CN104841345A - Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof - Google Patents

Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof Download PDF

Info

Publication number
CN104841345A
CN104841345A CN201510189334.2A CN201510189334A CN104841345A CN 104841345 A CN104841345 A CN 104841345A CN 201510189334 A CN201510189334 A CN 201510189334A CN 104841345 A CN104841345 A CN 104841345A
Authority
CN
China
Prior art keywords
nano particle
emulsion
tio
solution
reaction system
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.)
Granted
Application number
CN201510189334.2A
Other languages
Chinese (zh)
Other versions
CN104841345B (en
Inventor
孟涛
谢春燕
张青
郭婷
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.)
Southwest Jiaotong University
Original Assignee
Southwest Jiaotong 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 Southwest Jiaotong University filed Critical Southwest Jiaotong University
Priority to CN201510189334.2A priority Critical patent/CN104841345B/en
Publication of CN104841345A publication Critical patent/CN104841345A/en
Application granted granted Critical
Publication of CN104841345B publication Critical patent/CN104841345B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a photomagnetic dual-response Pickering emulsion coalescence reaction system and its application. Firstly, Fe3O4 nano-particles are prepared by a hydrolysis process; secondly, the Fe3O4 nano-particles are used as crystal nucleus to prepare Fe3O4/TiO2 composite nano-particles by a butyl titanate hydrolysis process; thirdly, surface hydrophobic chemical modification is carried out on the Fe3O4/TiO2 composite nano-particles by the use of alkylsilane; and finally, emulsification is carried out to obtain the photomagnetic dual-response Pickering emulsion coalescence reaction system. The above method is simple and has strong operationality. Directional migration of the emulsion and recovery of the nano-particles can be realized through magnetic response (magnetism method). By photoresponse (UV irradiation), the nano-particles adsorbed on the surface of the emulsion are changed from the non-active property to the active property, thus leading to coalescence between adjacent emulsions. By simple non-intrusive methods such as the magnetism method and UV irradiation, etc., the emulsion coalescence reaction system undergoes a chemical reaction at fixed point (reaction site) and at a fixed time (response time). The photomagnetic dual-response Pickering emulsion coalescence reaction system has a good application prospect in the industry field.

Description

The Pickering emulsion coalescence reaction system that a kind of optomagnetic double-bang firecracker is answered and application thereof
Technical field
The present invention relates to field of fine chemical, especially micro-reaction field.
Background technology
Many industrial process, such as medicine synthesis, agricultural chemicals preparation, functional material, food processing, Cosmetic Manufacture etc. all need micro-reaction system.The target that reaction is rapider, operation is simpler, the safer each micro-reaction system often of process is pursued.The micro-reaction system of emulsion greatly strengthen two alternate mass transfer reaction speed with its great specific area, and in parcel, the foreign minister of phase has intercepted the volatilization of poisonous and harmful substances in interior phase reaction thing and caused the injury to human body.The main abutment surface activating agent of traditional emulsion system carrys out stable emulsion, and most surfactant is organic compound, there is the excitant to nasal membrane, the sensitization to skin, toxicity, heredity, carcinogenicity and emulsion and preserve the series of problems such as unstable.Pickering emulsion (referring to by the stable class emulsion of the solia particle being adsorbed onto two-phase interface) then solves above-mentioned industrial problem, the nano particle forming Pickering emulsion relies on few, the easy recovery of its amount of particles, human body is poisoned and environmental pollution little, advantages such as stability is high and receiving much concern.
But the high stability of Pickering emulsion and microsize make people be difficult to effectively control its coalescence reactive switches from outside.The micro-reaction system of response type Pickering emulsion then overcomes this limitation, and under the stimulation of outside environmental elements, coalescence emulsion, open chemical reaction, prospects for commercial application widely.Existing Pickering emulsion coalescence Response System comprises shearing force response, ionic strength response, pH response, electric field response etc.
In most of the cases, chemical reaction often needs it to react under a certain moment (regularly), a certain ad-hoc location (fixed point) and specified conditions (non-intervention type).Now, dexterity, simple, clean outside stimulus-" a light-operated+magnetic control " are excited into as first-selection.The Pickering emulsion coalescence reaction system that optomagnetic double-bang firecracker is answered possesses the born advantage such as non-intervention type and right place regulation and control; Without the need to changing system ambient parameter, simple operation, and be applicable to Long-distance Control or toxic occasion; Be particularly useful for the micro-fluidic microreactor etc. of the transparent Cosmetic Manufacture of reactant liquor, transparent channel.Photoresponse is mainly used in the response time controlling coalescence reactive switches, magnetic response is mainly used in the displacement of emulsion and the recycling of nano particle, will be used widely by means of its inherent environmental friendliness, high security and high recuperability in cosmetics, coating, food and field of biological pharmacy.
Summary of the invention
In view of the above deficiency of prior art, the present invention aims to provide the Pickering emulsion coalescence reaction system that a kind of optomagnetic double-bang firecracker is answered, and makes it the above shortcoming overcoming prior art.
Object of the present invention is realized by following means.
The Pickering emulsion coalescence reaction system that optomagnetic double-bang firecracker is answered, in micro-reaction system emulsion-mass, adds and uses TiO 2coated magnetic Fe 3o 4nano particle carry out stable emulsion and played the effect of emulsion coalescence reactive switches by photoresponse, realize emulsion displacement by magnetic response and realize the recycling of nano particle; The Pickering emulsion coalescence reaction system that optomagnetic double-bang firecracker is answered obtains according to following step:
(a) Fe 3o 4the preparation of nano particle: by FeCl 36H 2o crystal joins in a certain amount of deionized water, is stirred to dissolve completely to obtain FeCl 3solution, wherein FeCl 36H 2o: deionized water=27:100 (mass percent); By FeCl 24H 2o crystal joins in a certain amount of deionized water, is stirred to and is uniformly dispersed, and add a certain amount of commercial available quality percentage is the concentrated hydrochloric acid of 36% simultaneously, is stirred to crystal and dissolves obtain FeCl completely 2solution, wherein FeCl 24H 2o: deionized water: hydrochloric acid=9:25:5 mass percent; By above-mentioned FeCl 3solution is added to FeCl 2in solution, supplement a certain amount of deionized water, be stirred to and be uniformly dispersed; In mixed liquor, add a certain amount of commercial available quality percentage is the ammoniacal liquor of 25%, and vigorous stirring, to being uniformly dispersed, namely generates containing Fe 3o 4the black suspension of particle; Each component proportion FeCl 3solution: FeCl 2solution: hydrochloric acid: deionized water: ammoniacal liquor=10:7:1:12:10 mass percent; Fe in solution will be generated 3o 4nano particle washes 3 ~ 5 times until supernatant is transparent after being separated with magnet; Add the aqueous solution of 1mol/L TMAH, until flood Fe completely 3o 4nano particle, stirring is spent the night, and vacuum drying is dried, for subsequent use;
(b) Fe 3o 4/ TiO 2prepared by nano particle: 1) in reactant liquor, each volume components ratio is butyl titanate: absolute ethyl alcohol=5:35, operates: be added drop-wise to by butyl titanate in absolute ethyl alcohol, 500rpm electric stirring is to solution clear according to the following steps; By Fe prepared in (a) 3o 4nano particle is added in the butyl titanate ethanolic solution of clear, ultrasonic disperse 5 minutes, 1000rpm electric stirring 15 minutes, obtains containing Fe 3o 4the butyl titanate mixed liquor of nano particle; 2) measuring deionized water joins in glacial acetic acid, and be made into 7:2 volume ratio glacial acetic acid aqueous solution, magnetic agitation is to solution bubble-free; With glue head dropper by glacial acetic acid aqueous solution 15 seconds/drip drip speed be dropwise added drop-wise under 760rpm electric stirring state containing Fe 3o 4in the butyl titanate mixed liquor of nano particle, until stop when solution colour is become canescence from grey black and no longer changed dripping, period mechanical agitator Keep agitation under 760rpm, about 1 hour time, obtain containing Fe 3o 4/ TiO 2the mixed liquor of nano particle; 3) attract the Fe generated in solution at beaker sidewall with magnet 3o 4/ TiO 2nano particle, abandoning supernatant and precipitation, use absolute ethanol washing sidewall, and ultrasonic disperse is even, repeats aforesaid operations 5 times, obtains the Fe containing purifying 3o 4/ TiO 2nano particle ethanolic solution; 4) Fe will be contained above 3o 4/ TiO 2nano particle ethanolic solution is placed in the oven dry of 60 DEG C, baking oven, obtains purer Fe 3o 4/ TiO 2crystal; 5) Fe of will dry 3o 4/ TiO 2crystal is crushed to powder, is placed in 500 DEG C of Muffle furnace calcinings 30 minutes, obtained Fe 3o 4/ TiO 2nano particle;
(c) Fe 3o 4/ TiO 2the hydrophobic modification of nano particle: 1) get the Fe with photoelectric activity that (a) step obtains 3o 4/ TiO 2nano particle, is poured into appropriate H 2o 2in, guarantee H 2o 2the complete submergence Fe of solution 3o 4/ TiO 2nano particle, ultrasonic disperse 5 minutes; 2) dispersion liquid is sealed, be placed in dark place magnetic agitation after 4 hours, remove and seal and be placed in the oven dry of 45 DEG C, baking oven; 3) be that the trim,ethylchlorosilane of 1 ~ 5% or the mixed liquor of dodecyltrichlorosilane or silicon fluoride and n-hexane join in the powder after oven dry by the volume ratio prepared, ultrasonic disperse is after 5 minutes, and magnetic agitation, after 12 hours, obtains the Fe of modification 3o 4/ TiO 2dispersion liquid; 4) modified Fe will be left standstill 3o 4/ TiO 2dispersion liquid, removing supernatant liquor, lower sediment is placed in the oven dry of 50 DEG C, baking oven; 5) oven dry powder is dispersed in n-hexane, penetrates lower magnetic force in UV illumination and stir 24 hours, uviol lamp wavelength 254nm, power 12W used, solution distance uviol lamp 10 ~ 15cm; Constantly supplement n-hexane therebetween to maintain initial soln liquid level; 6) leave standstill suspension, removing upper strata n-hexane, lower sediment is dried, fully after grinding, and obtained Fe 3o 4/ TiO 2nano particle, is the hydrophobic Fe for the preparation of emulsion coalescence reaction system 3o 4/ TiO 2nano particle.
The preparation of (d) Pickering emulsion coalescence reaction system: 1) get a certain amount of hydrophobic Fe 3o 4/ TiO 2nano particle, joins in the oil phase be made up of n-hexane or kerosene, ultrasonic disperse 5 minutes, and the mass percent being mixed with nano particle/oil phase is 1% ~ 3% suspension; 2) in the suspension after ultrasonic disperse, isopyknic aqueous solution containing reactant A is added.3) Portable high speed refiner at 15000rpm rotating speed emulsified 1 minute, namely obtains A emulsion.4) same method obtains B emulsion; 5) taking-up A emulsion and B emulsion put into a certain amount of oil phase be made up of n-hexane or kerosene, by magnet displacement two emulsion, make A and B emulsion close to each other, namely prepare the Pickering emulsion coalescence reaction system that the optomagnetic double-bang firecracker of object is answered.
Another object of the present invention is to provide a kind of chemical reaction purposes of non-intervention type, that is:
The purposes of the Pickering emulsion coalescence reaction system that optomagnetic double-bang firecracker is answered, the Pickering emulsion coalescence reaction system adopting above-mentioned optomagnetic double-bang firecracker to answer generates the course of reaction of target product C for reactant A and reactant B, by magnetic response---attraction realizes the displacement of emulsion and the recovery of nano particle, passing through photoresponse---UV irradiates the nano particle character making to be adsorbed on emulsion surface to be changed to activity by nonactive, and then cause between adjacent emulsion coalescence occurs, regularly---the response time, fixed point---response location, carries out chemical reaction.
Adopt the Pickering emulsion coalescence reaction system that the optomagnetic double-bang firecracker of the present invention is answered, under magnetic fields, there is excellent Pickering emulsion magnetic response and drive effect; Under UV illumination condition, there is good photoresponse and cause emulsion coalescence, open chemical reaction effect.Stable Pickering emulsion reaction system to irradiate after about 2 hours coalescence gradually at UV, initiating chamical reaction.This kind of Pickering emulsion coalescence reaction system possesses the Fe that optomagnetic double responsiveness mainly relies on Pickering emulsion adsorption 3o 4/ TiO 2nano particle realizes.Fe 3o 4/ TiO 2nano particle is with Fe 3o 4for core, be wrapped in the TiO of one deck densification around 2layer.Due to Fe 3o 4/ TiO 2fe in nano particle 3o 4existence, and Fe 3o 4possess again stronger paramagnetism, cause Fe 3o 4/ TiO 2the Pickering emulsion of nanoparticles stable has magnetic responsiveness.Fe 3o 4/ TiO 2nano particle short carbon chain in modified grafting, the profit wellability that this group is suitable, can form stable W/O emulsion.After W/O emulsion a period of time is penetrated in UV illumination, Fe 3o 4/ TiO 2the outer field TiO of composite nanometer particle 2surface produces great amount of hydroxy group, and hydroxyl has stronger hydrophily, causes Fe 3o 4/ TiO 2the wellability change that composite nanometer particle had originally, the W/O stability of emulsion of formation is affected, and causes W/O emulsion generation coalescence gradually, final initiating chamical reaction.That make Pickering emulsion coalescence reaction system possess photoresponse effect is Fe 3o 4/ TiO 2tiO in composite nanometer particle 2nano-particle layer, UV illumination is penetrated and is made it produce both hole and electron, brings out TiO 2surface produces hydroxyl, impels composite nanometer particle wellability to change, emulsion generation coalescence.
Accompanying drawing illustrates:
Accompanying drawing 1 is the Pickering emulsion coalescence reaction system fundamental diagram that optomagnetic double-bang firecracker of the present invention is answered.
Detailed description of the invention
Below in conjunction with accompanying drawing, enforcement of the present invention is further described.But it is emphasized that embodiment is below exemplary, instead of in order to limit the scope of the invention and apply.In processing step, involved chemical raw material and reagent are conventional commercial technical pure.
Embodiment one
By the FeCl of 8.1g 36H 2o joins in 30mL deionized water, and 500rpm magnetic agitation obtains FeCl to dissolving completely 3solution; By the FeCl of 7.2g 24H 2o is added in 20mL deionized water, 500rpm electric stirring, adds 4mL concentrated hydrochloric acid (36% ~ 38%) simultaneously, is stirred to dissolve completely to obtain FeCl 2solution; By the FeCl of 29mL 3solution is added to FeCl 2in solution, supplement 47mL deionized water, 500rpm electric stirring is even, and in mixed liquor, add 40mL ammoniacal liquor, namely the violent electric stirring of 1000rpm obtained nanometer Fe after 30 minutes 3o 4particle; Beaker bottom is placed on by the nanometer Fe in solution with magnet 3o 4particle precipitates, and then abandons supernatant, spends deionized water, ultrasonic dispersed, the violent electric stirring of 1000rpm, then is placed on beaker bottom with magnet, by the nanometer Fe in solution 3o 4particles settling gets off, and repeats aforesaid operations 3 ~ 5 times until supernatant is transparent; Add TMAH (TMAH) aqueous solution of 1mol/L, until flood nanometer Fe completely 3o 4particle, 500rpm electric stirring spends the night, and vacuum drying is dried, and obtains the nanometer Fe of favorable dispersibility 3o 4particle.
Be added to by 14mL glacial acetic acid in 4mL deionized water, 500rpm magnetic agitation is to solution bubble-free; Be added in 12mL absolute ethyl alcohol by 3mL butyl titanate (TBOT), 500rpm electric stirring is to solution clear; Be the Fe of 1.25mg/mL by the concentration of 8mL 3o 4pour in butyl titanate/ethanol solution with the mixed solution of ethanol, ultrasonic disperse 20 minutes; Scattered is contained butyl titanate, Fe 3o 4, ethanol mixed solution be again placed in 500rpm electric stirring environment, after solution stirs, glacial acetic acid aqueous solution is dropwise dripped (about 15 seconds/drip drip speed) to containing butyl titanate, Fe 3o 4, ethanol mixed solution in, and along with 760rpm electric stirring 120 minutes; Magnet is placed on beaker sidewall after being changed completely to milky by grey black by solution colour to be mixed, attracts the Fe generated in mixed liquor 3o 4/ TiO 2nano particle, removes supernatant liquor and bottom sediment, with absolute ethyl alcohol by the linen Fe of magnetic absorption on sidewall 3o 4/ TiO 2nano particle elutes, and ultrasonic disperse makes Fe in 5 minutes 3o 4/ TiO 2nano particle is uniformly dispersed again.Repeat aforesaid operations 5 times, obtain pure Fe 3o 4/ TiO 2nano particle, will contain pure Fe 3o 4/ TiO 2the absolute ethyl alcohol of nano particle is dried in 60 DEG C of drying boxes, finally obtains Fe 3o 4/ TiO 2nano particle.
By the Fe obtained 3o 4/ TiO 2particle fully grinds to form homogeneous fine powder in mortar, is transferred to by fine powder in a culture dish, calcines in Muffle furnace under 500 DEG C of conditions; Powder mull after calcining is become fine powder, and be transferred in beaker, the mass percent adding 3 times of volumes is the H of 30% 2o 2solution, ultrasonic disperse 5 minutes, 500rpm electric stirring 4 hours under dark condition, dries at 45 DEG C; Measure 0.3mL dodecyltrichlorosilane with syringe, be added to the dodecyltrichlorosilane weak solution being made into mass percent 5% in 5.7mL n-hexane, ultrasonic disperse is even; By the H of drying 2o 2modified Fe 3o 4/ TiO 2powder is added in the dodecyltrichlorosilane weak solution of mass percent 5%, ultrasonic disperse 5 minutes, 500rpm electric stirring 12 hours, and period supplements n-hexane, avoids n-hexane to volatilize; By centrifugal 10 minutes of above-mentioned stirring liquid normal temperature under 15000rpm, abandon supernatant, dry at being deposited in 45 DEG C; More than dry powder medication spoon pressure thin, fine powder is dispersed in n-hexane, penetrates lower magnetic force in UV illumination and stir 24 hours (uviol lamp wavelength 254nm, power 12W, solution distance uviol lamp 10 ~ 15cm), period constantly supplements n-hexane to maintain initial soln liquid level; Dry at stirring the solution 45 DEG C after 24 hours, grinding, obtains the Fe of modification 3o 4/ TiO 2composite particles.
By the Fe of 0.1g 3o 4/ TiO 2composite particles is dissolved in 10mL n-hexane, ultrasonic disperse 5 minutes, adds the NaOH alkaline solution (drip and have 2 ~ 3 methyl orange indicators) that 10mL concentration is 0.01mol/L in the solution after ultrasonic disperse; Portable high speed refiner emulsified 1 minute at 15000rpm rotating speed, namely obtains yellow Pickering latex A.By the Fe of 0.1g 3o 4/ TiO 2composite particles is dissolved in 10mL n-hexane, ultrasonic disperse 5 minutes, adds the 0.01mol/L aqueous hydrochloric acid solution of 10mL in the solution after ultrasonic disperse; Portable high speed refiner emulsified 1 minute at 15000rpm rotating speed, namely obtains colourless Pickering emulsion B.Latex A and emulsion B are taken out respectively, puts into oil phase solvent (n-hexane), by magnet displacement, make it close to each other, after ultra violet lamp a period of time, A emulsion and B emulsion coalescence are an emulsion, the inner acid-base neutralization that occurs reacts, and because of excessive acid, emulsion is aobvious red.
Embodiment two
Make Fe 3o 4/ TiO 2the process of particle is with embodiment one.
By the Fe obtained 3o 4/ TiO 2particle fully grinds to form homogeneous fine powder in mortar, is transferred to by fine powder in a culture dish, calcines in Muffle furnace under 500 DEG C of conditions; Powder mull after calcining is become fine powder, and be transferred in beaker, the mass percent adding 3 times of volumes is the H of 30% 2o 2solution, ultrasonic disperse 5 minutes, 500rpm electric stirring 4 hours under dark condition, dries at 45 DEG C; Measure 0.3mL dodecyltrichlorosilane with syringe, be added to the dodecyltrichlorosilane weak solution being made into mass percent 5% in 5.7mL n-hexane, ultrasonic disperse is even; By dry after through H 2o 2the Fe of modification 3o 4/ TiO 2powder is added in the dodecyltrichlorosilane weak solution of mass percent 5%, and ultrasonic disperse is even, 500rpm electric stirring 12 hours, and period supplements n-hexane, avoids n-hexane to volatilize; By centrifugal 10 minutes of above-mentioned stirring liquid normal temperature under 15000rpm, abandoning supernatant, dry at being deposited in 45 DEG C; Above ovendry power grinds to form fine powder, fine powder is dispersed in kerosene, penetrates lower magnetic force in UV illumination and stir 24 hours (uviol lamp wavelength 254nm, power 12W, solution distance uviol lamp 10 ~ 15cm), period constantly supplements kerosene to maintain initial soln liquid level; Stir the solution after 24 hours, dry at 45 DEG C, dry powder is ground to form fine powder, obtains the Fe of modification 3o 4/ TiO 2composite particles.
By the Fe of 0.1g 3o 4/ TiO 2composite particles is dissolved in 10mL kerosene, ultrasonic disperse 5 minutes, in the solution after ultrasonic disperse, add the sodium alginate aqueous solution that 10mL mass percent is 0.5%; Portable high speed refiner emulsified 1 minute at 15000rpm rotating speed, namely obtains Pickering latex A.By the Fe of 0.1g 3o 4/ TiO 2composite particles is dissolved in 10mL kerosene, and ultrasonic disperse 5 minutes, makes Fe 3o 4/ TiO 2nano particle fully disperses; The calcium chloride water that 10mL mass percent is 1% is added in the beaker after ultrasonic disperse; Portable high speed refiner emulsified 1 minute at 15000rpm rotating speed, namely obtains Pickering emulsion B.Latex A and emulsion B are taken out respectively, put into oil phase solvent (kerosene), by magnet displacement, make it close to each other, after ultra violet lamp a period of time, A emulsion and B emulsion coalescence are an emulsion, and inner emulsion generates calcium alginate gel.
The Pickering emulsion coalescence reaction system that the optomagnetic double-bang firecracker that the present invention obtains is answered is significant in industrial production.This achievement in research has very wide application prospect in fields such as medicine synthesis, agricultural chemicals preparation, functional material, food processing, Cosmetic Manufacture.

Claims (2)

1. an optomagnetic double-bang firecracker Pickering emulsion coalescence reaction system of answering, is characterized in that, in micro-reaction system emulsion-mass, add and use TiO 2coated magnetic Fe 3o 4nano particle carry out stable emulsion and played the effect of emulsion coalescence reactive switches by photoresponse, realize emulsion displacement by magnetic response and realize the recycling of nano particle; The Pickering emulsion coalescence reaction system that optomagnetic double-bang firecracker is answered obtains according to following step:
(a) Fe 3o 4the preparation of nano particle: by FeCl 36H 2o crystal joins in a certain amount of deionized water, is stirred to dissolve completely to obtain FeCl 3solution, wherein FeCl 36H 2o: deionized water=27:100 mass percent; By FeCl 24H 2o crystal joins in a certain amount of deionized water, is stirred to and is uniformly dispersed, and adds the concentrated hydrochloric acid that a certain amount of mass percent is 36% simultaneously, is stirred to crystal and dissolves obtain FeCl completely 2solution, wherein FeCl 24H 2o: deionized water: hydrochloric acid=9:25:5 mass percent; By above-mentioned FeCl 3solution is added to FeCl 2in solution, supplement a certain amount of deionized water, be stirred to and be uniformly dispersed; In mixed liquor, add a certain amount of commercial available quality percentage is the ammoniacal liquor of 25%, and vigorous stirring, to being uniformly dispersed, namely generates containing Fe 3o 4the black suspension of particle; Each component proportion FeCl 3solution: FeCl 2solution: hydrochloric acid: deionized water: ammoniacal liquor=10:7:1:12:10 mass percent; Fe in solution will be generated 3o 4nano particle washes 3 ~ 5 times until supernatant is transparent after being separated with magnet; Add the aqueous solution of 1mol/L TMAH, until flood Fe completely 3o 4nano particle, stirring is spent the night, and vacuum drying is dried, for subsequent use;
(b) Fe 3o 4/ TiO 2prepared by nano particle: 1) in reactant liquor, each volume components ratio is butyl titanate: absolute ethyl alcohol=5:35, operates: be added drop-wise to by butyl titanate in absolute ethyl alcohol, 500rpm electric stirring is to solution clear according to the following steps; By Fe prepared in (a) 3o 4nano particle is added in the butyl titanate ethanolic solution of clear, ultrasonic disperse 5 minutes, 1000rpm electric stirring 15 minutes, obtains containing Fe 3o 4the butyl titanate mixed liquor of nano particle; 2) measuring deionized water joins in glacial acetic acid, and be made into 7:2 volume ratio glacial acetic acid aqueous solution, magnetic agitation is to solution bubble-free; With glue head dropper by glacial acetic acid aqueous solution 15 seconds/drip drip speed be dropwise added drop-wise under 760rpm electric stirring state containing Fe 3o 4in the butyl titanate mixed liquor of nano particle, until stop when solution colour is become canescence from grey black and no longer changed dripping, period mechanical agitator Keep agitation under 760rpm, about 1 hour time, obtain containing Fe 3o 4/ TiO 2the mixed liquor of nano particle; 3) attract the Fe generated in solution at beaker sidewall with magnet 3o 4/ TiO 2nano particle, abandoning supernatant and precipitation, use absolute ethanol washing sidewall, and ultrasonic disperse is even, repeats aforesaid operations 5 times, obtains the Fe containing purifying 3o 4/ TiO 2nano particle ethanolic solution; 4) Fe will be contained above 3o 4/ TiO 2nano particle ethanolic solution is placed in the oven dry of 60 DEG C, baking oven, obtains purer Fe 3o 4/ TiO 2crystal; 5) Fe of will dry 3o 4/ TiO 2crystal is crushed to powder, is placed in 500 DEG C of Muffle furnace calcinings 30 minutes, obtained Fe 3o 4/ TiO 2nano particle;
(c) Fe 3o 4/ TiO 2the hydrophobic modification of nano particle: 1) get the Fe with photoelectric activity that (a) step obtains 3o 4/ TiO 2nano particle, is poured into appropriate H 2o 2in, guarantee H 2o 2the complete submergence Fe of solution 3o 4/ TiO 2nano particle, ultrasonic disperse 5 minutes; 2) dispersion liquid is sealed, be placed in dark place magnetic agitation after 4 hours, remove and seal and be placed in the oven dry of 45 DEG C, baking oven; 3) be that the trim,ethylchlorosilane of 1 ~ 5% or the mixed liquor of dodecyltrichlorosilane or silicon fluoride and n-hexane join in the powder after oven dry by the volume ratio prepared, ultrasonic disperse is after 5 minutes, and magnetic agitation, after 12 hours, obtains the Fe of modification 3o 4/ TiO 2dispersion liquid; 4) modified Fe will be left standstill 3o 4/ TiO 2dispersion liquid, removing supernatant liquor, lower sediment is placed in the oven dry of 50 DEG C, baking oven; 5) oven dry powder is dispersed in n-hexane, penetrates lower magnetic force in UV illumination and stir 24 hours, uviol lamp wavelength 254nm, power 12W used, solution distance uviol lamp 10 ~ 15cm; Constantly supplement n-hexane therebetween to maintain initial soln liquid level; 6) leave standstill suspension, removing upper strata n-hexane, lower sediment is dried, fully after grinding, and obtained Fe 3o 4/ TiO 2nano particle, is the hydrophobic Fe for the preparation of emulsion coalescence reaction system 3o 4/ TiO 2nano particle.
The preparation of (d) Pickering emulsion coalescence reaction system: 1) get a certain amount of hydrophobic Fe 3o 4/ TiO 2nano particle, joins in the oil phase be made up of n-hexane or kerosene, ultrasonic disperse 5 minutes, and the mass percent being mixed with nano particle/oil phase is 1% ~ 3% suspension; 2) in the suspension after ultrasonic disperse, isopyknic aqueous solution containing reactant A is added.3) Portable high speed refiner at 15000rpm rotating speed emulsified 1 minute, namely obtains A emulsion.4) same method obtains B emulsion; 5) taking-up A emulsion and B emulsion put into a certain amount of oil phase be made up of n-hexane or kerosene, by magnet displacement two emulsion, make A and B emulsion close to each other, namely prepare the Pickering emulsion coalescence reaction system that the optomagnetic double-bang firecracker of object is answered.
2. the optomagnetic double-bang firecracker purposes of Pickering emulsion coalescence reaction system of answering, it is characterized in that, the Pickering emulsion coalescence reaction system adopting the optomagnetic double-bang firecracker described in claim 1 to answer generates the course of reaction of target product C for reactant A and reactant B, by magnetic response---attraction realizes the displacement of emulsion and the recovery of nano particle, passing through photoresponse---UV irradiates the nano particle character making to be adsorbed on emulsion surface to be changed to activity by nonactive, and then cause between adjacent emulsion coalescence occurs, regularly---the response time, fixed point---response location, carry out chemical reaction.
CN201510189334.2A 2015-04-21 2015-04-21 Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof Active CN104841345B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510189334.2A CN104841345B (en) 2015-04-21 2015-04-21 Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510189334.2A CN104841345B (en) 2015-04-21 2015-04-21 Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof

Publications (2)

Publication Number Publication Date
CN104841345A true CN104841345A (en) 2015-08-19
CN104841345B CN104841345B (en) 2017-05-17

Family

ID=53841558

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510189334.2A Active CN104841345B (en) 2015-04-21 2015-04-21 Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof

Country Status (1)

Country Link
CN (1) CN104841345B (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106117403A (en) * 2016-07-27 2016-11-16 常州大学 A kind of formation Fe2cdO4the method of presoma nanometer polymer particle
CN106311074A (en) * 2016-07-25 2017-01-11 中国石油大学(华东) Defoaming-controllable multiphase foam system and preparation method thereof
CN106674555A (en) * 2016-12-28 2017-05-17 西南交通大学 Calcium alginate composite microsphere for stabilizing water-in-oil Pickering emulsion and preparation method thereof
CN107383536A (en) * 2017-08-05 2017-11-24 福建师范大学 The preparation method and device of a kind of photocatalysis film
CN112301733A (en) * 2020-10-19 2021-02-02 西安工程大学 Preparation method of three-dimensional light-weight structural composite electromagnetic shielding material
CN113201150A (en) * 2021-04-29 2021-08-03 陕西科技大学 Preparation method of photoresponse Pickering emulsion
CN115121007A (en) * 2021-03-24 2022-09-30 南开大学 Dynamic intelligent membrane based on pH-magnetism dual response and used for efficiently and accurately separating complex oil-water system
CN115318335A (en) * 2022-08-22 2022-11-11 中节能工程技术研究院有限公司 Magnetic TiO 2 Preparation method of Pickering photocatalyst

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503554A (en) * 2011-11-02 2012-06-20 西南交通大学 Method for preparing oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on silicon substrate surface
WO2013169395A1 (en) * 2012-05-09 2013-11-14 Sun Chemical Corporation Surface modified pigment particles, method of preparation and application thereof
CN103540926A (en) * 2013-09-24 2014-01-29 西南交通大学 Light control SiO2/TiO2 composite micro-nano structure micro-channel valve and preparation method thereof
CN103881422A (en) * 2014-03-21 2014-06-25 西南交通大学 Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503554A (en) * 2011-11-02 2012-06-20 西南交通大学 Method for preparing oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on silicon substrate surface
WO2013169395A1 (en) * 2012-05-09 2013-11-14 Sun Chemical Corporation Surface modified pigment particles, method of preparation and application thereof
CN103540926A (en) * 2013-09-24 2014-01-29 西南交通大学 Light control SiO2/TiO2 composite micro-nano structure micro-channel valve and preparation method thereof
CN103881422A (en) * 2014-03-21 2014-06-25 西南交通大学 Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311074A (en) * 2016-07-25 2017-01-11 中国石油大学(华东) Defoaming-controllable multiphase foam system and preparation method thereof
CN106311074B (en) * 2016-07-25 2019-02-05 中国石油大学(华东) Defoam controllable type multiphase foam system and preparation method thereof
CN106117403A (en) * 2016-07-27 2016-11-16 常州大学 A kind of formation Fe2cdO4the method of presoma nanometer polymer particle
CN106117403B (en) * 2016-07-27 2018-12-07 常州大学 A kind of formation Fe2CdO4The method of presoma nanometer polymer particle
CN106674555A (en) * 2016-12-28 2017-05-17 西南交通大学 Calcium alginate composite microsphere for stabilizing water-in-oil Pickering emulsion and preparation method thereof
CN107383536A (en) * 2017-08-05 2017-11-24 福建师范大学 The preparation method and device of a kind of photocatalysis film
CN112301733A (en) * 2020-10-19 2021-02-02 西安工程大学 Preparation method of three-dimensional light-weight structural composite electromagnetic shielding material
CN112301733B (en) * 2020-10-19 2022-10-25 西安工程大学 Preparation method of three-dimensional light-weight structural composite electromagnetic shielding material
CN115121007A (en) * 2021-03-24 2022-09-30 南开大学 Dynamic intelligent membrane based on pH-magnetism dual response and used for efficiently and accurately separating complex oil-water system
CN115121007B (en) * 2021-03-24 2024-05-24 南开大学 Dynamic intelligent membrane based on pH-magnetic dual response for separating complex oil-water system
CN113201150A (en) * 2021-04-29 2021-08-03 陕西科技大学 Preparation method of photoresponse Pickering emulsion
CN115318335A (en) * 2022-08-22 2022-11-11 中节能工程技术研究院有限公司 Magnetic TiO 2 Preparation method of Pickering photocatalyst

Also Published As

Publication number Publication date
CN104841345B (en) 2017-05-17

Similar Documents

Publication Publication Date Title
CN104841345A (en) Photomagnetic dual-response Pickering emulsion coalescence reaction system and application thereof
Xie et al. Light and magnetic dual-responsive Pickering emulsion micro-reactors
Al-Buriahi et al. Elimination of rhodamine B from textile wastewater using nanoparticle photocatalysts: A review for sustainable approaches
Hemmati et al. Green fabrication of reduced graphene oxide decorated with Ag nanoparticles (rGO/Ag NPs) nanocomposite: A reusable catalyst for the degradation of environmental pollutants in aqueous medium
Joshi et al. Metal oxide nanoparticles and their nanocomposite-based materials as photocatalysts in the degradation of dyes
Chen et al. Visible light-controlled inversion of Pickering emulsions stabilized by functional silica microspheres
Bethi et al. Investigation of TiO2 photocatalyst performance for decolorization in the presence of hydrodynamic cavitation as hybrid AOP
Rossi et al. Stöber synthesis of monodispersed luminescent silica nanoparticles for bioanalytical assays
CN103599751B (en) The preparation method of thiol-functionalizedmagnetic magnetic silica nano-material
CN103521191B (en) A kind of preparation method of titanium dioxide/chitosan/oxigraphene graphene composite material and application
Dehghani et al. Photocatalytic oxidation of organophosphorus pesticides using zinc oxide
Wang et al. Effect of UV irradiation on the aggregation of TiO2 in an aquatic environment: Influence of humic acid and pH
Keerthana et al. Fabrication of Ce doped TiO2 for efficient organic pollutants removal from wastewater
Wu et al. Intensified photocatalytic degradation of nitrobenzene by Pickering emulsion of ZnO nanoparticles
CN104250350A (en) Method for preparing porous polymer material with through-pore structure
Zhang et al. Designing, characterization, and evaluation of chitosan-zinc selenide nanoparticles for visible-light-induced degradation of tartrazine and sunset yellow dyes
Wang et al. Impact of montmorillonite clay on the homo-and heteroaggregation of titanium dioxide nanoparticles (nTiO2) in synthetic and natural waters
CN106268680A (en) Magnetic Nano microcapsule adsorbent and its preparation method and application
CN103894625A (en) Preparation method for bionic nano-silver
Kumar et al. Green synthesis of iron nanoparticles: Sources and multifarious biotechnological applications
CN103881422B (en) Light-operated switch type TiO2 nano-particles surfactant and preparation method thereof
Araujo et al. Photobiosynthesis of stable and functional silver/silver chloride nanoparticles with hydrolytic activity using hyperthermophilic β-glucosidases with industrial potential
Sun et al. Dual-responsive pickering emulsion stabilized by Fe3O4 nanoparticles hydrophobized in situ with an electrochemical active molecule
Wu et al. Cotransport of nano-hydroxyapatite and different Cd (II) forms influenced by fulvic acid and montmorillonite colloids
Zhang et al. Flexible fabrication of lipophilic-hydrophilic micromotors by off-chip photopolymerization of three-phase immiscible flow induced Janus droplet templates

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant