CN105944637B - A kind of method for fixing metal nano catalyst in microreactor channel wall - Google Patents

A kind of method for fixing metal nano catalyst in microreactor channel wall Download PDF

Info

Publication number
CN105944637B
CN105944637B CN201610321271.6A CN201610321271A CN105944637B CN 105944637 B CN105944637 B CN 105944637B CN 201610321271 A CN201610321271 A CN 201610321271A CN 105944637 B CN105944637 B CN 105944637B
Authority
CN
China
Prior art keywords
substrate
metal nano
water
catalyst
dopamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610321271.6A
Other languages
Chinese (zh)
Other versions
CN105944637A (en
Inventor
张磊
褚良银
刘壮
谢锐
巨晓洁
汪伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN201610321271.6A priority Critical patent/CN105944637B/en
Publication of CN105944637A publication Critical patent/CN105944637A/en
Application granted granted Critical
Publication of CN105944637B publication Critical patent/CN105944637B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00835—Comprising catalytically active material

Abstract

The method provided by the invention for fixing metal nano catalyst in microreactor channel wall, step are as follows：(1) substrate that microchannel is provided with to surface is cleaned and dried, then dried substrate is dipped to substrate surface in aqueous dopamine solution under agitation and forms poly-dopamine coating, cleaning removes the unstable poly-dopamine nano particle of substrate surface；(2) substrate by step (1) processing is soaked at least 3h so that metal nano catalyst to be fixed on the substrate in the aqueous solution containing metal catalyst ion under agitation, cleaning removes the unstable metal nano catalyst of substrate surface and drying, produces the substrate that surface is fixed with metal nano catalyst；(3) sheet glass is covered and be fixed with surface on the substrate of metal nano catalyst, be bonded sheet glass and substrate using ultraviolet cured adhesive water.The method of the invention can simplify the operation of the fixation of metal nano catalyst, reduces fixed cost and improve fixed efficiency.

Description

A kind of method for fixing metal nano catalyst in microreactor channel wall
Technical field
It is more particularly to a kind of to fix metal nano catalysis in microreactor channel wall the invention belongs to microreactor field The method of agent.
Background technology
For the channel size of microreactor typically at tens to hundreds of microns, this causes microreactor to have larger ratio surface Product, so as to significantly improve its mass transfer, diabatic process.When integrated metal nanocatalyst is used to urge in the passage in microreactor When changing reaction, catalytic efficiency, increase products collection efficiency can be significantly improved, shorten the reaction time so that microreactor is urged in multiphase flow Changing reaction field has important application prospect., can according to integration mode of the metal nano catalyst in microreactor passage Catalytic micro-reactor is divided into filling bed type and wall carries formula.Filling bed type microreactor is usually that catalyst is loaded into porous branch Support on carrier, then open support carrier is loaded into the passage of microreactor, this microreactor has larger catalysis Specific surface area and shorter reaction length, but can not accurately control residence time of reaction solution, easy blocking channel, need it is higher Operating pressure and pressure drop is larger.It is usually the channel wall that catalyst is affixed directly to microreactor that wall, which carries the reactor that declines, Compared to filling bed type microreactor, this microreactor has larger reaction compartment, is not easily blocked passage, can effectively reduce The pressure loss, this causes wall to carry the extensive concern that the reactor that declines receives researcher.
At present, the method for fixing metal nano catalyst in microreactor channel wall mainly has physical method and chemistry side Method.Catalyst is fixed on channel wall by physical method typically by Van der Waals force or charge effect, but passes through physical method The antiscour stability of fixed metal nano catalyst is poor, is unfavorable for prolonged catalytic reaction, and some physical methods also need To use and arrive this kind of expensive instrument of femtosecond laser instrument, be unfavorable for the reduction of fixed cost.Chemical method is generally required to micro- anti- Answer device channel wall to carry out multi-step chemical modification, small molecule or polymer brush are grafted on channel wall as catalyst carrier. For example, Costantini etc. is grafted poly- first using microchannel surface of ATRP (ATRP) method in glass substrate The polymer brush gel of base ethyl acrylate-polyethylene glycol, then silver and palladium nano-particles are fixed on by local reduction way In the macromolecule network, this method carries out silanization treatment firstly the need of to glass baseplate surface, then will be used for ATRP reactions Initiator molecule dibromo-isobutyl acylbromide fix, then the surface that polymer brush is grafted on to glass substrate is reacted by ATRP, most Metallic particles in-situ reducing is fixed in the macromolecule network afterwards (see F.Costantini, E.M.Benetti, R.M.Tiggelaar,et al.,Chem.Eur.J.,2010,16,12406.)；Kim etc. is by titania nanoparticles to change The mode for learning key is fixed on dimethyl silicone polymer (PDMS) microreactor channel wall, and this method needs first synthesizing o-dihydroxybenzene It is then that this is polymer-modified in microreactor channel wall with the high molecular polymer of polyvinylpyrrolidone, finally by two Titan oxide particles fix (see S.M.Kim, Y.H.Park, S.W.Seo, et al., Adv.Mater.Interfaces, 2015,2, 1500174.).The operation of above-mentioned chemical method all very very complicateds, the fixation difficulty of metal nano catalyst is big, both unfavorable In the raising of fixed efficiency, also it is unfavorable for the reduction of fixed cost.Therefore, if can develop it is simpler, efficiently, cost it is cheap and The immobilized channel wall to microreactor of blanket method, for promoting microreactor by metal nano catalyst stabilization Application in metal-based catalyzed reaction field will produce important meaning.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind metal is fixed in microreactor channel wall The method of nanocatalyst, simplifying the operation of the fixation of metal nano catalyst, reducing fixed cost and improving fixed efficiency.
The method provided by the invention for fixing metal nano catalyst in microreactor channel wall, step are as follows：
(1) substrate for being provided with microchannel to surface with acetone or alcohol, deionized water successively is cleaned to remove The organic pollution and solid particle of substrate surface are stated, the water of the substrate surface after removing cleaning is then dried, in stirring condition It is lower that dried substrate is dipped to substrate surface formation poly-dopamine coating in aqueous dopamine solution, then by after immersion Substrate is cleaned under ultrasound condition with deionized water to remove the unstable poly-dopamine nano particle of substrate surface；
The aqueous dopamine solution is formed by Dopamine hydrochloride with pH value for 7~12 buffer, prepares dopamine During the aqueous solution, the mass ratio for the buffer solution that Dopamine hydrochloride is 7~12 with pH value is 1:(500~1000)；The microchannel is set It is equipped with entrance and exit；
(2) substrate by step (1) processing is soaked in the aqueous solution containing metal catalyst ion under agitation At least 3h is steeped so that metal nano catalyst to be fixed on the substrate, then spends the substrate after immersion under ultrasound condition To remove the unstable metal nano catalyst of substrate surface, the water for drying the substrate surface after removing cleaning is for ionized water cleaning The substrate that surface is fixed with metal nano catalyst must be arrived；
(3) sheet glass is covered and be fixed with surface obtained by step (2) on the substrate of metal nano catalyst, use ultraviolet light Sheet glass and substrate are bonded by solidified glue；The sheet glass is provided with logical with the microchannel entrance on substrate and outlet corresponding section Hole.
In the step of above method (1), soak time of the dried substrate in aqueous dopamine solution is 12~16h.
In the step of above method (1), the temperature of aqueous dopamine solution is 20~25 DEG C when controlling immersion.
In the step of above method (1), the buffer solution that the pH value is 7~12 is preferably Tris buffer solutions.
In the step of above method (2), the substrate handled by step (1) is in the aqueous solution containing metal catalyst ion Soak time be preferably 3~5h.
In the step of above method (2), the temperature of the aqueous solution containing metal catalyst ion described in when controlling immersion for 5~ 40℃。
In the step of above method (1), the effect of stirring is that poly-dopamine coating in uniform thickness is formed on substrate, on In the step of stating method (2), the effect of stirring is that metal nano catalyst is uniformly fixed on substrate, step (1) and (2) In, 200~800r/min of generally use rotating speed is stirred.
In the above method, the species root of the metal catalyst ion contained in the aqueous solution containing metal catalyst ion Factually the demand of border catalytic reaction is determined, and the conventional aqueous solution containing metal catalyst ion can be by water soluble silver salt, water Dissolubility gold salt, water-soluble palladium salt, water-soluble mantoquita or water-soluble molysite and deionized water are formulated；Preparation contains metallic catalyst During the aqueous solution of ion, water soluble silver salt, water-soluble gold salt, water-soluble palladium salt, water-soluble mantoquita or water-soluble molysite and go from The mass ratio of sub- water is preferably 1:(200~1000).
In the above method, if step (2) obtained by surface be fixed with the substrate of metal nano catalyst only include one it is micro- Passage, then the microchannel on substrate should be at least completely covered in step (3) glass sheet shapes and size；If obtained by step (2) Surface, which is fixed with the substrate of metal nano catalyst, includes multiple microchannels, then surface first should be fixed with metal by step (3) The substrate of nanocatalyst is divided into the fritter for only including a microchannel, and the shapes and sizes of step (3) described sheet glass are extremely The microchannel that the fritter surface after the segmentation is fixed with the substrate of metal nano catalyst should be completely covered less.
In the step of above method (1), the substrate that the surface is provided with microchannel can be glass substrate, silicon substrate, no Become rusty steel substrate, polymethyl methacrylate (PMMA) substrate, dimethyl silicone polymer (PDMS) substrate etc.；The surface is provided with The substrate of microchannel can directly be bought, and can also entrust manufacturer's customized production, can also use existing method in the base of blank Plate surface, which makes microchannel, must arrive the substrate that surface is provided with microchannel, the method being combined for example with photoetching with wet etching Make, the method that for details, reference can be made in CN 104190482B makes.
The principle that the method for the invention fixes metal nano catalyst using poly-dopamine coating reducing metal ion is shown It is intended to as shown in figure 1, because dopaminergic forms stable poly-dopamine coating on almost all of organic or inorganic substrate, The surface (including microchannel wall on the substrate) that this method is provided with the substrate of microchannel on surface first forms poly- DOPA Amine coating, then using the reproducibility of catechol group on poly-dopamine coating by metal catalyst ion in-situ reducing Cheng Na Rice metal catalyst atoms are simultaneously fixed on poly-dopamine coating, by follow-up microreactor bonding operation, you can led to The microreactor of metal nano catalyst is secured on road wall.Due to the catechol group in poly-dopamine reproducibility compared with By force, therefore the method for the invention can be realized in the case where not adding any assistant reducing agent and various metals catalyst is carried out Large area and uniform fixation.
Compared with prior art, the invention has the advantages that：
1. the invention provides a kind of new method that metal nano catalyst is fixed in microreactor channel wall, due to more Bar amine can form poly-dopamine coating in substrate surface, the catechol group on poly-dopamine coating can by metallic catalyst from Son reduction and stably, be uniformly fixed on coating, therefore the method for the invention is by the immersion of two steps simple solution Fixation of the metallic catalyst on the substrate of microchannel is provided with is realized, then can be led to by sheet glass bonding operation The microreactor of metal nano catalyst is secured on road wall.The operation very simple of the method for the invention, can not only have Effect reduces the difficulty that metallic catalyst is fixed in microreactor channel wall, and can shorten the set time, improves fixed efficiency.
2. in the method for the invention, because dopamine can be on almost all of organic or inorganic substrate Poly-dopamine coating is formed, and then realizes fixation of the metal nano catalyst in the substrate surface for being provided with microchannel, therefore this Invention methods described is applied to the microreactor of nearly all material, is not influenceed by substrate material type and surface state, fits It is wide with scope.
3. in the method for the invention, because the reproducibility of the catechol group in poly-dopamine coating is stronger, therefore The method of the invention can be achieved to metal nano catalyst large area, in the case of without using any assistant reducing agent Homogenized fixation, it is all suitable for for metallic catalysts such as the common silver of fixation, gold, palladium, copper, iron.
4. experiment shows, the metal nano catalyst fixed using the method for the invention in microreactor channel wall Resisting fluid scouring stability is high, and after prolonged fluid scouring and catalytic reaction, metal nano catalyst is still stable to be consolidated Be scheduled on the channel wall of microreactor and there is higher reactivity (see embodiment 1).
5. the reaction condition of the method for the invention is simple, gentle, can be achieved using the instrument of routine, without using spy Different experiment reagent and expensive instrument, therefore the method for the invention application easy to spread, it is advantageously implemented answering for scale With.
Brief description of the drawings
Fig. 1 is the original that the method for the invention fixes metal nano catalyst using poly-dopamine coating reducing metal ion Manage schematic diagram, in figure, 1-poly-dopamine coating, 2-metal catalyst ion (Mn+), 3-metallic catalyst simple substance (M0)、4— Substrate.
Fig. 2 is to fix the process schematic of metal nano catalyst in microreactor channel wall in each embodiment, wherein, Figure a) is provided with the glass substrate of microchannel for surface, and figure is b) to carry out glass substrate at immersion in aqueous dopamine solution Reason, figure are c) glass substrate with poly-dopamine coating, and figure is d) to urge the glass substrate with poly-dopamine coating containing metal Immersion treatment is carried out in the aqueous solution of agent ion, figure e) is fixed with the glass substrate of metal nano catalyst for surface, and figure is f) To be bonded obtained microreactor, in figure, 5-surface is provided with the glass substrate, 6-aqueous dopamine solution, 7-band of microchannel The glass substrate of poly-dopamine coating, the 8-aqueous solution containing metal catalyst ion, 9-glass slide, 10-surface are fixed There are glass substrate, the 11-polyethylene hose of metal nano catalyst.
Fig. 3 is the schematic shapes for the microchannel designed in embodiment 1.
Fig. 4 is the atomic force microscopy diagram of the glass baseplate surface in different disposal stage in embodiment 1, wherein, figure a) is Blank glass substrate, figure b) are provided with microchannel for surface and are c) microchannel wall with the glass substrate of poly-dopamine coating, figure Face is fixed with the glass substrate of Nano Silver.
Fig. 5 is the x-ray photoelectron energy spectrum diagram of the glass baseplate surface in different disposal stage in embodiment 1, wherein, figure is a) For the full spectral curve of glass baseplate surface：A1 be) blank glass substrate, a2) for surface it is provided with microchannel and with poly-dopamine The glass substrate of coating, a3) glass substrate of Nano Silver is fixed with for microchannel wall, figure b) is fixed with for microchannel wall and received The high-resolution spectrum curve of silver element on meter Yin glass substrate.
Fig. 6 is the low power scanning electron microscope (SEM) photograph at the microchannel for the glass substrate that Nano Silver is fixed with embodiment 1.
Fig. 7 is the high power scanning electron microscope (SEM) photograph at the microchannel for the glass substrate that Nano Silver is fixed with embodiment 1.
Fig. 8 is the x-ray photoelectron spectrum curve for the glass baseplate surface that Nano Silver is fixed with embodiment 1.
Fig. 9 is the optical photograph of the microreactor that channel wall is fixed with Nano Silver in embodiment 1.
Figure 10 is the catalysis performance test result figure of the microreactor in embodiment 1, wherein, figure is a) continuous catalysis During reaction conversion ratio with the reaction time variation diagram, figure b) be continuous catalysis 24h after microreactor channel wall high power Scanning electron microscope (SEM) photograph, the elementary analysis curve of microreactor channel wall after figure is c) continuous catalysis 24h.
Figure 11 is that the glass substrate in embodiment 2 is soaked to being fixed in the silver ionized water solution of different temperatures and concentration The influence figure of Nano Silver particle diameter on glass substrate, wherein, surface of figure a) to soak to obtain under different temperatures and concentration is consolidated Surely there is the atomic force microscopy diagram of the glass baseplate surface of Nano Silver, it b) is the table for soaking to obtain under different temperatures and concentration to scheme Face is fixed with the grain size distribution of the Nano Silver on the glass substrate of Nano Silver.
Embodiment
Below by embodiment combination accompanying drawing metal nano catalysis is fixed to of the present invention in microreactor channel wall The method of agent is described further.In following each embodiments, the Dopamine hydrochloride is purchased from Sigma-Aldrich (sigma- Aldrich) chemical company；Trishydroxymethylaminomethane (Tris) is bought from Ke Long Chemical Industry Science Co., Ltd.Following each realities Apply in example, there is provided the instrument of ultrasound condition is ultrasonic cleaner.
Embodiment 1
In the present embodiment, microreactor channel wall fix metal nano catalyst process schematic as shown in Fig. 2 Microreactor channel wall fix metal nano catalyst the step of it is as follows：
(1) using the microchannel of AutoCAD Software on Drawing serpentine shape as shown in Figure 3, the width of microchannel is 400 μm, length 810mm, referring next to the method in CN 104190482B embodiments 1 in the blank glass that size is 76mm × 25mm Glass substrate surface produces the microchannel of design shape, obtains to surface and is provided with the glass substrate of microchannel, and the microchannel is set It is equipped with two entrances and one outlet.
(2) successively with acetone, deionized water enter to be provided with surface the glass substrate of microchannel under ultrasound condition it is each clear 10min is washed, to remove the organic pollution of the glass baseplate surface and solid particle, the glass substrate after cleaning is placed in very In 50 DEG C of dry 30min to remove the water of glass baseplate surface in empty drying box.
Prepare aqueous dopamine solution：It is 1 according to trishydroxymethylaminomethane (Tris) and the mass ratio of deionized water:500 Trishydroxymethylaminomethane and deionized water are measured, trishydroxymethylaminomethane dissolving is obtained into trihydroxy methyl in deionized water Aminomethane solution, then watery hydrochloric acid is added dropwise into tris solution and adjusts its pH value and produces Tris to 8.5 and delays Fliud flushing, then by Dopamine hydrochloride according to the mass ratio of Dopamine hydrochloride and Tris buffer solutions be 1:500 ratio is dissolved in hydrochloric acid Aqueous dopamine solution is produced in dopamine.
Under the stirring condition that rotating speed is 450r/min by drying after glass substrate it is water-soluble in the dopamine that temperature is 25 DEG C 12h is soaked in liquid, the glass baseplate surface forms poly-dopamine coating, then by the glass substrate after immersion in ultrasound Under the conditions of with deionized water clean 30s to remove the unstable poly-dopamine nano particle of glass baseplate surface, save it in It is standby in deionized water.
From Fig. 4 a), Fig. 4 b), relative to blank glass substrate, the surface of the glass substrate after the step process The obvious film for occurring being formed by the accumulation of poly-dopamine nano particle, from Fig. 5 a2), the glass after the step process There is the characteristic peak of nitrogen in poly-dopamine in the surface of glass substrate, illustrates that the step has successfully formed on the glass substrate Poly-dopamine coating.
(3) according to AgNO3Mass ratio with deionized water is 1:333 metering AgNO3And deionized water, by AgNO3Addition is gone In ionized water and stir and form AgNO3Solution, step (2) place will be passed through in the case where rotating speed is 300r/min stirring condition The glass substrate of reason is in the AgNO that temperature is 20 DEG C35h is soaked in solution, that is, the fixation of Nano Silver is completed, then by after immersion Glass substrate cleans 30s to remove the unstable Nano Silver of glass baseplate surface under ultrasound condition with deionized water, will clean Glass substrate afterwards, which is placed in vacuum drying chamber, to be removed the water of glass baseplate surfaces in 50 DEG C of dry 30min and obtains surface and fix There is the glass substrate of Nano Silver.
From Fig. 4 c), the glass baseplate surface that the surface that the step obtains is fixed with Nano Silver significantly occurs Even scattered nano particle, as shown in Figure 5, the composition of these nano particles is elemental silver, illustrates that the step utilizes poly-dopamine Nano-Ag particles have successfully been fixed on glass baseplate surface by the reduction characteristic of coating.
Fig. 6 and Fig. 7 is the low power and high power scanning electricity at the microchannel for the glass substrate that Nano Silver is fixed with the step Mirror figure, from Fig. 6 and Fig. 7, the fixation of Nano Silver is not influenceed on the macro morphology of microchannel, and Nano Silver is equably fixed On glass substrate, Fig. 8 is the x-ray photoelectron spectrum curve for the glass baseplate surface that Nano Silver is fixed with the step, Fig. 8 also demonstrate that Nano Silver has had been fixed in glass baseplate surface.
(4) slide that size is 75mm × 25mm is covered in the glass that surface obtained by step (3) is fixed with Nano Silver On substrate, it is marked with marking pen in glass slide and the microchannel entrance on glass substrate and exit, ultrasound is set The electric current of ripple puncher is 1.2A or so, and regulating frequency knob makes circuit resonance, is punched on the position of mark, and punching is completed Load glass slide successively with deionized water and acetone clean and electricity consumption blowing drying, by the hole in glass slide and the glass Microchannel entrance on glass substrate and exit alignment, glass slide be bonded with the glass substrate edge click and enter it is ultraviolet Photocuring glue is simultaneously being observed under the microscope, with ultraviolet after ultraviolet cured adhesive water is full of bond area under capillary action Light irradiation 120s is solidified, finally in the tapping bonded polyethylene flexible pipe in glass panel with holes slide.Fig. 6 is the present embodiment Middle channel wall is fixed with the optical photograph of the microreactor of Nano Silver
By miniflow pump by the reactant p-nitrophenol aqueous solution (0.1mmol/L) and reducing agent sodium borohydride aqueous solution (0.1mol/L) is passed into catalytic micro-reactor manufactured in the present embodiment with 100 μ L/h flow velocity respectively, continuous catalytic reaction 24h investigates the performance of the microreactor.Figure 10 is that the catalysis performance for using the microreactor in the present embodiment is surveyed Test result, from Figure 10 a), after continuous catalysis 24h, the microreactor still has good catalytic performance, reactant Conversion ratio illustrates there is good catalytic activity and nanometer Ag by the nanometer Ag that the method for the invention is fixed more than 90% Fix sufficiently stable in microreactor channel wall；From Figure 10 b) and Figure 10 c), after continuous catalysis 24h, Nano Silver is still So microreactor channel wall is fixed on very well.
Embodiment 2
In the present embodiment, in the present embodiment, the process signal of metal nano catalyst is fixed in microreactor channel wall Figure as shown in Fig. 2 microreactor channel wall fix metal nano catalyst the step of it is as follows：
(1) using the microchannel of AutoCAD Software on Drawing serpentine shape as shown in Figure 3, the width of microchannel is 400 μm, length 810mm, referring next to the method in CN 104190482B embodiments 1 in the blank glass that size is 76mm × 25mm Glass substrate surface produces the microchannel of design shape, obtains to surface and is provided with the glass substrate of microchannel, and the microchannel is set It is equipped with two entrances and one outlet.
(2) successively with ethanol, deionized water enter to be provided with 9 pieces of surfaces the glass substrate of microchannel under ultrasound condition it is each 10min is cleaned, to remove the organic pollution of the glass baseplate surface and solid particle, the glass substrate after cleaning is placed in In 50 DEG C of dry 30min to remove the water of glass baseplate surface in vacuum drying chamber.
Prepare aqueous dopamine solution：It is 1 according to trishydroxymethylaminomethane (Tris) and the mass ratio of deionized water:500 Trishydroxymethylaminomethane and deionized water are measured, trishydroxymethylaminomethane dissolving is obtained into trihydroxy methyl in deionized water Aminomethane solution, then watery hydrochloric acid is added dropwise into tris solution and adjusts its pH value and produces Tris to 8.5 and delays Fliud flushing, then by Dopamine hydrochloride according to the mass ratio of Dopamine hydrochloride and Tris buffer solutions be 1:500 ratio is dissolved in hydrochloric acid Aqueous dopamine solution is produced in dopamine.
By dried 9 pieces of glass substrates in the dopamine that temperature is 25 DEG C under the stirring condition that rotating speed is 500r/min 12h is soaked in the aqueous solution, the glass baseplate surface forms poly-dopamine coating, by the glass substrate after immersion in ultrasound Under the conditions of with deionized water clean 30s to remove the unstable poly-dopamine nano particle of glass baseplate surface, save it in It is standby in deionized water.
(3) according to AgNO3Mass ratio with deionized water is 1:1000、1:333、1:200 measure different quality ratio respectively AgNO3And deionized water, by AgNO3Add in deionized water and stir to form three kinds of different AgNO of concentration3It is molten Liquid, three kinds of AgNO3In solution, AgNO3Concentration be respectively 1mg/mL, 3mg/mL, 5mg/mL.
Take the AgNO that concentration is 1mg/mL3Three parts of solution, step will be passed through in the case where rotating speed is 300r/min stirring condition (2) each one piece of the glass substrate of processing is fully immersed in three parts of AgNO respectively3In solution, respectively using circulator bath, three parts AgNO3The temperature of solution is respectively 5 DEG C, 20 DEG C, 40 DEG C, and immersion 5h is the fixation for completing Nano Silver, by the glass base after immersion Plate cleans 30s to remove the unstable Nano Silver of glass baseplate surface under ultrasound condition with deionized water, by the glass after cleaning Glass substrate, which is placed in vacuum drying chamber, to be obtained three pieces of surfaces to remove the water of glass baseplate surface in 50 DEG C of dry 30min and fixes There is the glass substrate of Nano Silver.
Take the AgNO that concentration is 3mg/mL3Three parts of solution, step will be passed through in the case where rotating speed is 300r/min stirring condition (2) each one piece of the glass substrate of processing is fully immersed in three parts of AgNO respectively3In solution, respectively using circulator bath, three parts AgNO3The temperature of solution is respectively 5 DEG C, 20 DEG C, 40 DEG C, and immersion 5h is the fixation for completing Nano Silver, then by the glass after immersion Glass substrate cleans 30s to remove the unstable Nano Silver of glass baseplate surface, after cleaning under ultrasound condition with deionized water Glass substrate be placed in vacuum drying chamber and obtain three pieces of surfaces in 50 DEG C of dry 30min to remove the water of glass baseplate surface It is fixed with the glass substrate of Nano Silver.
Take the AgNO that concentration is 5mg/mL3Three parts of solution, step will be passed through in the case where rotating speed is 300r/min stirring condition (2) each one piece of the glass substrate of processing is fully immersed in three parts of AgNO respectively3In solution, respectively using three parts of circulator bath, AgNO3The temperature of solution is respectively 5 DEG C, 20 DEG C, 40 DEG C, and immersion 5h is the fixation for completing Nano Silver, then by the glass after immersion Glass substrate cleans 30s to remove the unstable Nano Silver of glass baseplate surface, after cleaning under ultrasound condition with deionized water Glass substrate be placed in vacuum drying chamber and obtain three pieces of surfaces in 50 DEG C of dry 30min to remove the water of glass baseplate surface It is fixed with the glass substrate of Nano Silver.
Figure 11 is that the step is soaked in the silver ionized water solution of different temperatures and concentration to fixing on the glass substrate The influence figure of Nano Silver particle diameter, as shown in Figure 11, when the timing of concentration one of silver ionized water solution, the particle diameter of Nano Silver with silver from The rise of sub- aqueous temperature and increase, when the timing of temperature one of silver ionized water solution, with the increasing of silver ionized water solution concentration Add, significant changes do not occur for the particle diameter of fixed Nano Silver on the glass substrate.The process of actual fixed metal nano catalyst In, can be according to the concentration and reaction temperature of the specifically chosen metal ion solution of requirement of the particle diameter of different metal nano catalyst Degree.
(4) 9 pieces of surfaces that step (3) obtains are fixed with Nano Silver glass substrate carry out respectively it is following operate, i.e., it is complete Into the fixation of microreactor channel wall Nano Silver.
The slide that size is 75mm × 25mm is covered in the glass substrate that surface obtained by step (3) is fixed with Nano Silver On, it is marked with marking pen in glass slide and the microchannel entrance on glass substrate and exit, sets ultrasonic wave to beat The electric current of hole machine is 1.2A or so, and regulating frequency knob makes circuit resonance, is punched on the position of mark, will punch the load of completion Glass slide is cleaned successively with deionized water and acetone and electricity consumption blowing drying, by the hole in glass slide and the glass base Microchannel entrance and exit alignment on plate, are bonded edge with the glass substrate in glass slide and click and enter UV-curing Tensol is simultaneously being observed under the microscope, is shone after ultraviolet cured adhesive water is full of bond area under capillary action with uviol lamp Penetrate 120s to be solidified, finally in the tapping bonded polyethylene flexible pipe in glass panel with holes slide.
Embodiment 3
In the present embodiment, microreactor channel wall fix metal nano catalyst process schematic as shown in Fig. 2 Microreactor channel wall fix metal nano catalyst the step of it is as follows：
(1) using the microchannel of AutoCAD Software on Drawing serpentine shape as shown in Figure 3, the width of microchannel is 400 μm, length 810mm, referring next to the method in CN 104190482B embodiments 1 in the blank glass that size is 76mm × 25mm Glass substrate surface produces the microchannel of design shape, obtains to surface and is provided with the glass substrate of microchannel, and the microchannel is set It is equipped with two entrances and one outlet.
(2) successively with acetone, deionized water enter to be provided with surface the glass substrate of microchannel under ultrasound condition it is each clear 5min is washed, to remove the organic pollution of the glass baseplate surface and solid particle, the glass substrate after cleaning is placed in very In 100 DEG C of dry 15min to remove the water of glass baseplate surface in empty drying box.
Prepare aqueous dopamine solution：It is 1 according to trishydroxymethylaminomethane (Tris) and the mass ratio of deionized water:750 Trishydroxymethylaminomethane and deionized water are measured, trishydroxymethylaminomethane dissolving is obtained into trihydroxy methyl in deionized water Aminomethane solution, then into tris solution be added dropwise watery hydrochloric acid adjust its pH value to 7 produce Tris buffering Liquid, then by Dopamine hydrochloride according to the mass ratio of Dopamine hydrochloride and Tris buffer solutions be 1:It is more that 1000 ratio is dissolved in hydrochloric acid Aqueous dopamine solution is produced in bar amine.
By dried glass substrate in the DOPA aqueous amine that temperature is 20 DEG C under the stirring condition that rotating speed is 500r/min 16h is soaked in solution, the substrate surface forms poly-dopamine coating, by the glass substrate after immersion under ultrasound condition 30s is cleaned with deionized water to remove the unstable poly-dopamine nano particle of glass baseplate surface, saves it in deionization It is standby in water.
(3) according to HAuCl4·4H2O and the mass ratio of deionized water are 1:200 metering HAuCl4·4H2O and deionization Water, by HAuCl4·4H2O is added in deionized water and is stirred to form HAuCl4Solution, in the stirring that rotating speed is 200r/min Under the conditions of by the glass substrate by step (2) processing in temperature be 20 DEG C of HAuCl43h is soaked in solution, that is, completes nanometer The fixation of gold, then cleans 30s to remove glass substrate table under ultrasound condition by the glass substrate after immersion with deionized water The unstable nanogold in face, the glass substrate after cleaning is placed in vacuum drying chamber in 100 DEG C of dry 15min to remove glass The water of substrate surface is to obtain to surface the glass substrate for being fixed with nanogold.
(4) slide that size is 75mm × 25mm is covered in the glass that surface obtained by step (3) is fixed with nanogold On substrate, it is marked with marking pen in glass slide and the microchannel entrance on glass substrate and exit, ultrasound is set The electric current of ripple puncher is 1.2A or so, and regulating frequency knob makes circuit resonance, is punched on the position of mark, and punching is completed Load glass slide successively with deionized water and acetone clean and electricity consumption blowing drying, by the hole in glass slide and the glass Microchannel entrance on glass substrate and exit alignment, glass slide be bonded with the glass substrate edge click and enter it is ultraviolet Photocuring glue is simultaneously being observed under the microscope, with ultraviolet after ultraviolet cured adhesive water is full of bond area under capillary action Light irradiation 120s is solidified, finally in the tapping bonded polyethylene flexible pipe in glass panel with holes slide.
Embodiment 4
In the present embodiment, microreactor channel wall fix metal nano catalyst process schematic as shown in Fig. 2 Microreactor channel wall fix metal nano catalyst the step of it is as follows：
(1) using the microchannel of AutoCAD Software on Drawing serpentine shape as shown in Figure 3, the width of microchannel is 400 μm, length 810mm, referring next to the method in CN 104190482B embodiments 1 in the blank glass that size is 76mm × 25mm Glass substrate surface produces the microchannel of design shape, obtains to surface and is provided with the glass substrate of microchannel, and the microchannel is set It is equipped with two entrances and one outlet.
(2) successively with ethanol, deionized water enter to be provided with surface the glass substrate of microchannel under ultrasound condition it is each clear 5min is washed, to remove the organic pollution of the glass baseplate surface and solid particle, the glass substrate after cleaning is placed in very In 100 DEG C of dry 15min to remove the water of glass baseplate surface in empty drying box.
Prepare aqueous dopamine solution：It is 1 according to trishydroxymethylaminomethane (Tris) and the mass ratio of deionized water:500 Trishydroxymethylaminomethane and deionized water are measured, trishydroxymethylaminomethane dissolving is obtained into trihydroxy methyl in deionized water Aminomethane solution, then into tris solution be added dropwise watery hydrochloric acid adjust its pH value to 10 produce Tris buffering Liquid, then by Dopamine hydrochloride according to the mass ratio of Dopamine hydrochloride and Tris buffer solutions be 1:It is more that 500 ratio is dissolved in hydrochloric acid Aqueous dopamine solution is produced in bar amine.
By dried glass substrate in the DOPA aqueous amine that temperature is 20 DEG C under the stirring condition that rotating speed is 500r/min 12h is soaked in solution, the substrate surface forms poly-dopamine coating, by the glass substrate after immersion under ultrasound condition 30s is cleaned with deionized water to remove the unstable poly-dopamine nano particle of glass baseplate surface, saves it in deionization It is standby in water.
(3) according to PdCl2Mass ratio with deionized water is 1:1000 metering PdCl2And deionized water, by PdCl2Add In deionized water and stir to form PdCl2Solution, step (1) place will be passed through in the case where rotating speed is 800r/min stirring condition The glass substrate of reason is in the PdCl that temperature is 20 DEG C25h is soaked in solution, that is, the fixation of nanometer lead is completed, then by after immersion Glass substrate cleans 30s to remove the unstable nanometer lead of glass baseplate surface under ultrasound condition with deionized water, will clean Glass substrate afterwards is placed in vacuum drying chamber obtains surface in 100 DEG C of dry 15min to remove the water of glass baseplate surface It is fixed with the glass substrate of nanometer lead.
(4) slide that size is 75mm × 25mm is covered in the glass that surface obtained by step (3) is fixed with nanometer lead On substrate, it is marked with marking pen in glass slide and the microchannel entrance on glass substrate and exit, ultrasound is set The electric current of ripple puncher is 1.2A or so, and regulating frequency knob makes circuit resonance, is punched on the position of mark, and punching is completed Load glass slide successively with deionized water and acetone clean and electricity consumption blowing drying, by the hole in glass slide and the glass Microchannel entrance on glass substrate and exit alignment, glass slide be bonded with the glass substrate edge click and enter it is ultraviolet Photocuring glue is simultaneously being observed under the microscope, with ultraviolet after ultraviolet cured adhesive water is full of bond area under capillary action Light irradiation 120s is solidified, finally in the tapping bonded polyethylene flexible pipe in glass panel with holes slide.

Claims (9)

  1. A kind of 1. method for fixing metal nano catalyst in microreactor channel wall, it is characterised in that step is as follows：
    (1) substrate for being provided with microchannel to surface with acetone or alcohol, deionized water successively is cleaned to remove the base The organic pollution and solid particle of plate surface, the water of the substrate surface after removing cleaning is then dried, under agitation will Dried substrate is dipped to substrate surface in aqueous dopamine solution and forms poly-dopamine coating, then by the substrate after immersion Cleaned under ultrasound condition with deionized water to remove the unstable poly-dopamine nano particle of substrate surface；
    The aqueous dopamine solution is formed by Dopamine hydrochloride with pH value for 7~12 buffer, and it is water-soluble to prepare dopamine During liquid, mass ratio 1 of the Dopamine hydrochloride with pH value for 7~12 buffer solution:(500~1000)；The microchannel be provided with into Mouth and outlet；
    (2) substrate by step (1) processing is dipped in the aqueous solution containing metal catalyst ion under agitation Then substrate after immersion is used deionization by few 3h so that metal nano catalyst to be fixed on the substrate under ultrasound condition To remove the unstable metal nano catalyst of substrate surface, the water for drying the substrate surface after removing cleaning obtains for water cleaning Surface is fixed with the substrate of metal nano catalyst；
    (3) sheet glass is covered and be fixed with surface obtained by step (2) on the substrate of metal nano catalyst, solidified using ultraviolet light Sheet glass and substrate are bonded by glue；The sheet glass is provided with through hole with the microchannel entrance on substrate and outlet corresponding section.
  2. 2. the method for fixing metal nano catalyst in microreactor channel wall according to claim 1, it is characterised in that In step (1), soak time of the dried substrate in aqueous dopamine solution is 12~16h.
  3. 3. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist The temperature of aqueous dopamine solution is 20~25 DEG C when immersion is controlled in step (1).
  4. 4. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist In step (1), the buffer solution that the pH value is 7~12 is Tris buffer solutions.
  5. 5. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist In step (2), soak time of the substrate in the aqueous solution containing metal catalyst ion that handles by step (1) for 3~ 5h。
  6. 6. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist The temperature that the aqueous solution containing metal catalyst ion described in during immersion is controlled in step (2) is 5~40 DEG C.
  7. 7. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist The rotating speed of stirring operation is 200~800r/min in step (1) and step (2).
  8. 8. the method according to claim 1 or claim 2 for fixing metal nano catalyst in microreactor channel wall, its feature exist In the aqueous solution containing metal catalyst ion by water soluble silver salt, water-soluble gold salt, water-soluble palladium salt, water-soluble mantoquita or Water-soluble molysite is formulated with deionized water.
  9. 9. the method for fixing metal nano catalyst in microreactor channel wall according to claim 8, it is characterised in that When preparing the aqueous solution containing metal catalyst ion, water soluble silver salt, water-soluble gold salt, water-soluble palladium salt, water-soluble mantoquita or Water-soluble molysite and the mass ratio of deionized water are 1:(200~1000).
CN201610321271.6A 2016-05-16 2016-05-16 A kind of method for fixing metal nano catalyst in microreactor channel wall Active CN105944637B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610321271.6A CN105944637B (en) 2016-05-16 2016-05-16 A kind of method for fixing metal nano catalyst in microreactor channel wall

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610321271.6A CN105944637B (en) 2016-05-16 2016-05-16 A kind of method for fixing metal nano catalyst in microreactor channel wall

Publications (2)

Publication Number Publication Date
CN105944637A CN105944637A (en) 2016-09-21
CN105944637B true CN105944637B (en) 2018-03-02

Family

ID=56911909

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610321271.6A Active CN105944637B (en) 2016-05-16 2016-05-16 A kind of method for fixing metal nano catalyst in microreactor channel wall

Country Status (1)

Country Link
CN (1) CN105944637B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106975426B (en) * 2017-05-02 2019-07-12 重庆大学 High stability Catalytic Layer and preparation method thereof in micro passage reaction
CN112517053A (en) * 2020-12-30 2021-03-19 福州大学 Preparation method of high-performance supported catalytic filler

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6713519B2 (en) * 2001-12-21 2004-03-30 Battelle Memorial Institute Carbon nanotube-containing catalysts, methods of making, and reactions catalyzed over nanotube catalysts
CN103357452B (en) * 2013-06-29 2015-08-12 南昌大学 The preparation method of poly-dopamine/graphene oxide/BSA

Also Published As

Publication number Publication date
CN105944637A (en) 2016-09-21

Similar Documents

Publication Publication Date Title
CN101037185B (en) Method for making nano-groove on quartz glass
CN100583401C (en) Processes for fabricating conductive patterns using nanolithography as a patterning tool
CN106397797B (en) A kind of gold-MOFs- composite membrane of polymer and the preparation method and application thereof
Costantini et al. A Brush‐Gel/Metal‐Nanoparticle Hybrid Film as an Efficient Supported Catalyst in Glass Microreactors
Geissler et al. Microcontact-printing chemical patterns with flat stamps
Moghaddam et al. Highly efficient binding of DNA on the sidewalls and tips of carbon nanotubes using photochemistry
CN105944637B (en) A kind of method for fixing metal nano catalyst in microreactor channel wall
CN105671525B (en) A kind of method and products thereof of the preparation pattern metal film based on poly-dopamine
KR20060084736A (en) Pattern forming method of fine metal thin layer, biomolecular fixing substrate and biochip using the same
US9023458B2 (en) Patterning of ionic polymers
CN1212515C (en) Electrochemical detection-micro fluid control chip,and manufacturing method and regeneratnig method thereof
CN101560061B (en) Method for preparing patterned polymer brush
CN101315330A (en) Production method for surface plasma resonance imaging gold film spot micro-array
KR100953612B1 (en) Substrate for immobilizing physiological material, and a method of preparing the same
CN106914200A (en) A kind of capillary type efficiently carries palladium zirconium-based metallic organic framework film microreactor, dynamic in-situ preparation method and applications
JP2003301059A (en) Method for producing polymer-grafted substrate
CN108212211A (en) A kind of preparation method of the magnetic nano-catalyst of supported nano-gold
CN106890684B (en) Glass base chip and preparation method thereof
CN108579828A (en) A kind of Surface modification of microfluidic chip method that flow velocity is controllable
JP4742327B2 (en) Spatial precision placement technology for materials
JP2007033090A (en) Optical detecting substrate and its manufacturing method
Dabodiya et al. Sequential droplet reactions for surface-bound gold nanocrater array
CN108144559B (en) A kind of catalytic film reactor and preparation method thereof based on nuclear track membrane
Hung et al. Hierarchical Nanoparticle assemblies formed via one-step catalytic stamp pattern transfer
Carvalho et al. Mild Photochemical Biofunctionalization of Glass Microchannels

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant