CN102659190B - Method for synthesis of ferroferric oxide nano-crystals having prism structures - Google Patents
Method for synthesis of ferroferric oxide nano-crystals having prism structures Download PDFInfo
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- CN102659190B CN102659190B CN201210112777.8A CN201210112777A CN102659190B CN 102659190 B CN102659190 B CN 102659190B CN 201210112777 A CN201210112777 A CN 201210112777A CN 102659190 B CN102659190 B CN 102659190B
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Abstract
The invention discloses a method for synthesis of ferroferric oxide nano-crystals having prism structures. The method comprises the following steps that 1, anion monomers, a cross-linking agent methylene diacrylamide and an initiator undergo a polymerization reaction to produce polymeric hydrogel; 2, an iron ion solution is prepared; 3, the polymeric hydrogel is immersed in the iron ion solution; 4, an alkali solution is prepared; 5, nitrogen is respectively fed into the mixture obtained by the step 3 and the alkali solution obtained by the step 4; and the polymeric hydrogel treated by the step 3 is immersed in the alkali solution; 6, a pH value of the alkali solution with the polymeric hydrogel is adjusted; and then the alkali solution with the polymeric hydrogel is heated in a water bath and then is maintained at a constant temperature in a nitrogen atmosphere so that ferroferric oxide nano-crystals are synthesized; and 7, the ferroferric oxide nano-crystals are washed and dried to form black powder of the ferroferric oxide nano-crystals having prism structures. The method provided by the invention has the advantages that raw material requirements are simple; any organic reagents are not needed; used equipment is simple; a cost is low; reaction temperatures are low; operation is simple; a yield is high; product reappearance is good; and large-scale industrial production can be realized easily.
Description
Technical field
The invention belongs to a kind of magnetic Nano material technical field, be specifically related to a kind of method of synthetic prism structures ferroferric oxide nano crystal.
Background technology
Z 250 (Fe
3o
4) nano material is because having the advantages such as hypotoxicity, efficient adsorption, strong resistance to acids and bases, and become one of current most widely used magnetic Nano material, be widely used in the fields such as nuclear magnetic resonance, drug targeting, magnetic target thermotherapy, magnetic fluid, biological sample separation, genetically engineered, cell cultures and catalysis.Fe
3o
4magnetic performance (the superparamagnetism of nano material, saturation magnetization and coercive force etc.), (the magnetic hysteresis loss heat production of heat production effect, relaxation loss heat production and specific absorption rate etc.) and the performance such as catalytic performance (catalytic activity and analogue enztme) and biocompatibility and toxicity (apoptosis, oxidative stress and toxicant metabolism etc.) and its pattern, microtexture and size closely related.Therefore, research pattern, microtexture and the controlled synthetic Fe of size
3o
4the method of nano material has scientific meaning widely at basic scientific research and Application Areas.At present, adopted the methods such as chemical precipitation method, template, hydrothermal method, high-temperature decomposition, sol-gel method, polyvalent alcohol method, vapor phase process, sonolysis method, flow injection synthesis method and electrochemical process to synthesize several nanometers to the Fe of the various patterns of hundreds of nanometer
3o
4nano material, comprises spheroid, hollow ball, a shape, ring-type, wire, tubulose, sheet and the nano particle such as flower-shaped, and tetrahedron, octahedron and prism structures (nanoprism) nanocrystal.
In recent years, prism structures Fe is found in research
3o
4electrochemical activity and the catalytic activity of nanocrystal (220) crystal face are higher, and this nano material with specific function will be in biotechnology, and environmental chemistry and medicine and other fields play a significant role.But because the surface of bevelled mirror crystal (220) face can be higher, the synthetic bevelled mirror Fe that exposes (220) crystal face
3o
4nanocrystal is difficult to realize.Three kinds of prism structures Fe that report at present
3o
4the method of nanocrystal all adopts hydrothermal method, and these three kinds of synthetic methods are as follows respectively: (1) is by 5mmol iron trichloride (FeCl
3) be dissolved in 40ml ethylene glycol and form transparent settled solution, then add 50mmol anhydrous methanol sodium (CH
3oNa) and 1ml water, after forming homogeneous solution, ultrasonic dispersing and mixing transfers in teflon-lined stainless steel autoclave 200 ℃ of reactions 10 hours, be cooled to room temperature, with magnet, collect product, water and ethanol ultrasonic cleaning, vacuum-drying under room temperature (Chem.Eur.J.2011,17,620-625); (2) by 1g iron chloride hexahydrate (FeCl
36H
2o) be dissolved in 20ml ethylene glycol and form transparent settled solution, then add 3g sodium acetate (CH
3cOONa) and 10ml 1,3-propylene diamine, after being fully uniformly mixed, transfer in teflon-lined stainless steel autoclave 200 ℃ of reactions 12 hours, be cooled to room temperature, water and ethanol clean black product for several times, then 60 ℃ of dry 6 hours (CrystEngComm, 2010 in vacuum drying oven, 12,2060-2063); (3) by 1mmol ferric acetyl acetonade (Fe (acac)
3) and 5.0ml oleyl amine add in the autoclave that toluene is housed strong stirring to form after red solution, in reactor, 200 ℃ of reactions are 24 hours.Naturally cooling after reaction, adds 20mL dehydrated alcohol precipitated product, after then washing with dehydrated alcohol and normal hexane, be scattered in normal hexane (Chem.Commun., 2010,46,3920-3922).
In aforesaid method, use organic reagent, even the synthetic prism structures Fe of some poisonous reagent
3o
4nanocrystal, is unfavorable for the application in medical field, in addition, because reacting under High Temperature High Pressure, is difficult to extensive synthetic.Up to now, utilize the method for the synthetic prism structures ferroferric oxide nano crystal of polymer-network gel method to have no report.
Summary of the invention
In order to overcome the deficiency of above-mentioned prior art existence, the object of the present invention is to provide a kind of method of synthetic prism structures ferroferric oxide nano crystal, the synthetic prism structures Fe of the method step original position in macromolecule hydrogel network
3o
4nanocrystal, simple to ingredient requirement, do not need to add any organic reagent, pollution-free, thus guaranteed the biocompatibility of system; In addition, required equipment is simple, and cost is low, and temperature of reaction is low, easy and simple to handle, and productive rate is high, and product favorable reproducibility is easy to realize large-scale industrial production.
In order to achieve the above object, the technical solution adopted in the present invention is:
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 0.5-15mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid or ammonium persulphate, by 365nm UV-light cause or the synthesizing cross-linked density of Raolical polymerizable of thermal initiation at the anionic polymer hydrogel of 0.5-15mol%, anionic monomer group comprises sulfonic group, sulfonic group salt, Phenylsulfonic acid base, Phenylsulfonic acid base salt, phosphate, phosphate salt, carboxylic acid group or carboxylic acid group's salt, and anionic monomer is divided into natural and synthetic anionic hydrogel;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 2: 1-4: 1, adding deionized water to be mixed with concentration is 0.2M-0.4M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, iron protochloride FeCl
2, Iron nitrate Fe (NO
3)
2or containing the above-mentioned molysite of crystal water, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3), iron(ic) chloride (FeCl
3), iron nitrate (Fe (NO
3)
3) or containing the above-mentioned molysite of crystal water;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml-3g: 30ml, at room temperature soak 6-24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 0.5mol-1.5mol in beaker, alkali comprises sodium hydroxide, potassium hydroxide or ammoniacal liquor;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 6-18h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present invention is usingd the three-dimensional net structure of macromolecule hydrogel as template, positively charged iron ion enters into the three-dimensional net structure of anionic polymer hydrogel by diffusion, and by electrostatic interaction by electronegative in anionic hydrogel and the stable absorption of group be uniformly distributed in hydrogel network.Then the coprecipitation method by simple gentleness makes iron ion generate size at the prism structures Fe of 100nm～300nm left and right at special macromolecule hydrogel network microenvironment situ
3o
4nanocrystal.The three-dimensional network of macromolecule hydrogel is both as synthetic Fe
3o
4the microreactor of nanocrystal, again as dispersed Fe
3o
4the system of nanocrystal.The adjustable prism structures Fe of three-dimensional network cross-linking density of macromolecule hydrogel
3o
4the size of nanocrystal.Use the synthetic prism structures Fe of the present invention
3o
4nanocrystal size narrow distribution, stability is better.
Embodiment
Below in conjunction with embodiment, the present invention will be described in more detail.
Embodiment mono-
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 2mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable by 365nm thermal initiation is at the anionic polymer hydrogel of 2mol%; Anionic monomer group is sulfonic group;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate Fe
2(SO
4)
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 8h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 334nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment bis-
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 0.5mol% linking agent methylene diacrylamide and 0.1mol% initiator ammonium persulfate, the synthesizing cross-linked density of Raolical polymerizable by 365nm thermal initiation is at 0.5% anionic polymer hydrogel, and anionic monomer group is Phenylsulfonic acid base;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 2: 1, adding deionized water to be mixed with concentration is 0.2M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate Fe
2(SO
4)
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 30ml, at room temperature soak 6h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 0.5mol in beaker, alkali is potassium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 18h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 162nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment tri-
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 15mol% linking agent methylene diacrylamide and 0.1mol% initiator ammonium persulfate, the synthesizing cross-linked density of Raolical polymerizable by 365nm thermal initiation is at the anionic polymer hydrogel of 15mol%, and anionic monomer group is phosphate salt;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 3: 1, adding deionized water to be mixed with concentration is 0.3M ferric ion solutions, divalent iron salt is iron protochloride FeCl
2, trivalent iron salt is iron(ic) chloride FeCl
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 20ml, at room temperature soak 15h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1mol in beaker, alkali is ammoniacal liquor;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 15h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal.
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 257nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment tetra-
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 10mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable causing by 365nm UV-light is at the anionic polymer hydrogel of 10mol%, and anionic monomer group is carboxylic acid group's salt;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is Iron nitrate Fe (NO
3)
2, trivalent iron salt is iron nitrate (Fe (NO
3)
3);
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 15ml, at room temperature soak 18h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 0.8mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 14h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal.
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 254nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment five
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 15mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable by thermal initiation is at the anionic polymer hydrogel of 15mol%, and anionic monomer group is Phenylsulfonic acid base salt;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3);
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 8h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 143nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment six
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 4mol% linking agent methylene diacrylamide and 0.1mol% initiator ammonium persulfate, the synthesizing cross-linked density of Raolical polymerizable causing by 365nm UV-light is at the anionic polymer hydrogel of 15mol%, and anionic monomer is group 2-acrylamide-2-methylpro panesulfonic acid sodium;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.2M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3);
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 25ml, at room temperature soak 20h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 17h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal.
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 147nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment seven
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 15mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, by 365nm UV-light, cause the synthesizing cross-linked density of Raolical polymerizable at the anionic polymer hydrogel of 15mol%, anionic monomer is 2-acrylamide-2-methyl propane sulfonic acid sodium;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 2: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is iron protochloride FeCl
2, trivalent iron salt is iron(ic) chloride FeCl
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 20ml, at room temperature soak 6-24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.0mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 12h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal.
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 127nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment eight
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 15mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable by thermal initiation is at the anionic polymer hydrogel of 15mol%, and anionic monomer is 2-acrylamide-2-methyl propane sulfonic acid sodium;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 3: 1, adding deionized water to be mixed with concentration is 0.2M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3);
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 20ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali is potassium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 14h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal.
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 113nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment nine
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 8mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid or ammonium persulphate, the synthesizing cross-linked density of Raolical polymerizable causing by 365nm UV-light is at the anionic polymer hydrogel of 8mol%, and anionic monomer group is carboxylic acid group;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is iron protochloride FeCl
2, trivalent iron salt is iron(ic) chloride FeCl
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 15ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali is ammoniacal liquor;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 17h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 338nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment ten
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 4mol% linking agent methylene diacrylamide and 0.1mol% initiator ammonium persulfate, the synthesizing cross-linked density of Raolical polymerizable by thermal initiation is at the anionic polymer hydrogel of 4mol%, and anionic monomer is polyacrylic acid;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is Iron nitrate Fe (NO
3)
2, trivalent iron salt is ferric sulfate iron nitrate Fe (NO
3)
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.5mol in beaker, alkali comprises sodium hydroxide, potassium hydroxide or ammoniacal liquor;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 7h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 269nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment 11
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 45mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable causing by 365nm UV-light is at the anionic polymer hydrogel of 0.5-15mol%, and anionic monomer is methacrylic acid;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.4M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3);
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.0mol in beaker, alkali comprises sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 8h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 306nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Embodiment 12
A method for synthetic prism structures ferroferric oxide nano crystal, step is as follows:
Step 1: by 1M anionic monomer, 10mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid, the synthesizing cross-linked density of Raolical polymerizable by thermal initiation is at the anionic polymer hydrogel of 10mol%, and anionic monomer is methacrylic acid;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 4: 1, adding deionized water to be mixed with concentration is 0.2M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, trivalent iron salt is ferric sulfate Fe
2(SO
4)
3;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 20ml, at room temperature soak 24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 1.0mol in beaker, alkali is sodium hydroxide;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 13h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
The present embodiment gained the finished product are 147nm prism structures Fe with transmission electron microscope observation to the average length of side
3o
4nanocrystal.
Claims (1)
1. a method for synthetic prism structures ferroferric oxide nano crystal, is characterized in that, step is as follows:
Step 1: by 1M anionic monomer, 0.5-15mol% linking agent methylene diacrylamide and 0.1mol% initiator α-ketoglutaric acid or ammonium persulphate, by 365nm UV-light cause or the synthesizing cross-linked density of Raolical polymerizable of thermal initiation at the anionic polymer hydrogel of 0.5-15mol%, anionic monomer group comprises sulfonic group, sulfonic group salt, Phenylsulfonic acid base, Phenylsulfonic acid base salt, phosphate, phosphate salt, carboxylic acid group or carboxylic acid group's salt, and anionic monomer is divided into natural and synthetic anionic hydrogel;
Step 2: the divalent iron salt and the trivalent iron salt that take certain mol proportion add in beaker, and the mol ratio of divalent iron salt and trivalent iron salt is 2: 1-4: 1, adding deionized water to be mixed with concentration is 0.2M-0.4M ferric ion solutions, divalent iron salt is ferrous sulfate FeSO
4, iron protochloride FeCl
2, Iron nitrate Fe (NO
3)
2or containing the above-mentioned molysite of crystal water, trivalent iron salt is ferric sulfate (Fe
2(SO
4)
3), iron(ic) chloride (FeCl
3), iron nitrate (Fe (NO
3)
3) or containing the above-mentioned molysite of crystal water;
Step 3: the anionic hydrogel described in step 1 is dipped in the ferric ion solutions described in step 2, the volume ratio of anionic hydrogel quality and ferric ion solutions is 3g: 10ml-3g: 30ml, at room temperature soak 6-24h, iron ion is adsorbed onto in anionic hydrogel network;
Step 4: prepare the alkaline solution 10ml of 0.5mol-1.5mol in beaker, alkali comprises sodium hydroxide, potassium hydroxide or ammoniacal liquor;
Step 5: adsorbed the hydrogel of iron ion and the beaker of ferric ion solutions passes into nitrogen until remove the oxygen in solution to being equipped with in step 3, simultaneously also in the beaker of the alkaline solution of step 4, pass into nitrogen until remove the oxygen in solution, then the hydrogel that has adsorbed iron ion in step 3 is dipped in the alkaline solution of step 4;
Step 6: the pH value of the alkaline solution immersed with hydrogel of step 5 is adjusted to 11, heating in water bath to 40 ℃, under nitrogen atmosphere, constant temperature keeps 6-18h, at the synthetic Fe of anionic polymer hydrogel network situ
3o
4nanocrystal;
Step 7: will wrap up Fe
3o
4after distilled water cleaning for the anionic polymer hydrogel of nanocrystal, vacuum-drying, sintering in retort furnace is until remove after macromolecule hydrogel the synthetic prism structures Fe that obtains
3o
4the black powder of nanocrystal.
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| CN1580267A (en) * | 2003-08-14 | 2005-02-16 | 中国农业大学 | Magneto tactic bacteria nano magnetic particle extracting and purifying method |
| WO2009026141A1 (en) * | 2007-08-17 | 2009-02-26 | University Of Florida Research Foundation, Inc. | Supercrystalline colloidal particles and method of production |
| CN102391603A (en) * | 2011-07-22 | 2012-03-28 | 西安交通大学 | Preparation method of novel magnetism macromolecule hydrogel |
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| CN1580267A (en) * | 2003-08-14 | 2005-02-16 | 中国农业大学 | Magneto tactic bacteria nano magnetic particle extracting and purifying method |
| WO2009026141A1 (en) * | 2007-08-17 | 2009-02-26 | University Of Florida Research Foundation, Inc. | Supercrystalline colloidal particles and method of production |
| CN102391603A (en) * | 2011-07-22 | 2012-03-28 | 西安交通大学 | Preparation method of novel magnetism macromolecule hydrogel |
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