CN115744987A - 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 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 solvent, stirring, and adding additive; and 3, step 3: transferring the mixed solution into a three-neck flask, and injecting inert gas; and 4, step 4: reacting under the condition of heating and stirring, and controlling the reaction temperature and time to obtain a dispersion liquid; and 5: and collecting the precipitate from the dispersion liquid by a high-speed centrifuge, and washing the product by using a non-polar 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 superfine nano wire material, and an application of the rare earth-based oxide superfine nano wire material.
Background
Ultra-fine nanowires have received increasing attention in recent years, and can have diameters 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 a catalytic active center; the large length-diameter ratio is beneficial to enhancing the colloid stability of the composite material, so that the composite material has good solution processability; furthermore, due to their characteristic dimensions reaching a level comparable to that of molecules, it is possible to observe macromolecule-like properties in such inorganic materials. Rare earths are 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 rare earth elements have abundant optical, electrical and magnetic properties due to the special 4f electronic structure. The rare earth-based superfine nanowire material is expected to show more special electromagnetic performance, and the research on the material is also an important direction for developing a rare earth novel functional material and reasonably utilizing rare earth resources. At present, the performance of the material in the field of photocatalysis needs to be further improved, and theoretical basis and technical support are provided for the actual industrial application of the rare earth-based oxide superfine nanowire material.
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 existing 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 base oxide superfine nano-wire material, wherein, the chemical element composition of the rare earth base oxide superfine nano-wire 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 an RE element and a compound raw material containing an Mo element according to the components of the REMoO consisting of chemical elements 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 the Mo element is oxoacid of the Mo element or oxoacid ammonium salt of the 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 the RE element to the compound raw material containing the Mo element is 10:1-100:1; the molar ratio of the total molar weight of the additive to the mixed raw materials is 20: 1-30:1;
and 2, step: adding a solvent into the weighed raw materials, fully stirring, and then adding an additive into the mixture;
and 3, step 3: transferring the mixed solution of the raw materials and the additives into a three-neck flask, and replacing the gas atmosphere in the three-neck flask with inert gas;
and 4, step 4: starting reaction under the condition of heating and stirring, controlling the reaction temperature to be 30-120 ℃ and the reaction time to be 1-12 hours, and obtaining dispersion liquid;
and 5: and collecting the 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 non-polar solvent and a polar solvent to obtain the rare earth-based oxide superfine nanowire material.
The invention is also characterized in that;
the rare earth base oxide superfine nano wire material has diameter of 1nm and length greater than 1 micron.
In the step 2, the solvent is straight-chain alkane or alkene, the carbon chain length of the straight-chain alkane or alkene is 6-18, and the boiling point of the straight-chain 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, dichloromethane 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 be 6000rpm, and the time is controlled to be 3-7 minutes.
The rare earth-based oxide superfine nanowire material prepared by the preparation method can be applied to the field of photocatalysis: comprises that the catalyst is used as a photocatalyst for catalyzing the oxidation reaction of toluene, and the oxidation products of toluene are benzaldehyde and benzyl alcohol;
the rare earth base oxide superfine nano-wire material can be applied to the field of flexible materials; including that they can form organogels and can be processed using electrospinning, wet spinning operations.
The invention has the beneficial effects that: the rare earth-based oxide superfine nanowire material has macromolecule-like property, is a bridge for connecting inorganic materials and macromolecules, has high viscosity and strong processability of dispersion liquid, can be directly processed into films, fibers and the like by using a traditional macromolecule processing means, and has wide application prospect in the field of flexible materials. Tests show that the rare earth-based oxide superfine nanowire material has semiconductor properties, has better absorption in ultraviolet and visible light regions, and has excellent photocatalytic toluene oxidation performance, which indicates that the material has the potential to be used as a photocatalyst.
The rare earth-based oxide superfine nanowire material and the preparation method thereof 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 TEM image of a sample in example 1 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 2 is an X-ray powder diffraction pattern of a sample in example 1 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 3 is a TEM photograph of a sample in example 2 of the method for preparing a rare earth-based oxide ultrafine nanowire material and its application of the present invention;
FIG. 4 is a TEM image of a sample in example 3 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 5 is a TEM photograph of a sample in example 4 of the method for preparing a rare earth-based oxide ultrafine nanowire material and its application according to the present invention;
FIG. 6 is a TEM image of a sample in example 5 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 7 is a TEM image of a sample in example 6 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 8 is a TEM image of a sample in example 7 of the preparation method and application of a rare earth-based oxide ultrafine nanowire material according to the present invention;
FIG. 9 is a graph of a rheological curve and a photograph of a dispersion of a sample in example 1 of a method for preparing a rare earth-based oxide ultrafine nanowire material and an application thereof according to the present invention;
FIG. 10 is an optical band gap spectrum of a sample in example 1 of a method for preparing a rare earth-based oxide ultra-fine nanowire material and its application according to the present invention;
FIG. 11 is a digital photograph of organogel formed by the sample in example 3 of the method for preparing a rare earth-based oxide ultrafine nanowire material and the application thereof according to the present invention;
FIG. 12 is a digital photograph of a sample-formed thin film in example 8 of a method for preparing a rare earth-based oxide ultrafine nanowire material and its application according to the present invention;
FIG. 13 is a scanning electron microscope photograph of electrospun fibers formed by a sample in 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 microscope photograph of a cake-like structure formed by the sample in example 9 of the method for preparing a rare earth based oxide ultra-fine nano wire material and the use thereof according to the present invention;
FIG. 15 is a digital photograph of a sample formed into a wet-spun fiber in example 10 of a method for preparing a rare earth-based oxide ultra-fine nanowire material and an application thereof according to the present invention.
Detailed Description
The preparation method and the application of the rare earth-based oxide ultrafine nanowire material of the invention are further described in detail with reference to the specific embodiments.
The invention provides a preparation method of a rare earth-based oxide superfine nanowire material, wherein the prepared rare earth-based oxide superfine nanowire material comprises the chemical element composition of REMoO, wherein RE is selected from 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 base oxide superfine nano-wire material is 1nm, and the length is more than 1 μm.
The invention also provides a preparation method of the rare earth-based oxide superfine nanowire material, which is a solution chemical preparation method and specifically comprises the following steps:
step 1, according to the components of the REMoO composed of chemical elements, respectively weighing compounds containing corresponding elements as raw materials; then weighing the additive;
wherein the molar ratio of the compound raw material containing the RE element to the compound raw material containing the Mo element is 10:1-100:1; the molar ratio of the total molar weight of the additive to the mixed raw materials is 20: 1-30:1;
in the step 1, the compound raw materials containing RE elements comprise rare earth nitrate, acetate and halide; the compound raw material containing the Mo element is oxoacid of the Mo element or oxoacid ammonium salt of the 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 and the linear organic amine is between 6 and 22;
in the step 2, the solvents are various nonpolar organic solvents, the carbon chain length of the solvents is 6-18, and the boiling point of the solvents is higher than the reaction temperature;
3, transferring the mixed solution of the raw materials and the additives into a three-neck flask with proper volume, and replacing the gas atmosphere in the flask with inert gas;
step 4, starting 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, the solution is in a stirring state in the reaction process, and the stirring speed is 300-800rpm;
step 5, collecting precipitates from the dispersion liquid obtained by the reaction through a high-speed centrifuge, and washing the product for a plurality of times by using a low-boiling-point nonpolar solvent and a polar solvent to obtain the rare earth-based oxide superfine nanowire material;
the nonpolar organic solvent used in the washing process of the sample in the step 5 comprises solvents such as n-hexane, n-pentane, n-heptane, cyclohexane, chloroform, dichloromethane, toluene and the like; the polar solvent comprises acetone, ethanol, ethyl acetate and other solvents, 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 the application of the rare earth base oxide superfine nano-wire material, the application of the rare earth base oxide superfine nano-wire material in the field of photocatalysis, comprising the application of the rare earth base oxide superfine nano-wire material as a photocatalyst for catalyzing the oxidation reaction of methylbenzene, wherein the oxidation products of the methylbenzene are benzaldehyde and benzyl alcohol;
the rare earth-based oxide superfine nanowire material has polymer-like property, can form organogel, can be processed by using operations such as electrostatic spinning, wet spinning and the like, and has wide application prospect in the field of flexible materials.
The preparation method and the application of the rare earth-based oxide ultrafine nanowire material of the present invention are further described in detail by the following specific examples.
Example 1;
preparing rare earth base oxide superfine nano-wire CeMoO;
CeMoO is an example of a rare earth based oxide ultrafine nanowire REMoO;
RE is Ce;
the preparation process comprises the following steps:
taking 1mmol of cerium nitrate hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (the carbon chain length is 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (the carbon chain length is 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing and keeping the pressure N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 8 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with toluene, adding ethanol again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
The morphology of the resulting product was analyzed by transmission electron microscopy, as shown in fig. 1, the material produced had a linear morphology with a length greater than a few microns and a diameter of only 1 nanometer. The phase and structure characterization of the obtained product is carried out by using an X-ray powder diffractometer, as shown in figure 2, the diffraction peak of the prepared material X-ray powder is consistent with the diffraction peak corresponding to the cerium oxide standard PDF card. The characterization results show that the rare earth-based oxide superfine nanowire CeMoO is successfully prepared.
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 which has low fluidity and high viscosity, as shown in the middle diagram in FIG. 9, wherein the dispersion liquid locks air after shaking, and a large amount of bubbles appear inside; the rheological behavior was measured using a rheometer, and as shown in fig. 9, the dispersion exhibited a high viscosity at low shear rates, and the viscosity decreased with increasing shear rate, showing typical non-newtonian behavior.
The optical band gap of the sample is tested by using a UV-vis solid diffuse reflection spectrometer, as shown in FIG. 10, the sample has strong absorption in ultraviolet and visible light regions, the band gap is calculated to be 2.55eV, and the sample has the potential of becoming a photocatalytic material; this sample was used as a catalyst for photocatalytic toluene oxidation, and the conditions tested were as follows: 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 of one atmospheric pressure at room temperature, the reaction container is a self-made quartz tube, and the light source is one of a 300W xenon lamp and a 15W 365nm or 254nm LED lamp. The method is characterized in that chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of an 254nm LED lamp, the conversion rate of toluene reaches the highest value of 83.8 percent under the catalysis of 10mg of 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 is shown.
Example 2;
preparing rare earth base oxide superfine nano wire NdMoO;
NdMoO is an example of a rare earth based oxide ultrafine nanowire, REMoO;
RE is Nd;
the preparation process comprises the following steps:
taking 1mmol of neodymium acetate hydrate and 0.2mmol of ammonium heptamolybdate, adding 16mL of hexadecene (with the carbon chain length of 16), fully stirring, and then adding 20mmol of octylamine and 2mmol of oleic acid (with the 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 keeping the pressure N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 6 hours, and reacting in the processThe solution is in a stirring state, and the stirring speed is 800rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding acetone, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with n-hexane, adding acetone again, and centrifuging to 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, as shown in fig. 3, the prepared material has a linear morphology, the length of the material is more than several microns, and the diameter of the material is only 1 nanometer, which indicates that the rare earth-based oxide ultrafine nanowire NdMoO is successfully prepared.
Example 3;
preparing rare earth base oxide superfine nano wire EuMoO and organogel thereof;
EuMoO is an example of a rare earth based oxide ultrafine nanowire REMoO;
RE taking Eu;
the preparation process comprises the following steps:
1mmol of europium nitrate hydrate and 0.01mmol of phosphomolybdic acid are taken, 16mL of octadecene (with the carbon chain length of 18) is added, the mixture is fully stirred, and 27mmol of oleylamine and 2.7mmol of oleic acid (with the carbon chain length of 18) additive are added to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing and keeping the pressure N at one atmosphere 2 Heating to 120 ℃ under protection, reacting for 1.5 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 600rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with cyclohexane, adding ethanol again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the EuMoO superfine nanowire material.
The morphology of the obtained product was analyzed by a transmission electron microscope, as shown in fig. 4, the prepared material had a linear morphology with a length of more than several micrometers and a diameter of only 1 nanometer, indicating that the preparation of the rare earth-based oxide ultrafine nanowires EuMoO was successful.
The above sample was dispersed in 5mL of n-hexane, the dispersion was transferred to a glass bottle and sealed, and after 1 hour of sonication, it was allowed to stand for 1 day, as shown in fig. 11, whereby the fluidity of the dispersion was greatly reduced to form an organogel.
Example 4;
preparing rare earth base oxide superfine nano wire TbMoO;
TbMoO is an example of rare earth based oxide ultra-fine nanowire REMoO;
RE takes Tb;
the preparation process comprises the following steps:
taking 1mmol of terbium chloride hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of n-hexane (the carbon chain length is 6), fully stirring, and then adding 30mmol of octylamine and 1.5mmol of octanoic acid additive (the carbon chain length is 8) to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing and keeping the pressure N at one atmosphere 2 Heating to 30 ℃ under protection, reacting for 12 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 300rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; the precipitate is continuously dispersed by chloroform, and the product is centrifugally washed by adding ethanol again; repeating the steps for five times to finally obtain the TbMoO superfine nanowire material.
The morphology of the obtained product was analyzed by a transmission electron microscope, as shown in fig. 5, the prepared material had a linear morphology with a length of more than several micrometers and a diameter of only 1 nanometer, indicating that the rare earth-based oxide ultrafine nanowire TbMoO was successfully prepared.
Example 5;
preparing rare earth base oxide superfine nano wire ErMoO;
ErMoO is an example of a rare earth based oxide ultra fine nanowire REMoO;
RE takes Er;
the preparation process comprises the following steps:
taking 1mmol of erbium chloride hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of n-octane (the carbon chain length is 8), fully stirring, and then adding 27mmol of oleylamine and 5.4mmol of stearic acid (the carbon chain lengths are respectively 18 and 22) additives to obtain a precursor solution;
transferring the precursor solution to a three-neck flask, sealing, and keeping the pressure of N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 3 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 500rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with dichloromethane, adding ethanol again, and centrifuging to wash 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 several micrometers, and the diameter of the material is only 1 nanometer, which indicates that the rare earth-based oxide ultrafine nanowire ErMoO is successfully prepared.
Example 6;
preparing rare earth base oxide superfine nano-wire YbMoO;
YbMoO is an example of a rare earth based oxide ultrafine nanowire REMoO;
RE taking Yb;
the preparation process comprises the following steps:
taking 1mmol of ytterbium acetate hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of dodecane (with the carbon chain length of 12), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of lauric acid (with the carbon chain lengths of 18 and 12 respectively) additives to obtain a precursor solution;
transferring the precursor solution to a three-neck flask, sealing, and keeping the pressure of N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 2 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 600rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethyl acetate, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; 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, as shown in fig. 7, the prepared material has a linear morphology, the length of the material is more than several micrometers, and the diameter of the material is only 1 nanometer, which indicates that the rare earth-based oxide ultrafine nanowire YbMoO is successfully prepared.
Example 7;
preparing rare earth base oxide superfine nano wire YMoO;
YMoO is an example of rare earth based oxide ultra fine nanowire REMoO;
taking Y from RE;
the preparation process comprises the following steps:
taking 1mmol of yttrium nitrate hydrate and 0.02mmol of phosphomolybdic acid, adding 16mL of octadecene (the carbon chain length is 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (the carbon chain length is 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing and keeping the pressure N at one atmosphere 2 Heating to 100 ℃ under protection, reacting for 2 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 500rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with n-pentane, adding ethanol again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the YMoO superfine nanowire material.
The morphology of the obtained product was analyzed by a transmission electron microscope, as shown in fig. 8, the prepared material had a linear morphology with a length of more than several micrometers and a diameter of only 1 nanometer, indicating that the rare earth-based oxide ultrafine nanowire YMoO was successfully prepared.
Example 8;
preparing CeMoO superfine nanowires and thin films thereof;
CeMoO is an example of a rare earth based oxide ultrafine nanowire REMoO;
RE is Ce;
the preparation process comprises the following steps:
taking 1mmol of cerium chloride hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (the carbon chain length is 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (the carbon chain length is 18) additive to obtain a precursor solution;
transferring the precursor solution to a three-neck flask, sealing, and keeping the pressure of N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 8 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with n-hexane, adding ethanol again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
This sample was used as a catalyst for photocatalytic toluene oxidation, and the conditions tested were as follows: 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 under the oxygen atmosphere of one atmospheric pressure and at room temperature, the reaction container is a self-made quartz tube, and the light source is one of a 300W xenon lamp and a 15W 365nm or 254nm LED lamp. The method is characterized in that chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of an 254nm LED lamp, the conversion rate of toluene reaches the highest value of 83.8 percent under the catalysis of 10mg of 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 is shown.
The materials are dispersed in a mixed solution of normal hexane and acetone, the obtained turbid solution is dripped on filter paper for suction filtration to form a uniform film, the film is peeled off by tweezers after the filter paper and the film are dried, and the film formed by the superfine inorganic nanowires can be obtained, as shown in figure 12, letters below can be clearly seen through the film, the film can be curled by the tweezers and then clamped, the film is not cracked, and good flexibility is shown.
Example 9;
CeMoO superfine nanowire and electrostatic spinning processing thereof;
CeMoO is an example of rare earth based oxide ultra fine nano wire REMoO;
RE takes Ce;
the preparation process comprises the following steps:
taking 1mmol of cerium nitrate hydrate and 0.1mmol of ammonium tetramolybdate, adding 16mL of octadecene (the carbon chain length is 18), fully stirring, and then adding 26mmol of oleylamine and 2.6mmol of oleic acid (the carbon chain length is 18) additive to obtain a precursor solution;
transferring the precursor solution into a three-neck flask, sealing and keeping the pressure N at one atmosphere 2 Heating to 60 ℃ under protection, reacting for 7 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding ethanol, centrifuging at 6000rpm for 5 minutes, and keeping the precipitate; continuously dispersing the precipitate with toluene, adding ethanol again, and centrifuging to wash the product; repeating the steps for five times to finally obtain the CeMoO superfine nanowire material.
This sample was used as a catalyst for photocatalytic toluene oxidation, and the conditions tested were as follows: 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 of one atmospheric pressure at room temperature, the reaction container is a self-made quartz tube, and the light source is one of a 300W xenon lamp and a 15W 365nm or 254nm LED lamp. The method is characterized in that chloroform is used as a solvent, the reaction is carried out for 16 hours under the irradiation of an 254nm LED lamp, the conversion rate of toluene reaches the maximum value of 83.8 percent under the catalysis of 10mg CeMoO superfine nanowires, oxidation products only comprise benzaldehyde and benzyl alcohol, and the two products can be separated through column chromatography, so that the excellent photocatalytic performance is shown.
The materials are dispersed in 10mL of toluene, and clear dispersion liquid is obtained after ultrasonic treatment for 1 hour, and the dispersion liquid can be directly used as electrostatic spinning liquid without adding any additive. 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 rotating speeds. Observing the appearance of the sample by using a scanning electron microscope, and obtaining a fiber assembled by the nanowires when the applied voltage is 18kV and the rotating speed is 600rpm as shown in FIG. 13; as shown in fig. 14, when the voltage was 12kV and the rotation speed was 100rpm, a cake-like structure assembled from nanowires was obtained.
Example 10;
preparing rare earth base oxide superfine nano wire EuMoO and processing the solution thereof;
EuMoO is an example of a rare earth based oxide ultrafine nanowire REMoO;
RE taking Eu;
the preparation process comprises the following steps:
taking 1mmol of europium chloride hydrate and 0.1mmol of phosphomolybdic acid, adding 16mL of octadecene (the carbon chain length is 18), fully stirring, and then adding 27mmol of oleylamine and 2.7mmol of oleic acid (the carbon chain length is 18) additive to obtain a precursor solution;
transferring the precursor solution to a three-neck flask, sealing, and keeping the pressure of N at one atmosphere 2 Heating to 50 ℃ under protection, reacting for 3 hours, wherein the solution is in a stirring state in the reaction process, and the stirring speed is 800rpm;
after cooling, pouring the reaction solution into a centrifuge tube, adding acetone, centrifuging for 5 minutes at 6000rpm, and keeping the precipitate; continuously dispersing the precipitate with toluene, adding acetone again, and centrifugally washing the product; the above steps were repeated five times to finally obtain a EuMoO ultrafine nanowire material, and the final product was dispersed in 5mL of toluene.
And transferring the nanowire dispersion into a 10mL syringe, taking toluene/acetone as a coagulating bath, immersing a needle in the coagulating bath for wet spinning, aging the obtained fiber in the coagulating bath for 0.5 hour, taking out the fiber by using tweezers, and drying to obtain the EuMoO superfine nanowire-based fiber, wherein the formed fiber can be bent without breaking as shown in FIG. 15, so that the good flexibility of the EuMoO superfine nanowire-based fiber is proved.
The invention relates to a preparation method and application of rare earth-based oxide superfine nanowire material, which shows the property of organic polymer-like 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 region, and shows excellent performance in the fields of photocatalytic toluene oxidation and the like. The preparation method is simple and efficient, and the prepared material can be applied to the fields of flexible materials and 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 an RE element and a compound raw material containing an Mo element according to the components of the REMoO which is a 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 the Mo element is oxoacid of the Mo element or oxoacid ammonium salt of the 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 the RE element to the compound raw material containing the Mo element is 10:1-100:1; the molar ratio of the total molar amount 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;
and 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;
and 4, step 4: starting reaction under the condition of heating and stirring, controlling the reaction temperature to be 30-120 ℃ and the reaction time to be 1-12 hours, and obtaining dispersion liquid;
and 5: collecting the 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 non-polar solvent and a polar solvent to obtain the rare earth-based oxide superfine nanowire material.
2. The method of claim 1, wherein the rare earth-based oxide ultrafine nanowire material has a diameter of 1nm and a length of more than 1 μm.
3. The method as claimed in claim 1, wherein 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.
4. The method of 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 of claim 1, wherein in step 5, the non-polar solvent comprises one or more of n-hexane, n-pentane, n-heptane, cyclohexane, chloroform, dichloromethane, and toluene; the polar solvent comprises one or more of acetone, ethanol and ethyl acetate.
6. The method of claim 1, wherein the centrifugal speed of the high speed centrifuge is controlled to 6000rpm for 3-7 min.
7. The method for preparing 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 using the 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 they can form organogels and can be processed using electrospinning, wet spinning operations.
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| US20130090511A1 (en) * | 2010-06-28 | 2013-04-11 | William Marsh Rice University | Synthesis of ultrasmall metal oxide nanoparticles |
| 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 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130090511A1 (en) * | 2010-06-28 | 2013-04-11 | William Marsh Rice University | Synthesis of ultrasmall metal oxide nanoparticles |
| 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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