CN104511263A

CN104511263A - Microsphere with multiple magnetic nano cores@gaps@porous shell structures and preparation method thereof

Info

Publication number: CN104511263A
Application number: CN201310447529.3A
Authority: CN
Inventors: 潘纲; 毕磊
Original assignee: Research Center for Eco Environmental Sciences of CAS
Current assignee: Research Center for Eco Environmental Sciences of CAS
Priority date: 2013-09-27
Filing date: 2013-09-27
Publication date: 2015-04-15
Anticipated expiration: 2033-09-27
Also published as: CN104511263B

Abstract

The invention relates to a microsphere with multiple magnetic nano cores@gaps@porous shell structures and a preparation method thereof. The microsphere structure is characterized in that a porous hollow shell contains a plurality of magnetic nano cores. In the preparation method, iron (III) is taken as the single iron precursor, the spherical cell wall of unicellular algae is taken as the precursor of porous microsphere wall, the substances in the algae cells are used to replace chemical reagents to carry out reactions, and a hydrothermal method with mild conditions is performed to prepare the microsphere with multiple magnetic nano cores@gaps@porous shell structures. The preparation method is simple; a microsphere, which has a complicated structure composed of a porous hollow shell and a plurality of magnetic cores, can be produced without a template; the preparation process is green and environment-friendly; no organic reagent is added, and the obtained microsphere has the advantages of excellent magnet-response performance and large loading space.

Description

A kind of have microballoon of multiple magnetic Nano kernel@spaces@porous shell structure and preparation method thereof

Technical field

The present invention relates to and a kind of there is microballoon of many magnetic Nanos kernel@space@porous shell structure and preparation method thereof.

Background technology

The magnetic microsphere of bell structure or yolk shell structure, due to the magnetic kernel@space@Shell structure of its uniqueness, show excellent magnetic response ability, large inner space for the permeability of loading functional guest species and ball wall and environmental response characteristic, can obtain in fields such as separating substances purification, targeted delivery of drugs, NMR imaging and catalysis and pay close attention to widely and apply.This type of microballoon prepared at present mostly is the inner microballoon containing single magnetic kernel, and many inner cores significantly can improve avtive spot and the contact area of kernel compared with single kernel, thus improve the performance of microballoon, but this type of many magnetic kernels microspheres and complexity thereof, also do not have relevant report at present at present.And the preparation method of existing single magnetic kernel structure microspheres uses numerous organic chemicals such as crosslinking agent, emulsifying agent, stabilizing agent, reductant-oxidant mostly; and preparation process is very loaded down with trivial details time-consuming; the measures such as certain methods also needs high-temperature calcination, inert gas shielding.The use of a large amount of harmful chemical not only runs counter to the basic principle of Green Chemistry, and the preparation method of complexity and harsh preparation condition also limit it and produce on a large scale and application, therefore a kind of environmental protection of necessary exploitation and preparation method simply has microballoon of many magnetic Nanos kernel@space@porous shell structure and preparation method thereof.

Summary of the invention

The object of the invention is to overcome preparation at present and include the use of a large amount of organic reagent in the method for magnetic kernel microballoon and loaded down with trivial details preparation process, one is provided not adopt any organic reagent and template, the glomus cell wall utilizing unicellular alga self to have is as the presoma of porous polymer microsphere wall, and utilize frustule inner material to replace chemical reagent, take ferric iron as Single Iron presoma, adopt the hydro-thermal method of mild condition to prepare and there is the microballoon that hollow porous spherical shell includes multiple magnetic nanoparticle.It is characterized in that, it comprises the steps:

1) by unicellular spherical, and the complete algae alive of cell membrane or algae powder are scattered in the trivalent iron salt aqueous solution, ferric iron is made to be scattered in cell interior, the described ferric iron aqueous solution is ferric chloride hexahydrate, ferric sulfate, ferric nitrate, ferric citrate, the one in ammonium ferric sulfate that can be dissolved in the water, but is not limited to above-mentioned several ferric iron;

2) centrifugal or suction filtration is separated 1) in be loaded with ferric frustule, and substantially to clarify to cleaning solution with deionized water cyclic washing;

3) by 2) in be separated the frustule that obtains and be scattered in concentrated sodium hydroxide or potassium hydroxide aqueous solution, and be placed in autoclave or Pressure vessel, after adding thermal response a period of time under uniform temperature, be cooled to room temperature;

4) by 3) in the centrifugal or isolated by filtration of the solid product that obtains, and substantially to clarify to cleaning solution with deionized water cyclic washing;

5) by 4) in the solid product that obtains be scattered in alkaline aqueous solution, and be placed in autoclave or Pressure vessel, after adding thermal response a period of time under uniform temperature, be cooled to room temperature;

6) Magneto separate 5) middle solid product, and use deionized water cyclic washing, obtain the microballoon with many magnetic Nanos kernel space porous shell structure.

The present invention adopts gentle hydro-thermal method to prepare and includes multiple Fe ₃o ₄the polymer microballoon of nano particle, any organic chemicals is not used in synthesis material, utilize spherical structure and the reproducibility of natural algae, adopt very simple synthetic method, prepare baroque many magnetic kernels monoshell hollow structure microballoon, this method environmental protection, preparation technology is simple, cheap is suitable for large-scale production.

Accompanying drawing explanation

Fig. 1 is a kind of microballoon stereoscan photograph with many magnetic Nanos kernel@space@porous shell structure

Fig. 2 is a kind of microballoon high resolution scanning electromicroscopic photograph with many magnetic Nanos kernel@space@porous shell structure

Fig. 3 is a kind of microballoon transmission electron microscope photo with many magnetic Nanos kernel@space@porous shell structure

Fig. 4 is a kind of microballoon with many magnetic Nanos kernel space porous shell structure Separation of Solid and Liquid fast under extraneous magnetic fields

Fig. 5 is a kind of XRD diffraction pattern with the microballoon of many magnetic Nanos kernel@space@porous shell structure

Detailed description of the invention

Content of the present invention is further described once in conjunction with reference example:

Embodiment 1

Getting 2g iron chloride is dissolved in 100ml deionized water, by 5g chlorella dry powder dispersion in the ferric chloride solution prepared, be positioned over 160rpm in 25 DEG C of thermostat water baths and shake 6h, then by suspension at the centrifugal 10min of 5000rpm, centrifugal 4 times of gained sediment deionized water cyclic washing, again centrifugal sediment is scattered in 80ml containing in 8% sodium hydroxide solution and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 1h under 105 DEG C of conditions, after question response still cools naturally, get suspension centrifugal 8min under 9000rpm condition, and with deionized water cyclic washing and centrifugal sediment 5 times, again sediment is scattered in 80ml deionized water solution, be 9 with 0.5mol/L hydrochloric acid or 0.5mol/L NaOH regulation system pH, and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 6h under 180 DEG C of conditions, after question response still cools naturally, with the separating obtained black product of magnetic separation method, with deionized water cyclic washing products therefrom, namely a kind of microballoon with many magnetic Nanos kernel@space@porous shell structure is obtained.

Embodiment 2

Getting 1g ferric nitrate is dissolved in 100ml deionized water, by 5g chlorella dry powder dispersion in the iron nitrate solution prepared, be positioned over 150rpm in 25 DEG C of thermostat water baths and shake 12h, then by suspension at the centrifugal 10min of 5000rpm, centrifugal 4 times of gained sediment deionized water cyclic washing, again centrifugal sediment is scattered in 80ml containing in 10% potassium hydroxide solution and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 1h under 105 DEG C of conditions, after question response still cools naturally, get suspension centrifugal 8min under 9000rpm condition, and with deionized water cyclic washing and centrifugal sediment 5 times, again sediment is scattered in 80ml deionized water solution, be 9 with 0.5mol/L hydrochloric acid or 0.5mol/L NaOH regulation system pH, and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 4h under 200 DEG C of conditions, after question response still cools naturally, with the separating obtained black product of magnetic separation method, with deionized water cyclic washing products therefrom, namely a kind of microballoon with many magnetic Nanos kernel@space@porous shell structure is obtained.

Embodiment 3

Getting 6g ferric citrate is dissolved in 100ml deionized water, by 5g chlorella dry powder dispersion in the ironic citrate ammonium salt solution prepared, be positioned over 150rpm in 25 DEG C of thermostat water baths and shake 24h, then by suspension at the centrifugal 10min of 5000rpm, centrifugal 4 times of gained sediment deionized water cyclic washing, again centrifugal sediment is scattered in 80ml containing in 10% ammonia spirit and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 2h under 105 DEG C of conditions, after question response still cools naturally, get suspension centrifugal 8min under 9000rpm condition, and with deionized water cyclic washing and centrifugal sediment 5 times, again sediment is scattered in 80ml deionized water solution, be 10 with 0.5mol/L hydrochloric acid or 0.5mol/L NaOH regulation system pH, and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 3h under 220 DEG C of conditions, after question response still cools naturally, with the separating obtained black product of magnetic separation method, with deionized water cyclic washing products therefrom, namely a kind of microballoon with many magnetic Nanos kernel@space@porous shell structure is obtained.

Embodiment 4

Getting 4g ferric sulfate is dissolved in 100ml deionized water, by 5g chlorella dry powder dispersion in the ferrum sulfuricum oxydatum solutum prepared, be positioned over 150rpm in 25 DEG C of thermostat water baths and shake 10h, then by suspension at the centrifugal 10min of 5000rpm, centrifugal 4 times of gained sediment deionized water cyclic washing, again centrifugal sediment is scattered in 80ml containing in 6% sodium hydroxide solution and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 2h under 105 DEG C of conditions, after question response still cools naturally, get suspension centrifugal 8min under 9000rpm condition, and with deionized water cyclic washing and centrifugal sediment 5 times, again sediment is scattered in 80ml deionized water solution, be 10 with 0.5mol/L hydrochloric acid or 0.5mol/L NaOH regulation system pH, and to be placed in volume be that the hydrothermal reaction kettle of 100ml reacts 2h under 240 DEG C of conditions, after question response still cools naturally, with the separating obtained black product of magnetic separation method, with deionized water cyclic washing products therefrom, namely a kind of microballoon with many magnetic Nanos kernel@space@porous shell structure is obtained.

Claims

1. one kind has microballoon of multiple magnetic Nano kernel spaces porous shell structure and preparation method thereof, it is characterized in that described microballoon is containing multiple magnetic Nano kernel in spherical porous hollow shell.Described preparation method is take ferric iron as Single Iron presoma, the glomus cell wall utilizing unicellular alga self to have is as the presoma of porous microsphere wall, and utilize frustule inner material to replace chemical reagent to participate in reaction, adopt the hydro-thermal method of mild condition to prepare the microballoon with multiple magnetic Nano kernel@spaces@porous shell structure, it comprises the steps:

1) frustule is scattered in the trivalent iron salt aqueous solution, makes ferric iron be scattered in cell interior;

2) separating step 1) in be mounted with ferric frustule, wash frustule with water;

3) by step 2) in frustule be scattered in concentrated alkaline solution, be placed in closed container heat treatment certain hour;

4) separating step 3) in solid product, fully wash with water;

5) solid product obtained in step 4) is scattered in alkaline solution, and is placed in closed container hydrothermal treatment consists certain hour;

6) magnetic separation step 5) in the solid product arrived, fully wash with water.

2. one kind has microballoon of multiple magnetic Nano kernel spaces porous shell structure and preparation method thereof, it is characterized in that the described ferric iron aqueous solution is the aqueous solution of the trivalent iron salt that can be dissolved in the water;

3. one kind has microballoon of multiple magnetic Nano kernel spaces porous shell structure and preparation method thereof, it is characterized in that described algae is unicellular spherical, and the complete algae alive of cell membrane or algae powder;

4. one kind has microballoon of multiple magnetic Nano kernel spaces porous shell structure and preparation method thereof, it is characterized in that described strong base solution is the aqueous solution of NaOH or potassium hydroxide;

5. one kind has microballoon of multiple magnetic Nano kernel spaces porous shell structure and preparation method thereof, it is characterized in that described closed container is hydrothermal reaction kettle or Pressure vessel.

6. in claim 1 to 5 arbitrary described method prepare a kind of there is microballoon of multiple magnetic Nano kernel@spaces@porous shell structure and preparation method thereof.