CN113277561A - Nano Cr2V4O13Material, preparation method and application thereof - Google Patents
Nano Cr2V4O13Material, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nanometer Cr2V4O13Material of the nano Cr2V4O13The material is in a quasi-spherical hollow flower shape formed by stacking flaky nano particles, and the particle diameter of the flaky nano particles is as follows: the length is 100-500nm, the width is 20-100nm, and the thickness is 10-50 nm. The invention also discloses the nanometer Cr2V4O13A preparation method and application of the material. The invention selects carboxylic acid or carboxylic acid aqueous solution as solvent to carry out solvent thermal reaction in a pressure vessel to prepare the obtained Cr2V4O13Can be self-assembled into hollow flower-shaped spherical structure, Cr2V4O13The material has uniform particle size distribution, large specific surface area, high catalytic activity, simple method, easily obtained raw materials and low cost, and is suitable for large-scale preparation; cr of this structure2V4O13When the method is used for preparing aromatic nitrile through ammoxidation of methyl aromatic hydrocarbon, the ammoxidation temperature is 300-420 ℃; with othersCompared with the vanadium-chromium catalyst, the reaction temperature is obviously reduced, the selectivity is improved, and the reaction activity is improved by 10-40%.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to nano Cr2V4O13A material and a preparation method and application thereof.
Background
Nano Cr2V4O13Is an important inorganic functional material and is applied to the fields of catalysis, battery materials, adsorbing materials, sensors and the like. As an adsorption material, the material can be used for removing azo dyes in water; as a battery material, the lithium ion battery anode can be used for preparing a novel lithium battery anode.
Synthesis of Cr2V4O13The method of the material mainly comprises the following steps: cr is generated by high-temperature solid-phase reaction2O3And V2O5Multiple cycles of calcination at 635 ℃ according to 1:2 (E.Filipek, J.Walczak, P.Tabero.J.AlloyCompd.,1998,265: 121-124); or by chemical coprecipitation with Cr (NO)3)3·9H2O and NH4VO3Synthesized as raw materials (S.Kalal, A.Pandey, R.AmetaandP.B.Punjabi.CogentChem.,2016,2: 1143344; Jinzhi Shenng, QidongLi, QiulongWei, et al.NanoRes.,2014,7(11): 1604-. However, the particle size of the materials prepared by the methods is generally above micron level, the crystallinity is not high, the materials have no complete morphology, the particle size is large, the specific surface area is small, the surface activity of the particles is poor, and the contact surface of the chemical reaction is small, so that the application range of the particles is limited.
Disclosure of Invention
The invention aims to provide a nano Cr2V4O13Material of the nano Cr2V4O13The material is in a sphere-like shape, a hollow flower shape (which can be called hollow flower ball shape) formed by stacking flaky nano particles, wherein the particle diameter of the flaky nano particles is as follows: the length is 100-500nm, the width is 20-100nm, and the thickness is 10-50 nm. The hollow flower-shaped nano Cr2V4O13The material is used as a catalyst for ammoxidation catalytic reaction, and has better catalytic effect. The nanometer Cr of the invention2V4O13The material is prepared by the following method:
mixing a vanadium source and a chromium source according to a metal atom molar ratio of 2:1, putting the mixture into a pressure container, adding a solvent, uniformly mixing, sealing, heating to 120-300 ℃, carrying out solvothermal reaction for 2-200 hours, and filtering, washing and vacuum-drying a product to obtain a precursor;
calcining the precursor at the temperature of 300-800 ℃ for 0.1-10 hours, and cooling to room temperature to obtain the nano Cr2V4O13。
The vanadium source is vanadium oxide and/or vanadium salt, and the chromium source is chromium oxide and/or chromium salt.
The vanadium oxides include, but are not limited to, V2O5、V2O4And V2O3Including but not limited to NH4VO3、VOSO4、VOCl2At least one of; the chromium oxide includes but is not limited to Cr2O3And CrO3Including but not limited to CrCl3、Cr(NO3)3And (NH)4)2Cr2O7At least one of (1).
The solvent of the solvothermal reaction is carboxylic acid or an aqueous solution of the carboxylic acid.
The carboxylic acid is at least one of C1-C20 monobasic acid or polybasic acid, or an aqueous solution containing at least one of the foregoing acids.
The C1-C20 monobasic or polybasic acid includes but is not limited to formic acid, oxalic acid, citric acid, tartaric acid, malic acid, acetic acid, benzoic acid, etc.
The pressure vessel is an autoclave or a pressure-resistant reactor.
The solvothermal reaction temperature is 160-240 ℃, and the time is 12-72 hours.
The invention provides nano Cr2V4O13Can be used for catalyzing ammoxidation of methyl aromatic hydrocarbon to prepare aromatic nitrile.
The methyl aromatic hydrocarbon comprises toluene, halogenated toluene, methoxytoluene, hydroxytoluene, nitrotoluene, cyanotoluene, aminotoluene, xylene, methylpyridine, methylpyrazine or methylpyrimidine.
The invention selects carboxylic acid or carboxylic acid aqueous solution as solvent to carry out solvent thermal reaction in a pressure vessel to prepare the obtained Cr2V4O13Can be self-assembled into hollow flower-shaped spherical structure, Cr2V4O13The material has uniform particle size distribution, large specific surface area, high catalytic activity, simple method, easily obtained raw materials and low cost, and is suitable for large-scale preparation; cr of this structure2V4O13When the method is used for preparing aromatic nitrile through ammoxidation of methyl aromatic hydrocarbon, the ammoxidation temperature is 300-420 ℃; compared with other vanadium-chromium catalysts, the catalyst has the advantages that the reaction temperature is obviously reduced, the selectivity is improved, and the reaction activity is improved by 10-40%.
Drawings
FIG. 1 shows hollow flower-shaped spherical nano Cr obtained in example 1 of the present invention2V4O13Scanning electron micrograph (2 micron scale).
FIG. 2 shows hollow flower-shaped spherical nano Cr obtained in example 1 of the present invention2V4O13Scanning electron micrograph (1 micron scale).
FIG. 3 shows hollow flower-shaped nano Cr obtained in example 1 of the present invention2V4O13Transmission electron microscopy (1 micron scale).
FIG. 4 shows hollow flower-shaped nano Cr obtained in example 1 of the present invention2V4O13Transmission electron microscopy (500 nm scale).
FIG. 5 shows hollow ball-shaped nano Cr obtained in example 1 of the present invention2V4O13Transmission electron microscopy (100 nm scale).
FIG. 6 shows the nano-Cr obtained by the present invention2V4O13XRD pattern of (a).
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples.
Example 1
According to the following steps: 1 molar ratio of vanadium to chromium V was weighed to a total mass of 2.0g2O5And CrO3Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 80ml of formic acid, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 180 ℃, carrying out thermostatic hydrothermal treatment for 24 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, repeatedly washing with distilled water and ethanol respectively, and vacuum drying at 60 deg.C for 5 hr to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 600 ℃ for 2h to obtain the nano Cr2V4O13。
FIG. 1 and FIG. 2 show the nano Cr obtained in this example2V4O13Scanning electron micrographs of the material. Where fig. 1 is an SEM image on a 2 micron scale, it can be seen that the material as a whole appears spherical, hollow. Fig. 2 is an SEM image on a 1 micron scale, and it can be seen from fig. 1 and 2 that the material is in the form of hollow flower spheres. FIGS. 3-5 show the nano-Cr flakes obtained in this example2V4O13Transmission electron micrograph (D). FIG. 3 is a TEM image at 1 micron scale showing that the structure of the material is roughly in the shape of a hollow flower; FIG. 4 is a TEM image with scale reduced to 500nm and magnification increased, from which it can be seen that the material is formed by a stack of plate-like particles; FIG. 5 shows a further increase in magnification, and the flaky particles are clearly seen on a 100nm scale, and the particle diameters of the particles are measured as 100 to 500nm in length, 20 to 100nm in width, and 10 to 50nm in thickness.
FIG. 6 shows the nano-Cr obtained in this example2V4O13XRD pattern of (a). By comparison with a standard card, a complete match was obtained.
Example 2
This example 2 is a comparative example.
Comparative example 1: the preparation method and the treatment method of the catalyst are the same as the example 1, except that the solvent formic acid is changed into ethanol, the obtained catalyst precursor is in an amorphous state, and the Cr is obtained after calcining for 2 hours at 600 DEG C2V4O13And a small amount of V2O5、CrVO4The mixture of (a) and (b) has an irregular morphology, the particle size being greater than 100nm in all three dimensions.
Comparative example 2: preparation of Cr by coprecipitation2V4O13A material. 10g of tartaric acid is taken in a beaker, 100ml of distilled water is added, and the mixture is stirred, and then the weight ratio of the tartaric acid to the distilled water is calculated according to the following formula 2:1 molar ratio of vanadium to chromium V was weighed to a total mass of 2.0g2O5And CrO3Respectively and slowly adding into a beaker, adjusting pH to 9 with ammonia water, then stirring, condensing and refluxing the mixed solution at 180 ℃ for 48h, naturally cooling to room temperature, filtering the product, respectively and repeatedly washing with distilled water and ethanol to obtain a solid, vacuum-drying the solid at 60 ℃ for 5h to obtain an amorphous precursor, and calcining the precursor in a resistance furnace at 600 ℃ for 2h to obtain crystalline phase Cr2V4O13The material has no complete morphology, the particle size of the particles is more than 5 mu m, and the specific surface area is small.
Example 3
According to the following steps: 1 molar ratio of vanadium to chromium NH of 2.0g total mass was weighed4VO3And Cr (NO)3)3Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 80ml of malonic acid, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 240 ℃, carrying out thermostatic hydrothermal treatment for 24 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, repeatedly washing with distilled water and ethanol respectively, and vacuum drying at 60 deg.C for 5 hr to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 550 ℃ for 3h to obtain the nano Cr2V4O13。
Example 4
According to the following steps: 1 molar ratio of vanadium to chromium V was weighed to a total mass of 2.0g2O4And Cr2O3Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 10g of oxalic acid and 80ml of distilled water, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 200 ℃, carrying out thermostatic hydrothermal treatment for 24 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, repeatedly washing with distilled water and ethanol respectively, and vacuum drying at 60 deg.CDrying for 5h to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 500 ℃ for 5h to obtain the nano Cr2V4O13。
Example 5
According to the following steps: 1 vanadium chromium molar ratio VOSO with a total mass of 2.0g is weighed4And CrCl3Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 10g of citric acid and 80ml of distilled water, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 220 ℃, carrying out thermostatic hydrothermal treatment for 24 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, repeatedly washing with distilled water and ethanol respectively, and vacuum drying at 60 deg.C for 5 hr to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 630 ℃ for 2h to obtain the nano Cr2V4O13。
Example 6
According to the following steps: 1 molar ratio of vanadium to chromium V was weighed to a total mass of 2.0g2O3And CrO3Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 10g of tartaric acid and 80ml of distilled water, fully stirring and uniformly mixing, sealing, placing the reaction kettle into a resistance furnace, heating to 200 ℃, carrying out constant-temperature hydrothermal treatment for 48 hours, and naturally cooling to room temperature. Filtering the product in the reaction kettle, repeatedly washing with distilled water and ethanol respectively, and vacuum drying at 60 deg.C for 5 hr to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 600 ℃ for 2h to obtain the nano Cr2V4O13。
Example 7
According to the following steps: 1 molar ratio of vanadium to chromium NH of 2.0g total mass was weighed4VO3And (NH)4)2Cr2O7Placing the mixture into a hydrothermal reaction kettle with a polytetrafluoroethylene lining and a volume of 100ml, adding 5g of benzoic acid and 80ml of distilled water, fully stirring and uniformly mixing, sealing, placing the hydrothermal reaction kettle into a resistance furnace, heating to 210 ℃, reacting at constant temperature for 30 hours, and naturally cooling to room temperature. Will be reversedFiltering the product in the reactor, repeatedly washing with distilled water and ethanol, and vacuum drying at 60 deg.C for 5 hr to obtain amorphous Cr2V4O13Calcining the precursor in a resistance furnace at 550 ℃ for 2h to obtain the nano Cr2V4O13。
The SEM, TEM and XRD patterns of examples 3-7 are all approximately the same as example 1, with the material dimensions: the length is 100-500nm, the width is 20-100nm, and the thickness is 10-50 nm.
Example 8
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 10g of nano Cr prepared in example 12V4O13Preheating and mixing p-methoxytoluene, ammonia gas and air according to a molar ratio of 1:12:30, and then reacting through a catalyst bed layer, wherein the reaction temperature is 350 ℃. After 8 hours of reaction time, the conversion of p-methoxytoluene was 85.3% and the molar yield of Anisotropic nitrile was 73.2%.
Cr prepared by comparative example 12V4O13As a catalyst, the conversion rate of p-methoxytoluene at the reaction temperature of 410 ℃ is only 65.3 percent, and the molar yield of the anisyl nitrile is 46.8 percent.
Cr prepared by comparative example 22V4O13As a catalyst, the conversion rate of p-methoxytoluene at the reaction temperature of 400 ℃ is 75.1%, and the molar yield of the anisyl nitrile is 56.9%.
Example 9
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 8g of nano Cr prepared in example 32V4O13Preheating and mixing 3-methylpyridine, ammonia gas and air according to a molar ratio of 1:7:25, and then reacting through a catalyst bed layer, wherein the reaction temperature is 325 ℃. After 8 hours of reaction time, the conversion of 3-methylpyridine was 97.3% and the molar yield of 3-cyanopyridine was 85.5%.
Cr prepared by comparative example 12V4O13As a catalyst, the molar yield of 3-cyanopyridine was 66.8% at a reaction temperature of 380 ℃.
Cr prepared by comparative example 22V4O13As a catalystThe molar yield of 3-cyanopyridine was 73.2% at 360 ℃.
Example 10
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 12g of nano Cr prepared in example 42V4O13Preheating and mixing paraxylene, ammonia gas and air according to the molar ratio of 1:11:40, and then reacting the mixture through a catalyst bed layer, wherein the reaction temperature is 360 ℃. After 8 hours of reaction time, the conversion of p-xylene was 98.6%, and the molar yield of terephthalonitrile was 86.7%.
Cr prepared by comparative example 12V4O13As a catalyst, the molar yield of terephthalonitrile at a reaction temperature of 390 ℃ was 71.3%.
Cr prepared by comparative example 22V4O13As a catalyst, the molar yield of terephthalonitrile at a reaction temperature of 380 ℃ was 77.1%.
Example 11
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 15g of nano Cr prepared in example 62V4O13Preheating and mixing 2, 6-dichlorotoluene, ammonia gas and air according to the molar ratio of 1:8:35, and then reacting through a catalyst bed layer, wherein the reaction temperature is 340 ℃. After 8 hours of reaction, the conversion of 2, 6-dichlorotoluene was 93.2%, and the molar yield of 2, 6-dichlorobenzonitrile was 76.1%.
Cr prepared by comparative example 12V4O13As a catalyst, the molar yield of 2, 6-dichlorobenzonitrile at 430 ℃ was 51.4%.
Cr prepared by comparative example 22V4O13As a catalyst, the molar yield of 2, 6-dichlorobenzonitrile at 400 ℃ was 61.8%.
Example 12
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 10g of nano Cr prepared in example 72V4O13Preheating and mixing 2-methylpyrazine, ammonia gas and air according to a molar ratio of 1:5:25, and then reacting through a catalyst bed layer, wherein the reaction temperature is 320 ℃. After 8 hours of reaction, the conversion of 2-methylpyrazine was 964% 2-cyanopyrazine in a molar yield of 81.8%.
Cr prepared by comparative example 12V4O13As a catalyst, the molar yield of 2-cyanopyrazine was 54.9% at a reaction temperature of 360 ℃.
Cr prepared by comparative example 22V4O13As a catalyst, the molar yield of 2-cyanopyrazine was 73.7% at a reaction temperature of 330 ℃.
Example 13
A quartz tube fixed bed reactor having an inner diameter of 30mm was charged with 20g of nano Cr prepared in example 52V4O13Preheating and mixing 2-chlorotoluene, ammonia gas and air according to a molar ratio of 1:5:25, and then reacting through a catalyst bed layer, wherein the reaction temperature is 380 ℃. After 8 hours of reaction time, the conversion of 2-chlorotoluene was 93.4%, and the molar yield of 2-chlorobenzonitrile was 78.8%.
Cr prepared by comparative example 12V4O13As a catalyst, the molar yield of 2-chlorobenzonitrile was 44.9% at a reaction temperature of 400 ℃.
Cr prepared by comparative example 22V4O13As a catalyst, the molar yield of 2-chlorobenzonitrile at 380 ℃ was 60.6%.
As can be seen from the above examples, the choice of solvent has a crucial influence on the structure of the product, and as can be seen from the comparative example 1 of example 2, regular nano Cr with hollow flower-spherical shape can not be obtained by using alcohol as solvent2V4O13. The inventor also adopts an aqueous solution of alcohol and a mixed solution of alcohol and aldehyde as solvents to carry out the solvothermal reaction, and can not obtain the nano Cr2V4O13However, when acid or its water solution is used as solvent, regular nano Cr with hollow flower ball shape can be obtained2V4O13. It can be seen from the above examples that the material obtained by coprecipitation has no regular morphology, large particle size, small specific surface area, and relatively low catalytic activity and catalyst activity of the product prepared by using alcohol as solvent, indicating that the morphology of the product has an important influence on its performanceAnd (6) sounding.
Claims (11)
1. Nano Cr2V4O13The material is characterized in that the nano Cr2V4O13The material is in a quasi-spherical hollow flower shape formed by stacking flaky nano particles, and the particle diameter of the flaky nano particles is as follows: the length is 100-500nm, the width is 20-100nm, and the thickness is 10-50 nm.
2. The nano Cr of claim 12V4O13A method for preparing a material, the method comprising the steps of:
1) mixing a vanadium source and a chromium source according to a metal atom molar ratio of 2:1, putting the mixture into a pressure container, adding a solvent, uniformly mixing, sealing, heating to 120-300 ℃, carrying out solvothermal reaction for 2-200 hours, and filtering, washing and vacuum-drying a product to obtain a precursor;
2) calcining the precursor at the temperature of 300-800 ℃ for 0.1-10 hours, and cooling to room temperature to obtain the nano Cr2V4O13。
3. The method of claim 2, wherein: the vanadium source is vanadium oxide and/or vanadium salt, and the chromium source is chromium oxide and/or chromium salt.
4. The production method according to claim 3, characterized in that: the vanadium oxide is V2O5、V2O4And V2O3At least one of, the vanadium salt is NH4VO3、VOSO4、VOCl2At least one of; the chromium oxide is Cr2O3And CrO3At least one of, the chromium salt is CrCl3、Cr(NO3)3And (NH)4)2Cr2O7At least one of (1).
5. The method of claim 2, wherein: the solvent of the solvothermal reaction is carboxylic acid or an aqueous solution thereof.
6. The method of claim 5, wherein:
the carboxylic acid is at least one of C1-C20 monobasic acid or polybasic acid, or an aqueous solution containing at least one of the foregoing acids.
7. The method of claim 6, wherein:
the carboxylic acid is at least one of formic acid, oxalic acid, citric acid, tartaric acid, malic acid, acetic acid and benzoic acid, or an aqueous solution containing at least one of the foregoing acids.
8. The method of claim 2, wherein: the pressure vessel is an autoclave or a pressure-resistant reactor.
9. The method of claim 2, wherein: the reaction temperature of the solvothermal reaction is 160-240 ℃, and the reaction time is 12-72 hours.
10. The nano Cr of claim 12V4O13The application of the catalyst in preparing aromatic nitrile by methyl aromatic ammoxidation.
11. Use according to claim 10, characterized in that: the methyl aromatic hydrocarbon comprises toluene, halogenated toluene, methoxytoluene, hydroxytoluene, nitrotoluene, cyanotoluene, aminotoluene, xylene, methylpyridine, methylpyrazine or methylpyrimidine.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102557135A (en) * | 2012-01-13 | 2012-07-11 | 中南民族大学 | Nanometer chromium vanadate as well as preparation method and application thereof |
| CN102838164A (en) * | 2012-09-27 | 2012-12-26 | 电子科技大学 | Preparation method of metal-ion-modified vanadium dioxide flower-like powder material |
| WO2013107079A1 (en) * | 2012-01-19 | 2013-07-25 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide composite powder and preparation method thereof |
| CN109704405A (en) * | 2019-02-28 | 2019-05-03 | 陕西师范大学 | A kind of preparation method of hollow flower ball-shaped vanadium disulfide |
-
2021
- 2021-04-26 CN CN202110464630.4A patent/CN113277561B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700909A (en) * | 2009-11-25 | 2010-05-05 | 中国科学技术大学 | Method of preparing intelligent energy-saving vanadium dioxide by hydrothermal method |
| CN102557135A (en) * | 2012-01-13 | 2012-07-11 | 中南民族大学 | Nanometer chromium vanadate as well as preparation method and application thereof |
| WO2013107079A1 (en) * | 2012-01-19 | 2013-07-25 | 中国科学院上海硅酸盐研究所 | Vanadium dioxide composite powder and preparation method thereof |
| CN102838164A (en) * | 2012-09-27 | 2012-12-26 | 电子科技大学 | Preparation method of metal-ion-modified vanadium dioxide flower-like powder material |
| CN109704405A (en) * | 2019-02-28 | 2019-05-03 | 陕西师范大学 | A kind of preparation method of hollow flower ball-shaped vanadium disulfide |
Non-Patent Citations (6)
| Title |
|---|
| ELZBIETA FILIPEK ET AL.: "Synthesis and some properties of the phase Cr2V4O13", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 265, pages 121 - 124, XP085621852, DOI: 10.1016/S0925-8388(97)00403-9 * |
| S.J. PATWE ET AL.: "Crystal structure,thermal and magnetic properties of Cr2V4O13", 《JOURNAL OF SOLID STATE CHEMISTRY》, vol. 183, no. 12, pages 2770 - 2778 * |
| 宋学琴等: "《配位化学》", 30 April 2013, 西南交通大学出版社, pages: 156 * |
| 谢光勇等: "芳香腈的制备研究进展", 《中南民族大学学报(自然科学版)》, vol. 39, no. 3, pages 225 * |
| 黄业迎等: "纳米钒铬复合氧化物的溶剂热合成、表征及催化2,6-二氯甲苯氨氧化反应(英文)", 《催化学报》 * |
| 黄业迎等: "纳米钒铬复合氧化物的溶剂热合成、表征及催化2,6-二氯甲苯氨氧化反应(英文)", 《催化学报》, vol. 39, no. 011, 5 November 2018 (2018-11-05), pages 1814 - 1820 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114308009A (en) * | 2021-12-17 | 2022-04-12 | 中南民族大学 | Micro-nano vanadium-molybdenum composite oxide and preparation method and application thereof |
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