CN109250724B - Attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material and preparation method thereof - Google Patents
Attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material and a preparation method thereof, wherein the preparation method comprises the steps of preparing a suspension of attapulgite; adding Fe to the suspension2+And Fe3+Salt; and continuously adding an alkaline substance into the suspension, and reacting for a set time to obtain the attapulgite @ ferroferric oxide magnetic nano composite material. The preparation method has the advantages of simple conditions, short preparation period and environmental protection, and the prepared composite material has Fe on the surface3O4The material has the advantages of uniform distribution, controllable thickness and strong magnetic responsiveness, can be oriented along the direction of magnetic lines under the action of a magnetic field, and has high potential application value in the fields of special light, electricity, magnetism, heat and the like.
Description
Technical Field
The invention belongs to the field of magnetic nano material preparation, and particularly relates to magnetic coating and functionalization of natural one-dimensional nano mineral attapulgite.
Background
Attapulgite is a chain layered silicate, and is widely used in the fields of adsorbents, catalysts, catalyst carriers and the like because the surface of attapulgite contains abundant hydroxyl groups, permanent negative charges and porous structures. With the new technical innovation and the industrial upgrading, the use requirement of new materials is higher and higher, so that some inorganic minerals such as attapulgite which are widely applied need purposefully modified before being applied, so as to meet the development requirement of new technology. The modification treatment comprises surface modification or functional modification, wherein the surface modification utilizes coupling agent, surfactant and the like to graft and coat the modifier on the surface of inorganic mineral powder by means of chemical adsorption or chemical bonding reaction and the like, so as to improve the surface property of the inorganic mineral powder and achieve the purpose of modification; the functional modification is a further development of mineral surface modification, and inorganic nanoparticles or organic matters with specific functions are deposited on the surface of the mineral or assembled in pore channels or layers of the mineral by a physical, chemical or mechanical method, so that new functional characteristics are endowed to the inorganic mineral, and the functional composite material is formed.
In the field of attapulgite nano composite materials, supported ZnO, NiO, CuO and TiO have been developed2The attapulgite-based composite material of the nano particles generally focuses on the antibacterial or catalytic aspect, for example, the prepared ZnO/attapulgite composite material has enhanced antibacterial activity, and the CuO/attapulgite composite material has photocatalytic degradation capability on dye pollutants. However, the existing method loads Fe on attapulgite3O4And little research on the application thereof. Meanwhile, the surface of the attapulgite is loaded with the nano material, only the result of 'loading' is achieved, the uniformity of the distribution of the nano material on the surface of the matrix cannot be ensured, and an effective, simple and convenient method for solving the problem does not exist at present.
Therefore, the attapulgite with the magnetic nano particles uniformly coated on the surface, which is green and environment-friendly, needs to be developed, and meanwhile, the method has the advantages of simple conditions, short preparation period, low cost and convenience for industrial popularization, and provides important practical significance for optimizing the comprehensive utilization of attapulgite mineral resources.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the method has the advantages of simple conditions, short preparation period, controllable thickness of the ferroferric oxide on the surface of the attapulgite, strong magnetic responsiveness, environmental protection, orientation along the direction of magnetic force lines under the action of a magnetic field, and high potential application value of the displayed anisotropy in the fields of special light, electricity, magnetism, heat and the like, thereby completing the invention.
The invention aims to provide the following technical scheme:
(1) an attapulgite @ ferroferric oxide magnetic nano composite material has crystal face diffraction peaks on an XRD (X-ray diffraction) pattern of 8.50 degrees, 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees of 2 theta.
(2) A preparation method of an attapulgite @ ferroferric oxide magnetic nano composite material comprises the following steps:
and 3, continuously adding an alkaline substance into the suspension, and reacting for a set time to obtain the attapulgite @ ferroferric oxide magnetic nano composite material.
The method for preparing the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material based on the coprecipitation method has the following beneficial effects:
1) the invention takes polyethyleneimine as a macromolecular polyfunctional group organic ligand, adsorbs the macromolecular polyfunctional group organic ligand on the surface of attapulgite, and obtains ferroferric oxide particles uniformly coated on the surface of the attapulgite through in-situ synthesis.
2) In the preparation process, the thickness of the ferroferric oxide layer on the surface of the attapulgite can be controlled by adjusting the addition of the ferric salt, so that the simple and controllable magnetism of the attapulgite and the ferroferric oxide is realized.
3) The invention has simple preparation conditions and low reaction temperature, and has low cost compared with other one-dimensional magnetic composite materials such as silver nanowires and the like.
4) The attapulgite @ ferroferric oxide prepared by the method has strong magnetic responsiveness, can be oriented along the direction of a magnetic line under the action of a magnetic field, and has high potential application value in the fields of special light, electricity, magnetism, heat and the like.
Drawings
FIG. 1 shows XRD patterns of attapulgite @ ferroferric oxide prepared in example 1 of the invention and products of comparative example 1 and comparative example 2.
FIG. 2 shows transmission and scanning electron microscope spectra of attapulgite @ ferroferric oxide prepared in examples 1-3 of the present invention.
FIG. 3 shows transmission and scanning electron micrographs of products of comparative examples 1, 3 to 4 according to the invention.
FIG. 4 shows transmission and scanning electron micrographs of products of examples 3 to 4 and comparative examples 5 to 6 according to the present invention.
FIG. 5 is a hysteresis loop of attapulgite @ ferroferric oxide prepared in examples 1-3 of the present invention, and is compared with pure ferroferric oxide.
FIG. 6 is an orientation picture of the attapulgite @ ferroferric oxide prepared in the invention under a magnetic field, and is compared with the attapulgite @ ferroferric oxide without the magnetic field.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention aims to provide an attapulgite @ ferroferric oxide magnetic nano composite material, wherein the diameter of the attapulgite is 20-70 nm, and the length of the attapulgite is 0.2-5 mu m.
The XRD pattern of the composite material has crystal plane diffraction peaks at the 2 theta positions of 8.50 degrees, 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees.
The attapulgite @ ferroferric oxide magnetic nano composite material is an attapulgite magnetic nano composite material loaded with ferroferric oxide and prepared by the method.
The invention also aims to provide a preparation method of the attapulgite @ ferroferric oxide magnetic nano composite material, which comprises the following steps:
and 3, continuously adding an alkaline substance into the suspension, and reacting for a set time to obtain the attapulgite @ ferroferric oxide magnetic nano composite material.
In the step 1, attapulgite and water are uniformly mixed to prepare an attapulgite suspension, wherein the attapulgite is a fibrous mineral with the diameter of 20-70 nm and the length of 0.2-5 microns.
In a preferred embodiment, the suspension has a solids content of 0.1 to 10mg/m L, preferably 0.5 to 1.5mg/m L.
The attapulgite with high concentration and nanometer grain diameter is easy to agglomerate in water, and in the mass concentration range, the attapulgite with nanometer grain diameter can be uniformly dispersed in water, the agglomeration degree is extremely low, and the whole surface is convenient to load Fe3O4。
In a preferred embodiment, the attapulgite is further dispersed during the configuration in step 1 with stirring.
In step 2, Fe is added to the suspension2+Salt and Fe3+And (3) salt.
In a preferred embodiment, the Fe2+The salt is selected from one or more of ferrous sulfate, ferrous chloride and ferrous nitrate.
In a preferred embodiment, the Fe3+The salt is selected from any one of ferric chloride and ferric nitrate or the saltAnd (4) combining.
In a preferred embodiment, Fe2+And Fe3+Before the addition of salt, the attapulgite suspension is pretreated: to the suspension is added an organic ligand, preferably a multifunctional organic ligand.
In a further preferred embodiment, the organic ligand is any one or more of polyethyleneimine and derivatives thereof, polyacrylamide and derivatives thereof, or polyquaternary ammonium salts and derivatives thereof, preferably polyethyleneimine and derivatives thereof. The polyethyleneimine and the derivatives thereof, the polyacrylamide and the derivatives thereof, or the polyquaternary ammonium salt and the derivatives thereof are all substances with high molecular weight, have strong acting force with a base material, can be well adsorbed on the surface of the attapulgite, and simultaneously, the organic ligand and Fe2+And Fe3+Formation of a complex, Fe2+And Fe3+Uniformly distributed on the surface of attapulgite to synthesize Fe3O4The reaction is an in-situ synthesis reaction, and Fe is reduced3O4The aggregation degree on the surface of the attapulgite forms a uniform coating layer with 100 percent of coverage.
In addition, if the attapulgite is used well, the attapulgite needs to be further activated to increase the specific surface area and improve the adsorption activity. The common activation means of the attapulgite mainly comprise heat treatment, acidification activation and the like, but the heat treatment and the acidification activation have the risk of collapsing the structure of the attapulgite and eliminating micropores of the attapulgite; in addition, the activation of attapulgite complicates the operation steps and increases the industrialization difficulty of the preparation method. The pretreatment provided by the invention can omit the activation treatment step while providing conditions for the in-situ reaction, thereby optimizing the reaction procedure.
In a further preferred embodiment, the weight ratio of the organic ligand to the attapulgite is 1:2 to 1: 10.
In a further preferred embodiment, the weight ratio of the organic ligand to the attapulgite is 1:4 to 1: 5.
Notably, the amount of organic ligand added is such that a uniform load of Fe is formed3O4Attapulgite clay mineralIt is important. When the weight ratio of the organic ligand to the attapulgite is less than 1:10, a smaller amount of the organic ligand added results in bound Fe2+And Fe3+Less, Fe2+And Fe3+Most of the Fe is free in aqueous solution and formed3O4Dispersed in water and can not be effectively combined to the surface of the attapulgite; when the weight ratio of the organic ligand to the attapulgite is more than 1:2, the organic ligand exceeds the maximum adsorption capacity of the attapulgite, and the organic ligand is distributed in the whole system, so that the adsorbed Fe2+And Fe3+Fe loaded on attapulgite and uniformly distributed in the whole system3O4The weight ratio of the organic ligand to the attapulgite is also less, so the weight ratio of the organic ligand to the attapulgite is limited to 1: 2-1: 10.
In a preferred embodiment, in Fe2+And Fe3+Before adding salt, continuously introducing nitrogen into the suspension, discharging oxygen in the suspension, providing an inert reaction environment, and avoiding Fe2+And (4) oxidizing.
In a preferred embodiment, Fe2+Salt and Fe3+In salt, Fe2+And Fe3+The molar ratio of (A) to (B) is 0.80:2.0 to 1.5:2.0, and Fe can be most sufficiently synthesized at the molar ratio3O4。
In a preferred embodiment, the weight of attapulgite and Fe3+Fe in salt3+The ratio of the molar amount of (b) is 100 parts by weight to 1 part by weight to 100 parts by weight to 3.5 parts by weight, wherein 1g is 1 part by weight and 1mol is 1 part by weight.
Lower Fe3+The relative degree of supersaturation will promote Fe3O4Nucleation of nanoparticles on Attapulgite and resulting in larger Fe3O4Nanoparticles, while a higher relative supersaturation will result in homogeneous nucleation, with Fe3O4The particle size of the nano particles is smaller. When the iron concentration exceeds the above range, Fe is large3O4The nanoparticles lead to incomplete coverage of the attapulgite or small Fe on the attapulgite3O4The nano particles are seriously aggregated and are unevenly distributed.
Fe as described above3+Within the dosage range, the change of the concentration of the ferric salt is used for controlling the attapulgite-Fe3O4The morphology of the core-shell nanocomposite is effective: with increasing iron salt concentration, more and more Fe3O4The nanoparticles form on the attapulgite, resulting in thicker Fe3O4Shell, but once iron salt concentration exceeds a critical value, Fe3O4And the package is not uniformly packed.
In a preferred embodiment, the organic ligand, Fe2+Salt and Fe3+The addition of the salt was accompanied by stirring.
And step 3, continuously adding an alkaline substance into the suspension, and reacting for a set time to obtain the attapulgite @ ferroferric oxide magnetic nano composite material.
In a preferred embodiment, the alkaline substance is any one or more of sodium hydroxide, potassium hydroxide and ammonia water.
In a further preferred embodiment, the basic substance is preferably ammonia.
In a further preferred embodiment, after the alkaline substance is added, the pH of the system is 8-12.
In a further preferred embodiment, the alkaline substance may be added at once or in portions.
In a preferred embodiment, Fe3O4The reaction temperature is 50-90 ℃, and the reaction time is 20-60 min.
In a further preferred embodiment, Fe3O4The reaction temperature is 60-80 ℃, and the reaction time is 30-40 min.
In the above reaction temperature range, Fe3O4Can form a uniform coating layer on the surface of the attapulgite. At temperatures below 50 ℃, Fe3O4Mainly formed in liquid through self-nucleation, the surface formation amount of the attapulgite is reduced and uneven; fe in suspension when the temperature is higher than 90 DEG C3O4With increasing temperature, which results in Fe3O4The nano particles are beneficial to the nucleation on the attapulgite, but the nucleation rate is reduced due to the high temperature; on the other hand, molecular motion at high temperature makes Fe3O4The nanoparticles grow along the attapulgite nanorods, resulting in the appearance of very thick Fe in the attapulgite nanorods3O4The surface of the shell and the attapulgite is not uniform. When the alkaline substance is ammonia water, the ammonia water is easily decomposed, the high-temperature reaction increases the difficulty of operation, and the production cost is increased.
In a preferred embodiment, after the reaction is completed, solid-liquid separation, washing and drying are carried out.
The solid-liquid separation mode can be any one of normal pressure filtration, vacuum filtration and centrifugal separation, and the nano material has smaller particle size and larger filtration difficulty, and is preferably centrifugal separation.
In a preferred embodiment, the attapulgite @ ferroferric oxide one-dimensional magnetic nanocomposite is obtained, and crystal face diffraction peaks exist on an XRD pattern of the composite at 2 theta of 8.50 degrees, 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees.
The invention further provides application of the attapulgite @ ferroferric oxide magnetic nanocomposite to the aspect of functional electronic devices or photonic devices.
Examples
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the following examples and comparative examples, various materials or reagents are mentioned, which are not particularly limited, and commercially available raw materials may be used, or they may be prepared by a conventional method on a laboratory scale or a production scale.
Example 1
Preparing 1mg/m L attapulgite water suspension 100m L, adding 20mg polyethyleneimine into the dispersion, and stirring uniformly to obtain stable suspension;
adding 1.0mmol of ferric chloride and 0.5mmol of ferrous sulfate, reacting at 60 deg.C for 5 min, adding 5m of L ammonia water, and reacting at 60 deg.C for 30 min;
and centrifuging the suspension to obtain the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material.
Example 2
Preparing 1mg/m L attapulgite water suspension 100m L, adding 20mg polyethyleneimine into the dispersion, and stirring uniformly to obtain stable suspension;
adding 2.0mmol of ferric chloride and 1.0mmol of ferrous sulfate, reacting at 60 deg.C for 5 min, adding 5m of L ammonia water, and reacting at 60 deg.C for 30 min;
and centrifuging the suspension to obtain the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material.
Example 3
Preparing 1mg/m L attapulgite water suspension 100m L, adding 20mg polyethyleneimine into the dispersion, and stirring uniformly to obtain stable suspension;
adding ferric chloride 3.0mmol and ferrous sulfate 1.5mmol, reacting at 60 deg.C for 5 min, adding ammonia water 5m in L, and reacting at 60 deg.C for 30 min;
and centrifuging the suspension to obtain the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material.
Example 4
This embodiment is different from example 3 in that ammonia water was added and then the reaction was carried out at 80 ℃ and the other steps were the same as example 3.
Comparative example
Comparative example 1
Not loaded with Fe3O4The attapulgite (I) of (2).
Comparative example 2
Commercially available pure Fe3O4A material.
Comparative example 3 (without addition of organic ligand)
Preparing 1mg/m L attapulgite water suspension 100m L, introducing nitrogen gas for protection, and stirring;
adding 1.0mmol of ferric chloride and 0.5mmol of ferrous sulfate, reacting at 60 deg.C for 5 min, adding 5m of L ammonia water, and reacting at 60 deg.C for 30 min;
and centrifuging the suspension to obtain the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material.
Comparative example 4 (high Fe)3+Amount of salt added)
Preparing 1mg/m L attapulgite water suspension 100m L, adding 20mg polyethyleneimine into the dispersion, and stirring uniformly to obtain stable suspension;
adding 4.0mmol of ferric chloride and 2.0mmol of ferrous sulfate, reacting at 60 deg.C for 5 min, adding 5m of L ammonia water, and reacting at 60 deg.C for 30 min;
and centrifuging the suspension to obtain the attapulgite @ ferroferric oxide one-dimensional magnetic nano composite material.
Comparative example 5 (Low temperature reaction)
This embodiment is different from example 3 in that ammonia water was added and then the reaction was carried out at 40 ℃, and the other steps were the same as example 3.
Comparative example 6 (high temperature reaction)
This embodiment is different from example 3 in that ammonia water was added and then the reaction was carried out at 100 ℃, and the other steps were the same as example 3.
Examples of the experiments
X-ray diffraction the sample was analyzed using an X-ray powder diffractometer model Bruker D8Advance, Germany (Cu target K α radiation) at λ 0.15406nm, step width 0.02, operating voltage 40kV, operating current 40 mA.
Scanning electron microscope: adopt Hitachi novel high resolution field emission scanning electron microscope Hitachi SU8010, operating voltage: 10 kV.
Transmission electron microscope: the Hitachi H-8100 type transmission electron microscope is adopted, and the accelerating voltage is as follows: 200 kV.
Means for generating a magnetic field: the specification of the neodymium iron boron magnet 5 blocks is 60 × 20 × 5 mm.
Experimental example 1: XRD analysis
For the attapulgite @ ferroferric oxide prepared in the example 1 and the non-supported Fe in the comparative example 13O4Attapulgite of (2) and Fe in p3O4XRD testing was performed and the results are shown in FIG. 1.
As shown in figure 1, crystal face diffraction peaks exist at the positions of 8.50 degrees, 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees of 2 theta on the XRD pattern of the attapulgite @ ferroferric oxide, but Fe is not loaded3O4The attapulgite has crystal face diffraction peaks at the 2 theta positions of 8.50 degrees, 13.91 degrees, 16.40 degrees and 19.85 degrees on an XRD pattern, and Fe3O4The 2 theta on the XRD pattern of the crystal face diffraction peaks exists at the positions of 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees, which indicates that Fe is successfully loaded on the attapulgite3O4。
Experimental example 2: scanning electron microscope and transmission electron microscope I
For the attapulgite prepared in the examples 1-3 and the non-supported Fe in the comparative example 13O4The attapulgite and the products prepared in comparative examples 3-4 were subjected to scanning electron microscope and transmission electron microscope tests, and the results are shown in fig. 2 and 3.
FIGS. 2(a-1) and (a-2) are SEM and TEM photographs, respectively, of the product of example 1;
FIGS. 2(b-1) and (b-2) are SEM and TEM photographs, respectively, of the product of example 2;
FIGS. 2(c-1) and (c-2) are SEM and TEM photographs, respectively, of the product of example 3;
FIGS. 3(a-1) and (a-2) are the scanning electron microscope and transmission electron microscope photographs of the attapulgite crude ore of comparative example 1, respectively;
FIGS. 3(b-1) and (b-2) are scanning electron micrographs and transmission electron micrographs, respectively, of the product of comparative example 3.
FIGS. 3(c-1) and (c-2) are scanning electron micrographs and transmission electron micrographs, respectively, of the product of comparative example 4.
It can be seen from the scanning electron microscope and transmission electron microscope photographs shown in FIGS. 2 and 3 that the attapulgite has a smooth surface, Fe3O4The particles are uniformly coated on the concaveOn the surface of the attapulgite, the thickness of ferroferric oxide is increased along with the increase of the content of ferric salt. However, in the product prepared in comparative example 3 without adding an organic ligand, Fe3O4The particles are not uniformly distributed on the surface of the attapulgite. Comparative example 4 where the amount of ferric chloride added was too large, Fe3O4The particles are irregularly distributed on the surface of the attapulgite, and are seriously aggregated or the surface of the attapulgite is incompletely covered.
Experimental example 3: scanning electron microscope and transmission electron microscope II
Scanning electron microscope and transmission electron microscope tests are carried out on the attapulgite @ ferroferric oxide prepared in the examples 3-4 and the attapulgite @ ferroferric oxide prepared in the comparative examples 5-6, and the results are shown in fig. 4.
FIGS. 4(a-1) and (a-2) are SEM and TEM photographs, respectively, of the product of comparative example 5;
FIGS. 4(b-1) and (b-2) are SEM and TEM photographs, respectively, of the product of example 3;
FIGS. 4(c-1) and (c-2) are SEM and TEM photographs, respectively, of the product of example 4;
FIGS. 4(d-1) and (d-2) are SEM and TEM photographs of the product of comparative example 6, respectively.
As can be seen from FIG. 4, at a relatively low temperature (40 ℃ C.), Fe3O4The nano particles are adhered to the surface of the attapulgite in the form of irregular microspheres or islands, and a large amount of Fe exists in a sample3O4Nanoparticle aggregates and uncoated attapulgite. When the temperature rises to 60-80 ℃, Fe is obvious3O4Can be uniformly coated on the surface of attapulgite, and Fe3O4Nanoparticle aggregates are also significantly reduced. Fe in suspension3O4With increasing temperature, which results in Fe3O4The nanoparticles facilitate nucleation on attapulgite. In this case, attapulgite-Fe was obtained3O4Core-shell nanocomposites. High temperature favours Fe3O4Growth of nanoparticles and Fe3O4The nucleation of the nano-particles is carried out,whereas the opposite is true at low temperatures. Thus, larger and more sparse Fe can be found compared to the case of 60 deg.C3O4The nanoparticles are bound on the surface of the attapulgite at 80 ℃. At higher temperatures (100 ℃ C.), lower Fe3O4Further reduces its nucleation rate and allows the presence of uncovered ATP. At the same time, molecular motion at high temperature makes Fe due to surface energy minimization3O4The nanoparticles grow along the attapulgite nanorods, which in turn leads to the appearance of very thick Fe in some of the attapulgite nanorods3O4And (4) a shell. The data show that attapulgite-Fe with uniform surface coating is synthesized at the temperature of 60-80 DEG C3O4A one-dimensional nanocomposite.
Experimental example 4: saturation magnetization test
For the attapulgite @ ferroferric oxide prepared in the embodiments 1-3 and the non-supported Fe in the comparative example 13O4The saturated magnetization of the attapulgite was measured, and the results are shown in FIG. 5. Wherein the content of the first and second substances,
curve a is the saturation magnetization curve of the product of example 1;
curve b is the saturation magnetization curve of the product of example 2;
curve c is the saturation magnetization curve of the product of example 3;
curve d is the saturation magnetization curve of the product of comparative example 1.
According to the saturation magnetization curve diagram shown in fig. 5, the attapulgite @ ferroferric oxide composite material shows superparamagnetism as pure ferroferric oxide, and the saturation magnetization of the attapulgite @ ferroferric oxide one-dimensional magnetic nano material is increased along with the increase of the coating amount of the ferroferric oxide.
Experimental example 5: magnetic field reaction
The attapulgite @ ferroferric oxide prepared in example 1 was tested for orientation in a magnetic field and compared with attapulgite @ ferroferric oxide without a magnetic field, and the results are shown in fig. 6.
FIG. a is a drawing of an optical microscope under the action of a magnetic field;
FIG. a-1 is an optical microscope photograph in the absence of a magnetic field;
FIG. b is a transmission microscope photograph showing the magnetic field applied.
According to the graph 6, compared with random orientation in the absence of magnetic field, the attapulgite @ ferroferric oxide can be oriented along the direction of magnetic force lines in the presence of an external magnetic field, and the connected attapulgite @ ferroferric oxide one-dimensional magnetic nano materials can be arranged in a row end to end along the direction of the magnetic force lines. Therefore, the attapulgite @ ferroferric oxide one-dimensional magnetic nano material can be used as a photonic crystal and a construction element of liquid crystal, and has extremely high application potential in the fields of optics and magnetics.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (7)
1. A preparation method of an attapulgite @ ferroferric oxide magnetic nano composite material is characterized in that crystal face diffraction peaks exist at positions with 2 theta of 8.50 degrees, 30.20 degrees, 35.42 degrees, 43.10 degrees, 53.60 degrees, 57.09 degrees and 62.70 degrees on an XRD (X-ray diffraction) map of the composite material;
the preparation method comprises the following steps:
step 1, preparing attapulgite suspension;
the solid content of the suspension is 0.1-10 mg/m L;
step 2, adding Fe into the suspension2+And Fe3+Salt;
said Fe2+The salt is selected from one or more of ferrous sulfate, ferrous chloride and ferrous nitrate;
Fe2+and Fe3+Before the addition of salt, the attapulgite suspension is pretreated: adding an organic ligand to the suspension;
the organic ligand is one or more of polyethyleneimine and derivatives thereof, polyacrylamide and derivatives thereof or polyquaternary ammonium salt and derivatives thereof;
said Fe3+The salt is selected from any one of ferric chloride and ferric nitrate or the combination thereof;
step 3, continuously adding an alkaline substance into the suspension, and reacting for a set time to obtain the attapulgite @ ferroferric oxide magnetic nano composite material;
the alkaline substance is any one or more of sodium hydroxide, potassium hydroxide and ammonia water.
2. The production method according to claim 1,
the diameter of the attapulgite is 20-70 nm, and the length of the attapulgite is 0.2-5 mu m;
in the step 1, the solid content of the suspension is 0.5-1.5 mg/m L.
3. The method of claim 1, wherein the organic ligand is polyethyleneimine or a derivative thereof.
4. The method according to claim 1, wherein in step 2, Fe2+And Fe3+Continuously introducing nitrogen into the suspension before adding the salt; and/or
Fe2+Salt and Fe3+In salt, Fe2+And Fe3+The molar ratio of (A) to (B) is 0.80:2.0 to 1.5: 2.0.
5. The method according to claim 1, wherein in step 2, Fe2+Salt and Fe3+The addition of the salt was accompanied by stirring.
6. The production method according to claim 1, wherein in step 3, the basic substance is ammonia water.
7. The preparation method according to claim 6, wherein the pH of the system is 8 to 12 after the alkaline substance is added.
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