CN112811458B - Mesoporous rare earth hydroxide nano material and preparation method thereof - Google Patents

Mesoporous rare earth hydroxide nano material and preparation method thereof Download PDF

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CN112811458B
CN112811458B CN202110113753.3A CN202110113753A CN112811458B CN 112811458 B CN112811458 B CN 112811458B CN 202110113753 A CN202110113753 A CN 202110113753A CN 112811458 B CN112811458 B CN 112811458B
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chloride
hydroxide
rare earth
mesoporous
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CN112811458A (en
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李晓民
王文兴
于泓跃
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Fudan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

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Abstract

The invention belongs to the technical field of nano materials, and particularly relates to a mesoporous rare earth hydroxide nano material and a preparation method thereof. The mesoporous rare earth hydroxide nano material provided by the invention has a central divergent mesoporous pore canal with the adjustable size of 100-600 nm and the adjustable pore diameter of 3-15 nm. The invention provides a preparation method of the mesoporous rare earth hydroxide nano material. The mesoporous rare earth hydroxide nano material provided by the invention has good biocompatibility and is easy to degrade; enzymes, nanoparticles or other desired substances may be loaded.

Description

Mesoporous rare earth hydroxide nano material and preparation method thereof
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a mesoporous rare earth hydroxide nano material and a preparation method thereof.
Background
With the rapid development of nano materials and technologies, more and more nano materials are applied to the fields of disease diagnosis, drug transportation, living body detection and the like. Compared with the traditional diagnosis and treatment method, the nano material has great advantages due to unique physicochemical properties and in-vivo enrichment and metabolic mechanisms. The mesoporous nano material has the unique property of being capable of loading other functional units and integrating multiple functions, so that the mesoporous nano material is widely concerned by people.
Rare earth materials have been one of the research focuses due to their unique properties such as catalysis and magnetism. For example, gadolinium can be used as a contrast agent for magnetic resonance imaging to improve image resolution; cerium can be used as a catalytic site to catalyze and decompose hydrogen peroxide into active oxygen species to realize the chemodynamic treatment of tumors.
The invention realizes the organic combination of the rare earth material and the mesoporous nano material, and endows the material with the advantages of large specific surface area, capability of loading other substances and other mesoporous materials while keeping the functionality of the rare earth material.
Disclosure of Invention
The invention aims to provide a functional mesoporous rare earth hydroxide nano material with good biocompatibility and easy degradation and a preparation method thereof.
The mesoporous rare earth hydroxide nano material provided by the invention is spherical particles, has the size of 100-600 nm, is adjustable, and is distributed with central divergent mesoporous channels with adjustable aperture of 3-15 nm.
The preparation method of the mesoporous rare earth hydroxide nano material comprises the steps of carrying out a reaction in a water-cyclohexane system, taking cetyl trimethyl ammonium bromide and citric acid as structure directing agents, sodium salicylate as a pore-expanding agent, rare earth chloride as a rare earth source, and hexamethylenetetramine or urea as a catalyst, and carrying out a synthesis reaction under a heating condition; the method comprises the following specific steps:
(1) sequentially dissolving cetyl trimethyl ammonium bromide, rare earth chloride, citric acid, sodium salicylate, hexamethylenetetramine or urea in water to obtain a clear solution;
(2) adding cyclohexane, and stirring and mixing uniformly;
(3) controlling the temperature to be 50-70 ℃, and reacting for 6-7 hours;
(4) after the reaction is finished, taking the water phase in the reaction system, centrifuging and washing.
Preferably, in the step (1), the concentration of cetyl trimethyl ammonium bromide in the clear solution is 0.01-2 wt%; the concentration of the rare earth chloride is 0.03-1 wt%; the concentration of the citric acid is 0.001-0.1 wt%; the concentration of the sodium salicylate is 0.01-0.2 wt%; the concentration of the hexamethylenetetramine or urea is 0.005-0.5 wt%.
Preferably, in the step (2), the cyclohexane is added, and the volume ratio of water: cyclohexane =1 (0.05-2).
In step (1) of the present invention, the rare earth chloride species includes lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, or yttrium chloride.
The mesoporous rare earth hydroxide nano material provided by the invention has adjustable size and pore structure; good biocompatibility and easy degradation; enzymes, nanoparticles or other desired substances may be loaded.
The prepared mesoporous gadolinium hydroxide nano material has a large specific surface area and a pore confinement effect, shows an excellent nuclear magnetic resonance contrast effect, and can be used as a nuclear magnetic resonance contrast agent.
Drawings
FIG. 1 is a scanning electron microscope image of a mesoporous gadolinium hydroxide nanomaterial prepared by the present invention.
FIG. 2 is a transmission electron microscope image of the mesoporous gadolinium hydroxide nanomaterial prepared by the present invention.
Fig. 3 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared when the volume ratio of water to cyclohexane is =1: 0.3.
FIG. 4 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with 0.05% hexadecyltrimethylammonium bromide.
FIG. 5 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with 0.15% cetyltrimethylammonium bromide.
FIG. 6 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared at a gadolinium chloride concentration of 0.04%.
FIG. 7 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared at a gadolinium chloride concentration of 0.2%.
FIG. 8 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with 0.005% citric acid concentration.
FIG. 9 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with 0.08% citric acid concentration.
FIG. 10 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with sodium salicylate at a concentration of 0.02%.
FIG. 11 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with sodium salicylate at a concentration of 0.15%.
FIG. 12 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with a hexamethylenetetramine concentration of 0.001%.
FIG. 13 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared with a hexamethylenetetramine concentration of 0.1%.
FIG. 14 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared at a reaction temperature of 50 ℃.
FIG. 15 is a scanning electron microscope image of mesoporous gadolinium hydroxide prepared at a reaction temperature of 60 ℃.
FIG. 16 is a scanning electron microscope image of mesoporous neodymium hydroxide nanomaterial.
FIG. 17 is a scanning electron microscope image of mesoporous cerium hydroxide nanomaterial.
FIG. 18 is a transmission electron microscope image of mesoporous europium hydroxide nanomaterial.
FIG. 19 is a transmission electron microscope image of mesoporous erbium hydroxide nanomaterial.
Detailed Description
The invention provides a mesoporous rare earth hydroxide nano material.
The material is rare earth hydroxide, rare earth chloride is used as a rare earth source, the size of the rare earth hydroxide nano particle is 100-600 nm, and a central divergent mesoporous pore canal with adjustable pore diameter of 3-15 nm is distributed. The rare earth hydroxide nanomaterial comprises lanthanum hydroxide, cerium hydroxide, praseodymium hydroxide, neodymium hydroxide, promethium hydroxide, samarium hydroxide, europium hydroxide, gadolinium hydroxide, terbium hydroxide, dysprosium hydroxide, holmium hydroxide, erbium hydroxide, thulium hydroxide, ytterbium hydroxide, lutetium hydroxide and yttrium hydroxide.
The invention further provides a specific preparation method of the mesoporous rare earth hydroxide nano material, which comprises the following steps:
(1) sequentially dissolving cetyl trimethyl ammonium bromide, rare earth chloride, citric acid, sodium salicylate, hexamethylenetetramine or urea in water to obtain a clear solution;
(2) adding cyclohexane, and stirring and mixing uniformly;
(3) controlling the temperature to be 50-70 ℃, and reacting for 6-7 hours;
(4) after the reaction is finished, taking the water phase in the reaction system, centrifuging and washing.
In the step (1), the dosage relation of the hexadecyl trimethyl ammonium bromide and the clear solution is as follows: the concentration of hexadecyl trimethyl ammonium bromide is 0.01-2 wt%; the dosage relation of the rare earth chloride and the clear solution is as follows: the concentration of the rare earth chloride is 0.03-1 wt%; the dosage relationship of the citric acid and the clear solution is as follows: the concentration of the citric acid is 0.001-0.1 wt%; the dosage relationship of the sodium salicylate and the clear solution is as follows: the concentration of the sodium salicylate is 0.01-0.2 wt%; the dosage relation of the hexamethylene tetramine or the urea and the clear solution is as follows: the concentration of the hexamethylenetetramine or urea is 0.005-0.5 wt%. In the step (3), the reaction temperature is 50-70 ℃.
Example 1:
cetyl trimethylammonium bromide (0.1%), gadolinium chloride (0.5%), citric acid (0.01%), sodium salicylate (0.5%), hexamethylenetetramine (0.1%) was dissolved thoroughly in water to form a clear solution. Adding water to cyclohexane in a volume ratio of =1: 0.3 of cyclohexane, and stirring uniformly. The solution was transferred to a 70 ℃ oil bath for 7 hours. After the reaction, the aqueous phase was centrifuged. Extracting the product at 70 ℃ to remove hexadecyl trimethyl ammonium bromide to obtain the required nano particles. The scanning electron micrograph of the particles is shown in FIG. 1, and the transmission electron micrograph of the particles is shown in FIG. 2.
Example 2:
cetyl trimethylammonium bromide (0.1%), neodymium chloride (0.5%), citric acid (0.01%), sodium salicylate (0.5%), hexamethylenetetramine (0.1%) was dissolved thoroughly in water to form a clear solution. Adding water to cyclohexane in a volume ratio of =1: 0.3 of cyclohexane, and stirring uniformly. The solution was transferred to a 70 ℃ oil bath for 7 hours. After the reaction, the aqueous phase was centrifuged. Extracting the product at 70 ℃ to remove hexadecyl trimethyl ammonium bromide to obtain the required nano particles. The scanning electron micrograph of the particles is shown in FIG. 16.
Example 3:
cetyl trimethylammonium bromide (0.1%), cerium chloride (0.5%), citric acid (0.01%), sodium salicylate (0.5%), hexamethylenetetramine (0.1%) was dissolved thoroughly in water to form a clear solution. Adding water to cyclohexane in a volume ratio of =1: 0.3 of cyclohexane, and stirring uniformly. The solution was transferred to a 70 ℃ oil bath for 7 hours. After the reaction, the aqueous phase was centrifuged. Extracting the product at 70 ℃ to remove hexadecyl trimethyl ammonium bromide to obtain the required nano particles. The scanning electron micrograph of the particles is shown in FIG. 17.
Example 4:
cetyl trimethylammonium bromide (0.1%), europium chloride (0.5%), citric acid (0.01%), sodium salicylate (0.5%), hexamethylenetetramine (0.1%) was dissolved thoroughly in water to form a clear solution. Adding water to cyclohexane in a volume ratio of =1: 0.3 of cyclohexane, and stirring uniformly. The solution was transferred to a 70 ℃ oil bath for 7 hours. After the reaction, the aqueous phase was centrifuged. Extracting the product at 70 ℃ to remove hexadecyl trimethyl ammonium bromide to obtain the required nano particles. The transmission electron micrograph of the particles is shown in FIG. 18.
Example 5:
cetyl trimethylammonium bromide (0.1%), erbium chloride (0.5%), citric acid (0.01%), sodium salicylate (0.5%), hexamethylenetetramine (0.1%) was dissolved thoroughly in water to form a clear solution. Adding water to cyclohexane in a volume ratio of =1: 0.3 of cyclohexane, and stirring uniformly. The solution was transferred to a 70 ℃ oil bath for 7 hours. After the reaction, the aqueous phase was centrifuged. Extracting the product at 70 ℃ to remove hexadecyl trimethyl ammonium bromide to obtain the required nano particles. The transmission electron micrograph of the particles is shown in FIG. 19.

Claims (2)

1. A preparation method of mesoporous rare earth hydroxide nano material is characterized in that the material is spherical nano particles with the size of 100-600 nm, and central divergent mesoporous channels with adjustable aperture of 3-15 nm are distributed; specifically lanthanum hydroxide, cerium hydroxide, praseodymium hydroxide, neodymium hydroxide, promethium hydroxide, samarium hydroxide, europium hydroxide, gadolinium hydroxide, terbium hydroxide, dysprosium hydroxide, holmium hydroxide, erbium hydroxide, thulium hydroxide, ytterbium hydroxide, lutetium hydroxide, or yttrium hydroxide;
the method comprises the steps of carrying out a reaction in a water-cyclohexane system, taking cetyl trimethyl ammonium bromide and citric acid as structure directing agents, sodium salicylate as pore-enlarging agents, rare earth chloride as rare earth sources, and hexamethylenetetramine or urea as catalysts, and carrying out a synthetic reaction under a heating condition; the method comprises the following specific steps:
(1) sequentially dissolving cetyl trimethyl ammonium bromide, rare earth chloride, citric acid, sodium salicylate, hexamethylenetetramine or urea in water to obtain a clear solution;
(2) adding cyclohexane, and stirring and mixing uniformly;
(3) controlling the temperature to be 50-70 ℃, and reacting for 6-7 hours;
(4) after the reaction is finished, taking a water phase in the reaction system, centrifuging and washing;
in the clear solution obtained in the step (1), the concentration of hexadecyl trimethyl ammonium bromide is 0.01-2 wt%; the concentration of the rare earth chloride is 0.03-1 wt%; the concentration of the citric acid is 0.001-0.1 wt%; the concentration of the sodium salicylate is 0.01-0.2 wt%; the concentration of the hexamethylene tetramine or the urea is 0.005-0.5 wt%;
the rare earth chloride species in step (1) is lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride or yttrium chloride.
2. The process according to claim 1, wherein the cyclohexane is added in the step (2) in a volume ratio of water: cyclohexane =1 (0.05-2).
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CN101711881A (en) * 2009-12-22 2010-05-26 上海大学 Gadolinium-containing macromolecule magnetic resonance intravascular contrast medium and preparation method thereof
CN101829552A (en) * 2010-06-08 2010-09-15 浙江大学 Preparation method of mesoporous alumina catalyst
CN102908984A (en) * 2012-11-07 2013-02-06 武汉理工大学 Graded porous metal hydroxide-SiO2 compound formaldehyde adsorbent and preparing method thereof
CN106987229A (en) * 2017-03-01 2017-07-28 常州大学 A kind of composite particles of nucleocapsid clad structure and its production and use
CN107275611A (en) * 2017-06-19 2017-10-20 南昌航空大学 The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding

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US6680415B1 (en) * 1999-11-22 2004-01-20 Dow Global Technologies Inc. Oxyhalogenation process using catalyst having porous rare earth halide support

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Publication number Priority date Publication date Assignee Title
CN101711881A (en) * 2009-12-22 2010-05-26 上海大学 Gadolinium-containing macromolecule magnetic resonance intravascular contrast medium and preparation method thereof
CN101829552A (en) * 2010-06-08 2010-09-15 浙江大学 Preparation method of mesoporous alumina catalyst
CN102908984A (en) * 2012-11-07 2013-02-06 武汉理工大学 Graded porous metal hydroxide-SiO2 compound formaldehyde adsorbent and preparing method thereof
CN106987229A (en) * 2017-03-01 2017-07-28 常州大学 A kind of composite particles of nucleocapsid clad structure and its production and use
CN107275611A (en) * 2017-06-19 2017-10-20 南昌航空大学 The spherical zinc oxide material of nanometer and preparation method of a kind of polypyrrole cladding

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