient of TLC plate increases in the process of the sample that is used for analyzing moving phase.In one embodiment, be used for the analytic sample material according to the open formed TLC plate of method.In one embodiment, sample to be analyzed is put on the stationary phase structure 108' last (for example near end 110) of TLC plate 100'.Then, drag mobile phase solvent or solvent mixture (for example through TLC plate 100' is placed the container that comprises solvent or solvent mixture) through capillarity along TLC plate 100' (for example making progress).When through capillarity along TLC plate 100' towards the opposite end 112 when dragging solvent or solvent mixture, this sample dissolution is in moving phase and realize the separation of each component in the sample, this is because the different component of sample rises along TLC plate 100' with different rates.The stationary phase structure 108' of high aspect ratio and since each high aspect ratio stationary phase structure 108' between the body porosity that spacing caused; Make that the component in the sample has good separation efficiency when moving phase (for example solvent or solvent mixture) is carried sample component through stationary phase structure 108'.TLC plate 100' also can be used among the HPTLC, and wherein one or more methods of applying step can robotization, thereby improves the resolution that is reached and allow to quantize more accurately.
III Work embodiment
The embodiment that below works is not limited to the scope of this instructions or accompanying claims just for illustration purpose.
Embodiment 1
Put on through alumina layer and to form independent TLC plate on the back sheet 30nm.The iron catalyst film of 2-3nm is deposited on the alumina layer, and forms pattern, to form TLC plate intermediate structure through photoetching process.TLC plate intermediate structure is placed the quartzy support column of stove and is heated to about 750 ℃, simultaneously with about 500 standard cm 3The flow of/min makes H 2Process gas this quartz ampoule of flowing through.In case stove reaches about 750 ℃, then begin with about 700 standard cm 3The flow of/min flows through the C of carbon containing 2H 4Gas.After the growth of accomplishing CNT, turn off H 2And C 2H 4Gas stream, and with argon gas with about 350 standard cm 3The flow of/min purges quartz ampoule, simultaneously stove is cooled to about 200 ℃.The CNT of growth has the diameter that is about 8.5nm.
Use LPCVD to deposit undoped polysilicon, thereby the CNT of growth is applied with silicon.This CNT is placed the LPCVD stove, and under the pressure of about 200 millitorrs, be heated to about 580 ℃, simultaneously with about 20 standard cm 3The flow of/min makes SiH 4Flow through about 3 hours.The LPCVD method has applied CNT and alumina layer.After applying with silicon, this is placed stove and be heated to about 850 ℃ through the TLC plate intermediate structure that applies, and remain on and be exposed to simultaneously under this temperature in the atmosphere, remove CNT thus and the silica of deposition is changed into silicon dioxide.Make the different oxidation sample, wherein carried out oxidation about 5 hours, about 10 hours and about 24 hours.Test shows that increasing oxidization time has increased the ability of the analyte migration in the moving phase through the silicon/silicon dioxide stationary phase.
Figure 12 A and 12B show before the oxidation and the EDX spectrum of the plate after the oxidation.There is carbon before the oxidation.The carbon of remaining minute quantity after the oxidation.In addition, oxygen is grafted to through chemical method on the surface of silicon and forms silicon dioxide.
Embodiment 2-35
Put on through alumina layer and to form independent TLC plate on the base material 30nm.Afterwards, apply photoresist, carry out photoetching and development subsequently.After the development, then alumina layer and the photoresist catalyst material with scheduled volume is applied.In these examples, with 2,4,6 or 7nm iron be deposited upon photoresist and alumina layer top.After the iron catalyst deposition, place solvent acetone to bathe base material, it is used to remove stays top photoresist and iron, like finding among Figure 13 A-13D.Then through making 300cm 3/ min H 2Flow through 1 inch fused quartz tube and simultaneously stove is heated to 650-850 ℃ temperature from environment temperature catalyst material is annealed, thus TLC plate intermediate structure is used for the CNT growth.After the annealing, through making 100-1000cm 3/ min ethene and 300cm 3/ min H 2Mixed flow is crossed fused quartz tube and is made the CNT growth.Afterwards, the cooling stove is used 380cm simultaneously 3/ min argon purge fused quartz tube is to remove any remaining ethene and hydrogen.
Permeate CNT and be oxidized to SiO then with elemental silicon through LPCVD then 2Osmosis process uses 20cm under 530 ℃ and 160 millitorr pressure 3/ min SiH 4About 1 hour.Behind the silicon infiltration, in air, material put into stove and be heated to about 500-1000 ℃ about 1-10 hour, elemental silicon changed into silicon dioxide and to remove CNT simultaneously.This process makes the white SiO that is applicable to chromatographic applications 2Material.Figure 17 has described the oxidation and the oxidation example not of CNT TLC array of the silicon infiltration of formation like this.The CNT of silicon infiltration is brown (darker), and white plate is the TLC plate of oxidation.Figure 14 A-14P shows the other SEM image of these examples.Following Table I provides relevant these preparation examples each information.
Table I
Embodiment Figure Fe thickness SiO 2 The height of nanostructured
2 14A 7nm 105μm
3 14B 7nm 90μm
4 14C 7nm 80μm
5 14D 7nm 100μm
6 14E 6nm 100μm
7 14F 6nm 130μm
8 14G 6nm 140μm
9 14H 6nm 130μm
10 14I 4nm Warped boar (highly not measuring)
11 14J 4nm 190μm
12 14K 4nm 165μm
13 14L 4nm 220μm
14 14M 2nm 145μm
15 14N 2nm 125μm
16 14O 2nm 142μm
17 14P 2nm 7μm
Figure 15 A-15N is the other SEM image of the example of preparation.Each of Figure 15 A-15N comprises the triplex row photo.The first row photo is represented the CNT of the preceding silicon infiltration of oxidation.The second row photo representes that silicon has been oxidized to SiO 2The silicon nanostructure of oxidation.The third line photo is represented the view that some are other, and wherein first photo is the side view of silicon nanostructure, and second photo is SiO 2The side view of nanostructured and the 3rd photo are SiO 2The enlarged side view of nanostructured.Following Table II provides relevant these preparation examples each additional information.
Table II
Embodiment Figure Fe thickness
18 15A 2nm
19 15B 2nm
20 15C 2nm
21 15D 2nm
22 15E 4nm
23 15F 4nm
24 15G 4nm
25 15H 6nm
26 15I 6nm
27 15J 6nm
28 15K 6nm
29 15L 7nm
30 15M 7nm
31 15N 7nm
Figure 16 A-16D is the SEM image of several preparation samples, and several preparation sample be purchased TLC plate, conventional processing TLC plate with through plate being placed on the compare test result that 12M HCl top used the TLC plate of HCl steam treatment to compare in 5 minutes.In compare test, use three kinds of different analyte-rhodamine 6Gs, Sunset Yellow FCF and Sulforhodamine B.Analyte with the top order of listing at the 9:1 methylene chloride: separate in the methanol solvate system.The SEM image from left to right and is from top to bottom represented: the side view of (1) elongated nanostructured; (2) vertical view of elongated nanostructured; (3) plan view from above of elongated nanostructured; (4) enlarged drawing of elongated nanostructured.Illustrate in addition (and mark) be purchased the TLC plate, the conventional processing plate (is SiO 2Do not have hydroxylation) and SiO wherein 2By the compare test of hydroxylated HCl disposable plates.Like finding in the image, the conventional processing plate causes than is purchased the better analyte of TLC plate to separate, and causes separating than the better analyte of conventional processing TLC plate with the HCl disposable plates.Following Table III provides relevant these embodiment each additional information.
Table III
Embodiment Figure Fe thickness
32 16A 4nm
33 16B 4nm
34 16C 4nm
35 16D 6nm
Embodiment 36
The SEM graphical representation of Figure 18 A formed SiO 2The basic zigzag pattern continuously of stationary phase structure.For the chromatogram ability of the TLC plate that proves Figure 18 A, use the test solution of producing by CAMAG (Muttenz, Switzerland).Shown in Figure 18 B, point has the TLC plate of CAMAG test mixing thing to differentiate all 5 kinds of analytes fully.Utilize the range ability of toluene moving phase to be 45mm.The R of colored compound fBe worth as follows: yellow: 0.933, redness: 0.624, blueness 0.506, black: 0.32, purple: 0.231.Compare with being purchased plate (Figure 18 C), this plate demonstrates slightly different selectivity for CAMAG test mixing thing.Be used to be purchased the R of the colored compound of plate fBe worth as follows: yellow: 0.260, redness: 0.136, blueness 0.120, black: 0.098, purple: 0.002.With another kind of according to embodiments of the present invention similar little preparation TLC plate be purchased the Merck TLC of acquisition and the additional testing data of HPTLC plate comparison are shown in down in the Table IV.Proved that like higher plate number little according to embodiments of the present invention preparation TLC plate demonstrates than is purchased Merck TLC and the better separation efficiency of HPTLC plate of acquisition.
Table IV
Figure BDA00002050794800221
Figure 20 is illustrated in the SiO that forms on the TLC plate 2The another kind of basic SEM image of zigzag pattern continuously of stationary phase structure.
Said embodiment can be used for dissimilar liquid phases or gas chromatography, for example high speed liquid chromatography (" HPLC "), ultra performance liquid chromatography (" UPLC "), microfluidic applications, pressurization liquid chromatography, microfluid or nano-fluid chromatogram, annular or anti-annular TLC and any other type chromatographic applications.Different pillars or the separating medium of HPLC, UPLC or microfluidic applications that is used to comprise patterning or non-patterning infiltration CNT is all in the scope of the present disclosure.
Though this paper discloses each side and embodiment, others and embodiment have also been imagined.Each side disclosed herein and embodiment are for illustration purpose and are not used in restriction.In addition, this paper comprises that the employed word of claims " comprises ", " having " and variant thereof (for example " comprising " and " containing ") all are open and " comprise " with word and variant (for example " comprising ") has identical implication.

Claims (15)

1. method for preparing TLCP, said method comprises:
Formation is arranged on the catalyst layer on the base material, and said catalyst layer comprises first and second portion at least, said first and at least second portion demonstrate selected nonlinear organization separately;
Catalyst layer first and form elongated nanostructured layers at least on the second portion, wherein elongated nanostructured layers is included in first of growing in the first of catalyst layer and the second portion at least of on the second portion at least of catalyst layer, growing;
With coating at least part apply said elongated nanostructured, said coating comprises at least a of the stationary phase that is used for chromatogram or stationary phase precursor;
After part applied said elongated nanostructured at least with coating, part was removed said elongated nanostructured at least; With
Coating is immersed acidic liquid solution so that hydroxyl is attached on the said coating.
2. the method for claim 1, wherein said acidic liquid solution comprise and are selected from following acid: hydrochloric acid, nitric acid, hydrobromic acid, acetate, formic acid, trifluoroacetic acid and their combination.
3. the method for claim 1, wherein acidic liquid solution comprises the concentrated bath of HCl and the methyl alcohol of 50:50v/v.
4. like each described method of claim 1-3, the coating that wherein at least partly applies said elongated nanostructured has defined each slim-lined construction that extends longitudinally away from base material.
5. like each described method of claim 1-4, wherein said base material comprises the back sheet that catalyst layer is set on it, and said back sheet comprises at least a following material that is selected from: silicon dioxide, silicon, nickel aluminium oxide, borosilicate glass and steel.
6. like each described method of claim 1-5, wherein catalyst layer first and form elongated nanostructured layers on the second portion at least and comprise the carbon nano-tube layer.
7. like each described method of claim 1-6, wherein at least partly apply said elongated nanostructured and comprise that the formation coating is to comprise at least a following material that is selected from: silicon, silicon dioxide, silicon nitride, aluminium, aluminium oxide, titanium, titanium dioxide, zirconium and zirconia with coating.
8. method as claimed in claim 7, wherein form coating with comprise at least a be selected from silicon, silicon dioxide, silicon nitride, aluminium, aluminium oxide, titanium, titanium dioxide, zirconium and zirconic material comprise through low-pressure chemical vapor deposition with bleeding agent at least part permeate said elongated nanostructured.
9. like each described method of claim 1-8; Thereby wherein at least part remove said elongated nanostructured comprise oxidation at least the part coating that applies said elongated nanostructured form a plurality of stationary phase structures and the said elongated nanostructured of oxidation and make and be removed on said elongated nanostructured basically.
10. like each described method of claim 1-9, wherein said catalyst layer first and at least second portion all form the zigzag pattern.
11. method as claimed in claim 10, first and second parts of wherein said zigzag pattern relative to each other are about 90 °.
12. like each described method of claim 1-11, wherein at least a in stationary phase or the stationary phase precursor demonstrate about 10,000-2,000,000 average aspect ratio.
13. like each described method of claim 1-12, wherein at least a in stationary phase or the stationary phase precursor without adhesive attachment on base material.
14. like each described method of claim 1-13, wherein at least a part at least in stationary phase or the stationary phase precursor is tangled each other.
15. like each described method of claim 1-14, wherein at least a in stationary phase or the stationary phase precursor is in said first and demonstrate the equispaced of about 4-8 μ m at least between the second portion.
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