CN116375091B - Method for stably preparing needle-like nano tungsten oxide - Google Patents
Method for stably preparing needle-like nano tungsten oxide Download PDFInfo
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- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 118
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 112
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 67
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 64
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000003723 Smelting Methods 0.000 abstract description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention belongs to the technical field of tungsten smelting, and in particular relates to a method for stably preparing needle-like nano tungsten oxide, which comprises the steps of taking a tungstate solution, hydrochloric acid and nitric acid for later use, adding the tungstate solution into the hydrochloric acid for later use in a dropwise manner, immediately dropwise adding nitric acid after tungstic acid is generated, stirring in the dropwise process, filtering and washing after dropwise adding, roasting and sieving the filtered and washed tungstic acid to obtain nano tungsten oxide, adding a control substance in the dropwise adding step in the preparation process, accurately controlling the adding amount, and preparing the needle-like nano tungsten oxide with controllable morphology (the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80 percent) and having wide industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of tungsten smelting, and particularly relates to a method for stably preparing needle-like nano tungsten oxide.
Background
The advantages of nano tungsten oxide compared to general tungsten oxide are represented by the following two aspects: 1. the specific surface area is larger, and more reaction surfaces are provided for physical and chemical reactions; 2. the quantum confinement effect due to the small particle size has an important influence on charge transport and optical characteristics. The performance of the material not only depends on the particle size and the specific surface area, but also is an important influencing factor. The controllable preparation of the shape of the nano material plays an important role in the research and development of the performance of the material. Tungsten oxide is widely applied to the fields of fuel cells, chemical sensors and the like due to good gas sensitivity and proton transfer capability, and the shapes of the nano tungsten oxide prepared by most of the current processes are different and do not have uniformity, but in the back-end application, the requirements on high-orientation low-latitude tungsten oxide are more and more increased in recent years, and how to stably prepare the nano tungsten oxide with controllable shapes under the conditions of no impurity and purity guarantee is a problem to be solved.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide a method for stably preparing needle-like nano tungsten oxide, wherein a control substance is added in a dripping step in the preparation process, and the addition amount is accurately controlled, so that the purity of the obtained product can reach high purity standard, the needle-like nano tungsten oxide can be prepared in a shape-controllable manner, and the industrialization prospect is wide.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
a method for stably preparing needle-like nano tungsten oxide, which comprises the following steps:
s1, taking tungstate solution for standby;
s2, taking hydrochloric acid for standby, wherein the volume of the hydrochloric acid is 1.2-2.0 times of that of the tungstate solution;
s3, taking nitric acid for standby, wherein the volume of the nitric acid is 1/10-1/5 of that of hydrochloric acid;
s4, adding the standby tungstate solution into standby hydrochloric acid in a dropwise adding mode, immediately dropwise adding nitric acid after tungstic acid is generated, and stirring in the dropwise adding process;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid at 550-850 ℃, and sieving to obtain nano tungsten oxide, wherein the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80%.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S1, the tungstate solution is a solution with the concentration of 200-300 g/L calculated by tungsten trioxide.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S2, the concentration of the hydrochloric acid is 15-36wt%.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S3, the concentration of the nitric acid is 15-18 mol/L.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S4, the time from the beginning of dropwise adding of the tungstate solution to the completion of dropwise adding of the nitric acid is 1-2 hours.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S4, the tungstate solution is added dropwise via a separating funnel.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S4, nitric acid is added dropwise through a brown separating funnel.
As a preferable scheme of the method for stably preparing the needle-like nano tungsten oxide, the invention comprises the following steps: in the step S6, the roasting time is 2-4 hours, and the screen mesh adopted by the screening is 120-160 meshes.
The needle-shaped nano tungsten oxide is prepared by adopting the method for stably preparing the needle-shaped nano tungsten oxide, wherein the proportion of the needle-shaped nano tungsten oxide in the nano tungsten oxide is more than or equal to 80 percent; the length-diameter ratio of the needle-meter-shaped nano tungsten oxide is 3-12, the average particle diameter is 20-100 nm, and the BET (specific surface area) is more than or equal to 8m 2 /g。
The beneficial effects of the invention are as follows:
the invention provides a method for stably preparing needle-like nano tungsten oxide, which is characterized in that a tungstate solution, hydrochloric acid and nitric acid are taken for standby, the standby tungstate solution is added into the standby hydrochloric acid in a dropwise manner, nitric acid is immediately dropwise added after tungstic acid is generated, stirring is carried out in the dropwise process, filtering and washing are carried out after the dropwise process is completed, the filtered and washed tungstic acid is roasted and sieved to obtain the nano tungsten oxide, a control substance is added in the dropwise process of the preparation process, the addition amount is accurately controlled, the purity of the obtained product can reach high purity standard (the purity of the nano tungsten oxide is more than or equal to 99.99 percent), and the needle-like nano tungsten oxide can also be prepared in a shape-controllable manner (the ratio of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80 percent), so that the method has wide industrialization prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the nano tungsten oxide needle-like particles prepared in example 1 of the present invention;
FIG. 2 is an SEM image of the nano-tungsten oxide needle-like particles prepared in example 2 of the present invention;
FIG. 3 is an SEM image of the nano-tungsten oxide needle-like particles prepared in example 3 of the present invention;
FIG. 4 is an SEM image of nano tungsten oxide prepared in comparative example 1;
FIG. 5 is an SEM image of nano-tungsten oxide prepared according to comparative example 2;
fig. 6 is an SEM image of nano tungsten oxide prepared in comparative example 3.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The main purpose of the invention is to provide a method for stably preparing needle-like nano tungsten oxide, which is characterized in that a control substance is added in the dripping step of the preparation process, and the addition amount is precisely controlled, so that the purity of the obtained product can reach high-purity standard, the needle-like nano tungsten oxide can be prepared in a shape-controllable manner, and the industrialization prospect is wide.
According to one aspect of the invention, the invention provides the following technical scheme:
a method for stably preparing needle-like nano tungsten oxide, which comprises the following steps:
s1, taking tungstate solution for standby;
s2, taking hydrochloric acid for standby, wherein the volume of the hydrochloric acid is 1.2-2.0 times of that of the tungstate solution;
s3, taking nitric acid for standby, wherein the volume of the nitric acid is 1/10-1/5 of that of hydrochloric acid;
s4, adding the standby tungstate solution into standby hydrochloric acid in a dropwise adding mode, immediately dropwise adding nitric acid after tungstic acid is generated, and stirring in the dropwise adding process;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid at 550-850 ℃, and sieving to obtain nano tungsten oxide, wherein the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80%.
Preferably, in the step S1, the tungstate solution is a solution with a concentration of 200-300 g/L calculated by tungsten trioxide. Specifically, the concentration may be, for example, but not limited to, any one or a range between any two of 200g/L, 210g/L, 220g/L, 230g/L, 240g/L, 250g/L, 260g/L, 270g/L, 280g/L, 290g/L, 300g/L, in terms of tungsten trioxide;
preferably, in the step S2, the concentration of the hydrochloric acid is 15-36wt%. In particular, the concentration of hydrochloric acid may be, for example, but not limited to, any one of 15wt%, 18wt%, 21wt%, 24wt%, 27wt%, 30wt%, 33wt%, 36wt% or a range between any two thereof; the volume of the hydrochloric acid may be, for example, but not limited to, any one of 1.2 times, 1.3 times, 1.4 times, 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, 2.0 times or a range between any two of the above;
preferably, in the step S3, the concentration of the nitric acid is 15-18 mol/L. Specifically, the concentration of nitric acid may be, for example, but not limited to, a range between any one or any two of 15mol/L, 15.5mol/L, 16mol/L, 16.5mol/L, 17mol/L, 17.5mol/L, 18mol/L; the volume of nitric acid may be, for example, but not limited to, any one or between any two of 1/10, 1/8, 3/20, 7/40, 1/5 of the volume of hydrochloric acid;
preferably, in the step S4, the standby tungstate solution is added into the standby hydrochloric acid in a dropwise manner, and nitric acid is immediately added dropwise after tungstic acid is generated, and stirring is performed during the dropwise process; the reason why the invention does not start to add the standby tungstate solution into the standby hydrochloric acid in a dropwise manner is that at the beginning stage of adding the standby tungstate solution into the standby hydrochloric acid in a dropwise manner, as the ion concentration does not reach the condition of forming the tungstic acid, nitric acid is wasted because nitric acid is added at the moment and cannot play a role of morphology control, nitric acid is immediately added dropwise after tungstic acid is generated, the morphology of the tungstic acid is controlled by nitric acid serving as a morphology auxiliary agent, nitric acid is added dropwise in the subsequent process of adding the tungstate solution, and the time of adding nitric acid dropwise is not earlier than the time of adding the tungstate solution dropwise, thereby being beneficial to preparing the needle-like nano tungsten oxide with controllable morphology. The time from the beginning of dropwise adding the tungstate solution to the completion of dropwise adding the nitric acid is 1-2 h. The time from the start of dropping the tungstate solution until the completion of dropping the nitric acid may be, for example, but not limited to, any one of 1h, 1.25h, 1.5h, 1.75h, 2h or a range between any two thereof;
preferably, in the step S4, the tungstate solution is added dropwise through a separating funnel, and the nitric acid is added dropwise through a brown separating funnel, and the brown separating funnel is opaque to light, so that the nitric acid is prevented from being decomposed;
preferably, in the step S6, the baking temperature may be, for example, but not limited to, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ or any range between any two of them; the roasting time is 2-4 hours, a 120-160 mesh screen is adopted for sieving, and the screen can be any one or any range between the two of 120 mesh, 130 mesh, 140 mesh, 150 mesh and 160 mesh; specifically, the firing temperature may be, for example, but not limited to, any one or a range between any two of 2h, 2.5h, 3h, 3.5h, 4h;
needle-like nano tungsten oxide prepared by adopting the above methodThe nano needle-shaped tungsten oxide is prepared by a method, and the ratio of the nano needle-shaped tungsten oxide to the nano tungsten oxide is more than or equal to 80 percent. Preferably, the ratio of the needle-shaped nano tungsten oxide to the nano tungsten oxide is more than or equal to 85%, and more preferably, the ratio of the needle-shaped nano tungsten oxide to the nano tungsten oxide is more than or equal to 90%. The length-diameter ratio of the needle-meter-shaped nano tungsten oxide is 3-12, the average particle diameter is 20-100 nm, and the BET (specific surface area) is more than or equal to 8m 2 /g; preferably, BET (specific surface area) of the needle-like nano tungsten oxide is more than or equal to 20m 2 /g; further preferably, BET (specific surface area) of the needle-like nano tungsten oxide is not less than 30m 2 /g; specifically, the aspect ratio of the needle-like nano tungsten oxide may be, for example, but not limited to, any one or any two of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, and the average particle diameter may be, for example, but not limited to, any one or any two of 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100 nm.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
A method for stably preparing needle-like nano tungsten oxide, which comprises the following steps:
s1, taking 200mL of tungstate solution for standby; the tungstate solution is a solution with the concentration of 250g/L based on tungsten trioxide;
s2, 400mL of hydrochloric acid is taken for standby, wherein the volume of the hydrochloric acid is 2.0 times of that of the tungstate solution; the concentration of hydrochloric acid is 30wt%;
s3, taking 80mL of nitric acid for standby, wherein the volume of the nitric acid is 1/5 of that of hydrochloric acid; the concentration of the nitric acid is 15mol/L;
s4, placing the standby tungstate solution into a separating funnel, adding the standby nitric acid into the brown separating funnel, adding the standby tungstate solution into the standby hydrochloric acid in a dropwise manner, immediately dropwise adding the nitric acid after tungstic acid is generated, and stirring in the dropwise adding process, wherein the time from the beginning of dropwise adding the tungstate solution to the completion of dropwise adding the nitric acid is 1h;
s5, filtering and washing after the dripping is completed;
s6, passingRoasting the filtered and washed tungstic acid for 3 hours at 700 ℃, and sieving the tungstic acid with a 120-mesh sieve to obtain nano tungsten oxide, wherein the purity of the nano tungsten oxide is 99.993%, the ratio of the needle-like nano tungsten oxide to the nano tungsten oxide is 88%, the length-diameter ratio of the nano tungsten oxide is 5-11, the average particle diameter is 63.7nm, and the specific surface area is 23m 2 /g, as shown in figure 1.
Example 2
A method for stably preparing needle-like nano tungsten oxide, which comprises the following steps:
s1, taking 200mL of tungstate solution for standby; the tungstate solution is a solution with the concentration of 300g/L based on tungsten trioxide;
s2, taking 240mL of hydrochloric acid for standby, wherein the volume of the hydrochloric acid is 1.2 times of that of the tungstate solution; the concentration of hydrochloric acid is 36wt%;
s3, taking 24mL of nitric acid for standby, wherein the volume of the nitric acid is 1/10 of that of hydrochloric acid; the concentration of the nitric acid is 18mol/L;
s4, placing the standby tungstate solution into a separating funnel, adding the standby nitric acid into the brown separating funnel, adding the standby tungstate solution into the standby hydrochloric acid in a dropwise manner, immediately dropwise adding the nitric acid after tungstic acid is generated, and stirring in the dropwise adding process, wherein the time from the beginning of dropwise adding the tungstate solution to the completion of dropwise adding the nitric acid is 2 hours;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid for 2 hours at 850 ℃, and sieving the tungstic acid with a 160-mesh sieve to obtain nano tungsten oxide, wherein the purity of the nano tungsten oxide is 99.995%, the ratio of the needle-like nano tungsten oxide to the nano tungsten oxide is 91%, the length-diameter ratio of the nano tungsten oxide is between 6 and 12, the average particle size is 48.4nm, and the specific surface area is 32m 2 /g, as shown in figure 2.
Example 3
A method for stably preparing needle-like nano tungsten oxide, which comprises the following steps:
s1, 160mL of tungstate solution is taken for standby; the tungstate solution is a solution with the concentration of 200g/L calculated by tungsten trioxide;
s2, taking 240mL of hydrochloric acid for standby, wherein the volume of the hydrochloric acid is 1.5 times of that of the tungstate solution; the concentration of hydrochloric acid is 15wt%;
s3, taking 30mL of nitric acid for standby, wherein the volume of the nitric acid is 1/8 of that of hydrochloric acid; the concentration of the nitric acid is 16mol/L;
s4, placing the standby tungstate solution into a separating funnel, adding the standby nitric acid into the brown separating funnel, adding the standby tungstate solution into the standby hydrochloric acid in a dropwise manner, immediately dropwise adding the nitric acid after tungstic acid is generated, and stirring in the dropwise adding process, wherein the time from the beginning of dropwise adding the tungstate solution to the completion of dropwise adding the nitric acid is 1.5 hours;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid for 4 hours at 550 ℃, and sieving the tungstic acid with a 120-mesh sieve to obtain nano tungsten oxide, wherein the purity of the nano tungsten oxide is 99.991%, the ratio of the needle-like nano tungsten oxide to the nano tungsten oxide is 86%, the length-diameter ratio of the nano tungsten oxide is 3-7, the average particle size is 27.2nm, and the specific surface area is 43m 2 /g, as shown in figure 3.
Comparative example 1
A method for preparing nano tungsten oxide, comprising the steps of:
s1, taking 200mL of tungstate solution for standby; the tungstate solution is a solution with the concentration of 250g/L based on tungsten trioxide;
s2, 400mL of hydrochloric acid is taken for standby, wherein the volume of the hydrochloric acid is 2.0 times of that of the tungstate solution; the concentration of hydrochloric acid is 30wt%;
s3, placing the standby tungstate solution into a separating funnel, adding the tungstate solution into standby hydrochloric acid in a dropwise adding mode, and stirring; the dripping time is 1h;
s4, filtering and washing after the dripping is completed;
s5, roasting the filtered and washed tungstic acid for 3 hours at 700 ℃, and sieving the tungstic acid by a 120-mesh sieve to obtain nano tungsten oxide, wherein the purity of the nano tungsten oxide is 99.99%, and the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is 19%, as shown in figure 4.
Comparative example 2
A method for preparing nano tungsten oxide, comprising the steps of:
s1, taking 200mL of tungstate solution for standby; the tungstate solution is a solution with the concentration of 250g/L based on tungsten trioxide;
s2, 400mL of hydrochloric acid is taken for standby, wherein the volume of the hydrochloric acid is 2.0 times of that of the tungstate solution; the concentration of hydrochloric acid is 30wt%;
s3, taking 80mL of nitric acid for standby, wherein the volume of the nitric acid is 1/5 of that of hydrochloric acid; the concentration of the nitric acid is 15mol/L;
s4, placing the standby tungstate solution into a separating funnel, adding the standby nitric acid into the brown separating funnel, adding the nitric acid into the standby hydrochloric acid in a dropwise manner, adding the tungstate solution in the dropwise manner after the nitric acid is dropwise added, and stirring; the time from the start of adding nitric acid dropwise to the completion of adding tungstate solution is 1h;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid for 3 hours at 700 ℃, and sieving the tungstic acid by a 120-mesh sieve to obtain nano tungsten oxide, wherein the nano tungsten oxide is irregular nano tungsten oxide, the purity of the nano tungsten oxide is 99.992%, and the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is 28%.
Comparative example 3
A method for preparing nano tungsten oxide, comprising the steps of:
s1, taking 200mL of tungstate solution for standby; the tungstate solution is a solution with the concentration of 250g/L based on tungsten trioxide;
s2, 400mL of hydrochloric acid is taken for standby, wherein the volume of the hydrochloric acid is 2.0 times of that of the tungstate solution; the concentration of hydrochloric acid is 30wt%;
s3, taking 80mL of nitric acid for standby, wherein the volume of the nitric acid is 1/5 of that of hydrochloric acid; the concentration of the nitric acid is 15mol/L;
s4, placing the standby tungstate solution into a separating funnel, adding standby nitric acid into the brown separating funnel, adding the standby nitric acid into standby hydrochloric acid in a dropwise manner to generate tungstic acid, filling the tungstic acid into a container, adding the nitric acid, and stirring; the time from the beginning of dropwise adding tungstate solution to the completion of dropwise adding nitric acid is 1h;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid for 3 hours at 700 ℃, and sieving the tungstic acid by a 120-mesh sieve to obtain nano tungsten oxide, wherein the nano tungsten oxide is irregular nano tungsten oxide, the purity of the nano tungsten oxide is 99.991%, and the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is 36% as shown in figure 6.
According to the invention, tungstate solution, hydrochloric acid and nitric acid are taken for standby, the standby tungstate solution is added into the standby hydrochloric acid in a dropwise manner, nitric acid is immediately added dropwise after tungstic acid is generated, stirring is carried out in the dropwise process, filtering and washing are carried out after the dropwise addition is completed, nano tungsten oxide is obtained after the filtering and washing are carried out, roasting and sieving of tungstic acid, a control substance is added in the dropwise addition step in the preparation process, the addition amount is accurately controlled, the purity of the obtained product can reach high purity standard (the purity of nano tungsten oxide is more than or equal to 99.99%), and needle-like nano tungsten oxide with controllable morphology (the proportion of needle-like nano tungsten oxide in nano tungsten oxide is more than or equal to 80%) can be prepared, so that the method has wide industrial prospect.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (5)
1. The method for stably preparing the needle-like nano tungsten oxide is characterized by comprising the following steps of:
s1, taking tungstate solution for standby; the tungstate solution is a solution with the concentration of 200-300 g/L based on tungsten trioxide;
s2, taking hydrochloric acid for standby, wherein the volume of the hydrochloric acid is 1.2-2.0 times of that of the tungstate solution; the concentration of the hydrochloric acid is 15-36wt%;
s3, taking nitric acid for standby, wherein the volume of the nitric acid is 1/10-1/5 of that of hydrochloric acid; the concentration of the nitric acid is 15-18 mol/L;
s4, adding the standby tungstate solution into standby hydrochloric acid in a dropwise adding mode, immediately dropwise adding nitric acid after tungstic acid is generated, and stirring in the dropwise adding process; the time from the beginning of dropwise adding the tungstate solution to the completion of dropwise adding the nitric acid is 1-2 hours;
s5, filtering and washing after the dripping is completed;
s6, roasting the filtered and washed tungstic acid at 550-850 ℃ for 2-4 hours; sieving to obtain nano tungsten oxide, wherein the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80%.
2. The method for stably producing nano-tungsten oxide according to claim 1, wherein in the step S4, the tungstate solution is added dropwise through a separating funnel.
3. The method for stably producing needle-like nano-tungsten oxide according to claim 1, wherein in the step S4, nitric acid is added dropwise through a brown separating funnel.
4. The method for stably preparing the needle-like nano tungsten oxide according to claim 1, wherein in the step S6, a 120-160 mesh screen is adopted for sieving.
5. The needle-like nano tungsten oxide is characterized in that the needle-like nano tungsten oxide is prepared by adopting the method for stably preparing the needle-like nano tungsten oxide according to any one of claims 1-4, wherein the proportion of the needle-like nano tungsten oxide in the nano tungsten oxide is more than or equal to 80%; the length-diameter ratio of the needle-like nano tungsten oxide is 3-12, the average particle diameter is 20-100 nm, and the specific surface area is more than or equal to 8m 2 /g。
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