CN115744987B - Preparation method and application of rare earth-based oxide superfine nanowire material - Google Patents
Preparation method and application of rare earth-based oxide superfine nanowire material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a rare earth-based oxide superfine nanowire material, wherein the chemical element composition of the material is REMoO, and RE is selected from one of rare earth elements; the preparation method comprises the following steps: step 1: weighing a compound containing corresponding elements as a raw material; weighing the additive; step 2: adding a solvent, fully stirring, and then adding an additive; step 3: transferring the mixed solution into a three-neck flask, and injecting inert gas; step 4: reacting under the condition of heating and stirring, and controlling the reaction temperature and time to obtain a dispersion liquid; step 5: and collecting the precipitate from the dispersion liquid by a high-speed centrifuge, and washing the product by using a nonpolar solvent and a polar solvent to obtain the rare earth-based oxide superfine nanowire material. The preparation method is convenient, efficient and easy to operate, and the prepared material has good optical properties and can be applied to the fields of flexible materials and photocatalysis.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a rare earth-based oxide ultrafine nanowire material and application of the rare earth-based oxide ultrafine nanowire material.
Background
Ultrafine nanowires have received increasing attention in recent years, whose diameters can be as low as one to several unit cell size dimensions. The extremely high surface atom exposure rate of the superfine nanowire is beneficial to the improvement of the catalytic performance and the determination of the catalytic active center; the large length-diameter ratio is beneficial to enhancing the colloid stability, so that the solution has good solution processability; in addition, it is possible to observe polymer-like properties in such inorganic materials, because their characteristic dimensions reach a level comparable to that of the molecules. Rare earth is composed of seventeen elements including scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Er), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu). The special 4f electronic structure of the rare earth element endows the rare earth element with rich optical, electrical and magnetic properties. The rare earth-based superfine nanowire material is expected to show more special photo-electromagnetic performance, and the research on the rare earth-based superfine nanowire material is also an important direction for developing novel rare earth functional materials and reasonably utilizing rare earth resources. The performance of the material in the field of photocatalysis needs to be further improved at present, and theoretical basis and technical support are provided for practical industrial application of rare earth-based oxide superfine nanowire materials.
Disclosure of Invention
The invention aims to provide a preparation method and application of a rare earth-based oxide superfine nanowire material, and solves the problem that the performance of the rare earth-based superfine nanowire material in the field of photocatalysis needs to be further improved.
The technical scheme adopted by the invention is as follows:
a preparation method of rare earth-based oxide superfine nanowire material, wherein the chemical element composition of the rare earth-based oxide superfine nanowire material is REMoO, and the preparation method comprises the following steps: RE is one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; the preparation method comprises the following steps:
step 1: respectively weighing a compound raw material containing RE element and a compound raw material containing Mo element according to the components of REMoO with chemical element composition to obtain a mixed raw material, and then weighing an additive;
wherein the compound raw material containing RE element comprises rare earth nitrate, acetate and halide; the compound raw material containing Mo element is oxyacid of Mo element or oxyacid ammonium salt of Mo element; the additive is linear organic carboxylic acid and linear organic amine, wherein the molar ratio of the linear organic amine to the linear organic carboxylic acid is 5-20, and the carbon chain length of the linear organic acid to the linear organic amine is 6-22;
wherein the molar ratio of the compound raw material containing RE element to the compound raw material containing Mo element is 10:1-100:1, a step of; the molar ratio of the total molar quantity of the additive to the mixed raw materials is 20:1-30:1;
step 2: adding a solvent into the weighed raw materials, fully stirring, and then adding an additive into the mixture;
step 3: transferring the mixed solution of the raw materials and the additives into a three-neck flask, and changing the gas atmosphere in the three-neck flask into inert gas;
step 4: starting to react under the condition of heating and stirring, controlling the reaction temperature to be 30-120 ℃ and the reaction time to be 1-12 hours to obtain dispersion liquid;
step 5: collecting precipitate from the dispersion liquid obtained by the reaction through a high-speed centrifuge, and washing the product for 3-7 times by using a nonpolar solvent and a polar solvent to obtain the rare earth oxide superfine nanowire material.
The invention is also characterized in that;
the diameter of the rare earth-based oxide superfine nanowire material is 1nm, and the length is more than 1 mu m.
In the step 2, the solvent is linear alkane or alkene, the carbon chain length of the linear alkane or alkene is 6-18, and the boiling point of the linear alkane or alkene is higher than the reaction temperature.
In the step 4, the pressure of an inert gas system in the three-neck flask is one atmosphere; the stirring speed is controlled to be 300-800rpm in the reaction process.
In the step 5, the nonpolar solvent comprises one or more of n-hexane, n-pentane, n-heptane, cyclohexane, chloroform, methylene dichloride and toluene; the polar solvent comprises one or more of acetone, ethanol and ethyl acetate.
The centrifugal speed of the high-speed centrifugal machine is controlled to 6000rpm, and the time is controlled to 3-7 minutes.
The rare earth oxide superfine nanowire material prepared by the preparation method can be applied to the field of photocatalysis: the method comprises the steps of taking the catalyst as a photocatalyst for photocatalytic toluene oxidation reaction, wherein toluene oxidation products are benzaldehyde and benzyl alcohol;
a rare earth-based oxide superfine nanowire material can be applied to the field of flexible materials; including that it can form organogels, which can be processed using electrospinning, wet spinning operations.
The beneficial effects of the invention are as follows: the rare earth-based oxide superfine nanowire material has polymer-like properties, is a bridge for connecting inorganic materials and polymers, has high viscosity and strong processability, can be directly processed into films, fibers and the like by using a traditional polymer processing means, and has wide application prospect in the field of flexible materials. The rare earth oxide superfine nanowire material has semiconductor property, better absorption in ultraviolet and visible light regions and excellent photocatalytic toluene oxidation performance, and the material has potential as a photocatalyst.
The rare earth-based oxide superfine nanowire material and the preparation method thereof provided by the invention have the advantages of simplicity, high efficiency, low energy consumption, low pollution, high yield and the like, and the prepared material has excellent performance. Can provide reliable raw material supply for the application of photoelectric and structure-related rare earth functional materials, and has certain practical significance.
Drawings
FIG. 1 is a transmission electron micrograph of a sample of example 1 of a method for preparing a rare earth-based oxide ultrafine nanowire material of the present invention and its application;
FIG. 2 is an X-ray powder diffraction pattern of a sample in example 1 of a method for preparing rare earth-based oxide ultrafine nanowire materials and applications thereof according to the present invention;
FIG. 3 is a transmission electron micrograph of a sample of example 2 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 4 is a transmission electron micrograph of a sample of example 3 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 5 is a transmission electron micrograph of a sample of example 4 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 6 is a transmission electron micrograph of a sample of example 5 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 7 is a transmission electron micrograph of a sample of example 6 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 8 is a transmission electron micrograph of a sample of example 7 of a method for preparing a rare earth-based oxide ultrafine nanowire material and applications thereof according to the present invention;
FIG. 9 is a graph of a rheological curve and a dispersion photograph of a sample in example 1 of a preparation method of a rare earth-based oxide ultrafine nanowire material and application thereof according to the present invention;
FIG. 10 is an optical bandgap diagram of a sample of example 1 of a method for preparing rare earth-based oxide ultrafine nanowire materials and applications thereof according to the present invention;
FIG. 11 is a digital photograph of organogel formed from sample in example 3 of a method for preparing rare earth-based oxide ultrafine nanowire material and application thereof according to the present invention;
FIG. 12 is a digital photograph of a sample-formed film of example 8 of a method for preparing rare earth-based oxide ultrafine nanowire materials and applications thereof according to the present invention;
FIG. 13 is a scanning electron micrograph of a sample formed electrospun fiber of example 9 of a method for preparing a rare earth-based oxide ultrafine nanowire material and an application thereof according to the present invention;
FIG. 14 is a scanning electron micrograph of a sample formed into a pie-shaped structure in example 9 of a method for preparing a rare earth-based oxide ultrafine nanowire material of the invention and its application;
fig. 15 is a digital photograph of a sample formed wet spun fiber in example 10 of a method for preparing a rare earth based oxide ultra fine nanowire material of the present invention and its application.
Detailed Description
The preparation method and application of the rare earth oxide ultrafine nanowire material are described in further detail below with reference to specific embodiments.
The invention provides a preparation method of a rare earth-based oxide ultrafine nanowire material, wherein the chemical element composition of the prepared rare earth-based oxide ultrafine nanowire material is REMoO, and RE is one of fifteen rare earth elements of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu.
The diameter of the rare earth-based oxide superfine nanowire material is 1nm, and the length is more than 1 mu m.
The invention also provides a preparation method of the rare earth oxide superfine nanowire material, which is a solution chemical preparation method and specifically comprises the following steps:
step 1, respectively weighing compounds containing corresponding elements as raw materials according to components of REMoO composed of chemical elements; then, weighing the additive;
wherein the molar ratio of the compound raw material containing RE element to the compound raw material containing Mo element is 10:1-100:1, a step of; the molar ratio of the total molar quantity of the additive to the mixed raw materials is 20:1-30: 1, a step of;
in the step 1, the compound raw material containing RE element includes rare earth nitrate, acetate and halide; the compound raw material containing Mo element is oxyacid of Mo element or oxyacid ammonium salt of Mo element; the used additives are linear organic carboxylic acid and linear organic amine, wherein the molar ratio of the linear organic amine to the linear organic carboxylic acid is between 5 and 20, and the carbon chain length of the linear organic acid to the linear organic amine is between 6 and 22;
in the step 2, the solvent is various nonpolar organic solvents, the carbon chain length is between 6 and 18, and the boiling point is higher than the reaction temperature;
step 4, starting the reaction under the condition of heating and stirring, wherein the reaction temperature is 30-120 ℃ and the reaction time is 1-12 hours;
in the step 4, the reaction is carried out under the protection of inert gas, the pressure of an inert gas system is one atmosphere, and the solution is in a stirring state in the reaction process, and the stirring speed is 300-800rpm;
step 5, collecting precipitate from the dispersion liquid obtained by the reaction through a high-speed centrifuge, and washing the product with a low-boiling point nonpolar solvent and a polar solvent for several times to obtain the rare earth oxide superfine nanowire material;
the nonpolar organic solvent used in the washing process of the sample in the step 5 comprises n-hexane, n-pentane, n-heptane, cyclohexane, chloroform, methylene chloride, toluene and other solvents; the polar solvent used includes solvents such as acetone, ethanol, ethyl acetate, etc., wherein the polar solvent and the nonpolar solvent are required to be mutually soluble; the product was separated by centrifugation at 6000rpm for 3-7 minutes.
The invention also provides application of the rare earth-based oxide ultrafine nanowire material, and application of the rare earth-based oxide ultrafine nanowire material in the field of photocatalysis, wherein the rare earth-based oxide ultrafine nanowire material is used as a photocatalyst for photocatalytic toluene oxidation reaction, and toluene oxidation products are benzaldehyde and benzyl alcohol;
the rare earth-based oxide superfine nanowire material has polymer-like properties, can form organogel, can be processed by using operations such as electrostatic spinning and wet spinning, and has wide application prospects in the field of flexible materials.
The preparation method and application of the rare earth oxide ultrafine nanowire material are described in further detail by specific examples.
Example 1;
preparing rare earth-based oxide superfine nanowire CeMoO;
CeMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Ce;
the preparation process is as follows:
taking 1mmol of cerium nitrate hydrate, 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 8 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with toluene, adding ethanol again, and centrifugally washing the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
The morphology analysis of the obtained product was performed by transmission electron microscopy, as shown in fig. 1, and the prepared material had a linear morphology with a length of more than several micrometers and a diameter of only 1 nanometer. And (3) carrying out phase and structure characterization on the obtained product by using an X-ray powder diffractometer, wherein as shown in figure 2, the X-ray powder diffraction peak of the prepared material is matched with the diffraction peak corresponding to the standard PDF card of cerium oxide. The characterization result shows that the rare earth oxide superfine nanowire CeMoO is successfully prepared.
After centrifuging the sample obtained in example 1, dispersing with 5mL of toluene again, and performing ultrasonic treatment for 1 hour to obtain a clear dispersion liquid with low fluidity and high viscosity, wherein the dispersion liquid locks air after shaking and a large number of bubbles appear in the dispersion liquid as shown in an inserting chart in FIG. 9; the rheological behavior was measured using a rheometer, as shown in fig. 9, and the dispersion exhibited high viscosity at low shear rates, with viscosity decreasing with increasing shear rate, and exhibited typical non-newtonian fluid behavior.
The optical band gap of the sample is tested by using a UV-vis solid diffuse reflection spectrometer, as shown in figure 10, the sample has stronger absorption in ultraviolet and visible light regions, and the band gap is calculated to be 2.55eV, so that the sample has the potential of becoming a photocatalytic material; the sample was used as a catalyst for photocatalytic toluene oxidation under the following conditions: the catalyst amount is 10mg, the reaction solvent is one of chloroform, acetonitrile, dichloromethane, 1, 2-dichloroethane and tetrahydrofuran, the solvent volume is 0.5mL, the toluene amount is 0.1mmol, the reaction is carried out in an oxygen atmosphere with one atmosphere at room temperature, the reaction vessel is a self-made quartz tube, and the light source is one of a 300W xenon lamp, a 15W 365nm or a 254nm LED lamp. The chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of a 254nm LED lamp, the toluene conversion rate reaches the highest value of 83.8% under the catalysis of 10mg CeMoO superfine nanowire, the oxidation products only comprise benzaldehyde and benzyl alcohol, and the two products can be separated through column chromatography, so that the excellent photocatalytic performance of the products is shown.
Example 2;
preparing rare earth-based oxide superfine nanowire NdMoO;
NdMoO is one example of rare earth-based oxide ultrafine nanowires REMoO;
RE takes Nd;
the preparation process is as follows:
taking 1mmol of neodymium acetate hydrate, 0.2mmol of ammonium heptamolybdate, adding 16mL of hexadecene (with a carbon chain length of 16), fully stirring, and then adding 20mmol of octylamine and 2mmol of oleic acid (with carbon chain lengths of 8 and 18 respectively) additives to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 6 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding acetone, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with n-hexane, and adding acetone again to centrifugally wash the product; repeating the steps for five times to finally obtain the NdMoO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, and as shown in fig. 3, the prepared material has a linear morphology, the length of the material is more than a plurality of micrometers, and the diameter of the material is only 1 nanometer, which indicates that the preparation of the rare earth-based oxide superfine nanowire NdMoO is successful.
Example 3;
preparing rare earth-based oxide superfine nanowire EuMoO and organogel thereof;
EuMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Eu;
the preparation process is as follows:
taking 1mmol of europium nitrate hydrate, 0.01mmol of phosphomolybdic acid, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 120 ℃ under protection, and reacting for 1.5 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 600rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with cyclohexane, and adding ethanol again to centrifugally wash the product; repeating the steps for five times to finally obtain the EuMoO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, and as shown in fig. 4, the prepared material has a linear morphology, the length of the material is more than a plurality of micrometers, and the diameter of the material is only 1 nanometer, which indicates that the rare earth-based oxide superfine nanowire EuMoO is successfully prepared.
The above sample was dispersed in 5mL of n-hexane, the dispersion was transferred to a glass bottle to be sealed, and the mixture was allowed to stand for 1 day after 1 hour of ultrasonic treatment, as shown in fig. 11, the fluidity of the dispersion was greatly reduced to form an organogel.
Example 4;
preparing rare earth-based oxide superfine nanowire TbMoO;
TbMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE takes Tb;
the preparation process is as follows:
taking 1mmol terbium chloride hydrate, 0.1mmol phosphomolybdic acid, adding 16mL normal hexane (with a carbon chain length of 6), fully stirring, and then adding 30mmol octylamine and 1.5mmol octanoic acid additive (with a carbon chain length of 8) to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 30 ℃ under protection, and reacting for 12 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 300rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with chloroform, and adding ethanol again to centrifugally wash the product; repeating the steps for five times to finally obtain the TbMoO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, as shown in fig. 5, the prepared material has a linear morphology, the length of which is more than a few micrometers and the diameter of which is only 1 nanometer, which shows that the preparation of the rare earth-based oxide superfine nanowire TbMoO is successful.
Example 5;
preparing rare earth based oxide superfine nanowire ErMoO;
ErMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Er;
the preparation process is as follows:
taking 1mmol of erbium chloride hydrate, 0.1mmol of phosphomolybdic acid, adding 16mL of n-octane (with a carbon chain length of 8), fully stirring, and then adding 27mmol of oleylamine and 5.4mmol of stearic acid (with carbon chain lengths of 18 and 22 respectively) additives to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 3 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 500rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with dichloromethane, adding ethanol again, and centrifugally washing the product; repeating the steps for five times to finally obtain the ErMoO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, as shown in fig. 6, the prepared material has a linear morphology, the length of the material is more than a plurality of micrometers, and the diameter of the material is only 1 nanometer, which shows that the preparation of the rare earth-based oxide superfine nanowire ErMoO is successful.
Example 6;
preparing rare earth-based oxide superfine nanowire YbMoO;
YbMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Yb;
the preparation process is as follows:
taking 1mmol ytterbium acetate hydrate, 0.1mmol phosphomolybdic acid, adding 16mL dodecane (with a carbon chain length of 12), fully stirring, and then adding 27mmol oleylamine and 2.7mmol lauric acid (with carbon chain lengths of 18 and 12 respectively) additives to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 2 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 600rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethyl acetate, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with n-heptane, adding ethyl acetate again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the YbMoO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, and as shown in fig. 7, the prepared material has a linear morphology, the length of the material is more than a plurality of micrometers, and the diameter of the material is only 1 nanometer, which indicates that the preparation of the rare earth-based oxide superfine nanowire YbMoO is successful.
Example 7;
preparing rare earth-based oxide superfine nanowire YMOO;
YMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Y;
the preparation process is as follows:
taking 1mmol of yttrium nitrate hydrate, 0.02mmol of phosphomolybdic acid, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 100 ℃ under protection, and reacting for 2 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 500rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with n-pentane, adding ethanol again, and centrifugally washing the product; repeating the steps for five times to finally obtain the YMOO superfine nanowire material.
The morphology analysis of the obtained product is carried out by using a transmission electron microscope, and as shown in fig. 8, the prepared material has a linear morphology, the length of the material is more than a plurality of micrometers, and the diameter of the material is only 1 nanometer, which indicates that the preparation of the rare earth-based oxide superfine nanowire YMOO is successful.
Example 8;
preparing CeMoO superfine nanowires and films thereof;
CeMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Ce;
the preparation process is as follows:
taking 1mmol of cerium chloride hydrate, 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 8 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with n-hexane, and adding ethanol again to centrifugally wash the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
The sample was used as a catalyst for photocatalytic toluene oxidation under the following conditions: the catalyst amount is 10mg, the reaction solvent is one of chloroform, acetonitrile, dichloromethane, 1, 2-dichloroethane and tetrahydrofuran, the solvent volume is 0.5mL, the toluene amount is 0.1mmol, the reaction is carried out in an oxygen atmosphere with one atmosphere at room temperature, the reaction vessel is a self-made quartz tube, and the light source is one of a 300W xenon lamp, a 15W 365nm or a 254nm LED lamp. The chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of a 254nm LED lamp, the toluene conversion rate reaches the highest value of 83.8% under the catalysis of 10mg CeMoO superfine nanowire, the oxidation products only comprise benzaldehyde and benzyl alcohol, and the two products can be separated through column chromatography, so that the excellent photocatalytic performance of the products is shown.
Dispersing the materials in a mixed solution of normal hexane and acetone, dripping the obtained turbid liquid on filter paper, performing suction filtration to form a uniform film, peeling the filter paper and the film off by forceps after the filter paper and the film are dried, and obtaining the film formed by the superfine inorganic nanowires, wherein letters below can be clearly seen through the film, the film can be clamped after being curled by the forceps, and the film has no cracking and shows good flexibility.
Example 9;
CeMoO superfine nanowire and electrostatic spinning processing thereof;
CeMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Ce;
the preparation process is as follows:
taking 1mmol of cerium nitrate hydrate, 0.1mmol of ammonium tetramolybdate, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 26mmol of oleylamine and 2.6mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 60 ℃ under protection, and reacting for 7 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding ethanol, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with toluene, adding ethanol again, and centrifugally washing the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
The sample was used as a catalyst for photocatalytic toluene oxidation under the following conditions: the catalyst amount is 10mg, the reaction solvent is one of chloroform, acetonitrile, dichloromethane, 1, 2-dichloroethane and tetrahydrofuran, the solvent volume is 0.5mL, the toluene amount is 0.1mmol, the reaction is carried out in an oxygen atmosphere with one atmosphere at room temperature, the reaction vessel is a self-made quartz tube, and the light source is one of a 300W xenon lamp, a 15W 365nm or a 254nm LED lamp. The chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of a 254nm LED lamp, the toluene conversion rate reaches the highest value of 83.8% under the catalysis of 10mg CeMoO superfine nanowire, the oxidation products only comprise benzaldehyde and benzyl alcohol, and the two products can be separated through column chromatography, so that the excellent photocatalytic performance of the products is shown.
The above materials were dispersed in 10mL toluene and sonicated for 1 hour to give a clear dispersion which was used directly as an electrospinning solution without any additives. The dispersion is used for electrostatic spinning, and is collected by a rotary collector, so that different assembly products can be obtained under different voltages and rotation speeds. Observing the morphology of the obtained sample by using a scanning electron microscope, as shown in fig. 13, when the applied voltage is 18kV and the rotation speed is 600rpm, a fiber assembled from nanowires can be obtained; as shown in fig. 14, when the voltage was 12kV and the rotation speed was 100rpm, a pancake structure assembled from nanowires was obtained.
Example 10;
preparing rare earth-based oxide superfine nanowire EuMoO and processing the solution thereof;
EuMoO is one example of rare earth based oxide ultrafine nanowires REMoO;
RE is Eu;
the preparation process is as follows:
taking 1mmol of europium chloride hydrate, 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (with a carbon chain length of 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (with a carbon chain length of 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing, and introducing N under one atmosphere 2 Heating to 50 ℃ under protection, and reacting for 3 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
pouring the reaction solution into a centrifuge tube after cooling, adding acetone, centrifuging at 6000rpm for 5 minutes, and reserving sediment; dispersing the precipitate with toluene, and adding acetone again to centrifugally wash the product; repeating the steps for five times to finally obtain the EuMoO superfine nanowire material, wherein the final product is dispersed in 5mL of toluene.
Transferring the nanowire dispersion liquid into a 10mL syringe, taking toluene/acetone as a coagulating bath, immersing a needle in the coagulating bath for wet spinning, taking out the obtained fiber after aging for 0.5 hour in the coagulating bath by using forceps, and drying to obtain the EuMoO superfine nanowire-based fiber, wherein the formed fiber can be bent without breaking, as shown in figure 15, and the good flexibility of the fiber is proved.
The invention relates to a preparation method and application of rare earth oxide superfine nanowire material, which is characterized in that the material shows the property of organic polymer due to superfine size and extremely high length-diameter ratio, and can be processed into films, fibers and the like by using various polymer processing methods. In addition, the material has special optical properties, has good absorption in an ultraviolet-visible light region, and shows excellent performance in the fields of photocatalytic toluene oxidation and the like. The preparation method is simple, convenient and efficient, and the prepared material can be applied to the field of flexible materials and the field of photocatalysis.
Claims (7)
1. The preparation method of the rare earth-based oxide superfine nanowire material is characterized in that the chemical element composition of the rare earth-based oxide superfine nanowire material is REMoO, wherein: RE is one of Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb and Lu; the preparation method comprises the following steps:
step 1: respectively weighing a compound raw material containing RE element and a compound raw material containing Mo element according to the components of REMoO with chemical element composition to obtain a mixed raw material, and then weighing an additive;
wherein the compound raw material containing RE element comprises rare earth nitrate, acetate and halide; the compound raw material containing Mo element is oxyacid of Mo element or oxyacid ammonium salt of Mo element; the additive is linear organic carboxylic acid and linear organic amine, wherein the molar ratio of the linear organic amine to the linear organic carboxylic acid is 5-20, and the carbon chain length of the linear organic acid to the linear organic amine is 6-22;
wherein the molar ratio of the compound raw material containing RE element to the compound raw material containing Mo element is 10:1-100:1, a step of; the molar ratio of the total molar quantity of the additive to the mixed raw materials is 20:1-30:1;
step 2: adding a solvent into the weighed raw materials, fully stirring, and then adding an additive into the mixture;
step 3: transferring the mixed solution of the raw materials and the additives into a three-neck flask, and changing the gas atmosphere in the three-neck flask into inert gas;
step 4: starting to react under the condition of heating and stirring, controlling the reaction temperature to be 30-120 ℃ and the reaction time to be 1-12 hours to obtain dispersion liquid;
step 5: collecting precipitate from the dispersion liquid obtained by the reaction through a high-speed centrifuge, and washing the product for 3-7 times by using a nonpolar solvent and a polar solvent to obtain the rare earth oxide superfine nanowire material.
2. The method for preparing a rare earth-based oxide ultrafine nanowire material according to claim 1, wherein the diameter of the rare earth-based oxide ultrafine nanowire material is 1nm, and the length is greater than 1 μm.
3. The method for preparing rare earth oxide ultrafine nanowire material according to claim 1, wherein in the step 2, the solvent is a linear alkane or alkene, the carbon chain length of the linear alkane or alkene is 6-18, and the boiling point of the linear alkane or alkene is greater than the reaction temperature.
4. The method for preparing a rare earth-based oxide ultrafine nanowire material according to claim 1, wherein in the step 4, the pressure of the inert gas system in the three-neck flask is one atmosphere; the stirring speed is controlled to be 300-800rpm in the reaction process.
5. The method for preparing a rare earth-based oxide ultrafine nanowire material according to claim 1, wherein in the step 5, the nonpolar solvent comprises one or more of n-hexane, n-pentane, n-heptane, cyclohexane, chloroform, methylene chloride, toluene; the polar solvent comprises one or more of acetone, ethanol and ethyl acetate.
6. The method for preparing a rare earth-based oxide ultrafine nanowire material according to claim 1, wherein the centrifugal speed of the high-speed centrifuge is controlled to 6000rpm, and the time is controlled to 3-7 minutes.
7. The method for preparing a rare earth-based oxide ultrafine nanowire material according to any one of claims 1 to 6, wherein the prepared rare earth-based oxide ultrafine nanowire material can be applied to the field of photocatalysis: the method comprises the steps of taking the catalyst as a photocatalyst for photocatalytic toluene oxidation reaction, wherein toluene oxidation products are benzaldehyde and benzyl alcohol;
the rare earth-based oxide superfine nanowire material can be applied to the field of flexible materials; including that it can form organogels, which can be processed using electrospinning, wet spinning operations.
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| CN109266346A (en) * | 2018-09-30 | 2019-01-25 | 中山大学 | Superfine nano luminescent material and its preparation and application are converted on the wolframic acid double salt of rare earth ion doping |
| CN109810701A (en) * | 2019-01-23 | 2019-05-28 | 陕西科技大学 | A kind of solwution method prepares full-inorganic perovskite Cs4PbBr6The method and its application of nano wire |
| CN113637513A (en) * | 2021-08-11 | 2021-11-12 | 清华大学 | Use of inorganic sub-nanowires in organic solvent curing, transport and storage |
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| US9636664B1 (en) * | 2015-06-04 | 2017-05-02 | Alliance For Sustainable Energy, Llc | Metal phosphide catalysts and methods for making the same and uses thereof |
| CN109266346A (en) * | 2018-09-30 | 2019-01-25 | 中山大学 | Superfine nano luminescent material and its preparation and application are converted on the wolframic acid double salt of rare earth ion doping |
| CN109810701A (en) * | 2019-01-23 | 2019-05-28 | 陕西科技大学 | A kind of solwution method prepares full-inorganic perovskite Cs4PbBr6The method and its application of nano wire |
| CN113637513A (en) * | 2021-08-11 | 2021-11-12 | 清华大学 | Use of inorganic sub-nanowires in organic solvent curing, transport and storage |
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