CN110681395A - Cu with adjustable appearance and size+Doping with W18O49Composite material and preparation method thereof - Google Patents
Cu with adjustable appearance and size+Doping with W18O49Composite material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title description 12
- 239000002131 composite material Substances 0.000 claims abstract description 64
- 239000010949 copper Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 239000002070 nanowire Substances 0.000 claims abstract description 19
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 235000019441 ethanol Nutrition 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910003091 WCl6 Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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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Abstract
The invention discloses Cu with adjustable appearance and size+Doping with W18O49Composite material and method for its production, the composite material being assembled from nanowires, Cu+W doped in monoclinic system18O49In the crystal lattice, Cu accounts for 0.4-10% of the molar weight of W in terms of mole percent, wherein Cu+The doping amount can affect the size and shape of the nanowires in the composite material. The preparation method comprises the following steps: 1) mixing WCl6Dissolving in absolute ethyl alcohol; 2) adding copper chloride to WCl6Mixing in ethanol solution; 3) and carrying out solvent thermal reaction on the mixed solution, then naturally cooling to room temperature, and carrying out post-treatment to obtain the composite material. In the method, ethanol is used as a solvent and a reducing agent, and Cu2+Reduction to Cu+Post-doped in W18O49In, Cu is realized simultaneously+The doping and the regulation of the size and the shape of the nano-wire provide more choices for catalytic reaction.
Description
Technical Field
The invention belongs to the chemistryThe technical field of chemical industry, functional material and photocatalytic material preparation, in particular to Cu with adjustable appearance and size+Doping with W18O49Composite materials and methods for making the same.
Background
With the advance of the modernization process, the industrial civilization is rapidly developed, and the problems of environmental pollution and energy shortage are increasingly serious, so that the world faces a severe test at present. The rapid development of photocatalytic technology has become a potentially powerful means to address environmental and energy issues. However, a single semiconductor material generally exhibits poor activity due to intrinsic feature limitations of its own. Therefore, the method has important significance for modifying the semiconductor. Among many semiconductors, tungsten oxide has been widely studied as an important semiconductor material, and among them, non-stoichiometric tungsten oxide (W)18O49) Is an n-type semiconductor, has a band gap ranging from 1.6 to 2.9eV, and has a high absorption coefficient. And, W18O49A large number of oxygen vacancies exist, which can reduce the band gap and red-shift the absorption edge of the material, and can provide active sites to enhance the photocatalytic activity. Due to the above advantages W18O49Has great application potential in the field of catalysis. However, the application is limited by inherent defects such as low conduction band, instability under alkaline conditions and the like, and researches show that the application performance can be improved by metal doping or changing the morphological size.
Disclosure of Invention
The invention aims to provide Cu with adjustable appearance and size+Doping with W18O49Method for producing composite material, which can be carried out in W by simple operation18O49In which Cu is introduced+And the morphology and the size of the composite material can be regulated and controlled during doping, so that more choices are provided for catalytic reaction.
In order to solve the technical problems, the invention adopts the following technical scheme:
cu with adjustable appearance and size+Doping with W18O49A composite material assembled from nanowires,Cu+w doped in monoclinic system18O49In the crystal lattice, Cu accounts for 0.4-10% of the molar weight of W in terms of mole percentage.
In the scheme, when the molar weight of Cu is 0.4-2.5% of the molar weight of W in terms of mole percentage, the length of the nanowire in the composite material is 500-1000 nm, and the diameter of the nanowire is 25-40 nm; when Cu accounts for 2.5-10% of the molar weight of W, the length of the nanowire in the composite material is 50-500 nm, and the diameter of the nanowire is 25-40 nm.
Cu with adjustable appearance and size+Doping with W18O49The preparation method of the composite material specifically comprises the following steps:
1) mixing WCl6Dissolving in absolute ethyl alcohol;
2) adding copper chloride to WCl obtained in step 1)6Mixing in ethanol solution;
3) carrying out solvothermal reaction on the mixed solution in the step 2), naturally cooling to room temperature after the reaction is finished, and carrying out post-treatment to obtain the composite material.
In the above scheme, WCl in step 1)6The mass volume ratio of the alcohol to the absolute ethyl alcohol is 1-8 g/L.
In the scheme, the adding amount of the copper chloride is WCl in mole percentage60.4 to 10% by mole.
In the scheme, the solvothermal condition in the step 3) is that the reaction temperature is 160-200 ℃ and the reaction time is 8-12 h.
In the scheme, the post-treatment conditions in the step 3) are as follows: washing with water and absolute ethyl alcohol for 3 times respectively, and fully drying at 50-80 ℃.
The principle of the synthetic method of the invention is as follows: hydrothermal alcoholysis of tungsten hexachloride in anhydrous alcohol solution to produce W18O49Appearing as nanowires grown along the 010 crystal plane. When CuCl is present2When added into the system, the absolute ethyl alcohol has reducibility, and Cu2+Is reduced to Cu+，Cu+And W6+W is easily replaced by the similar ionic radius6+Successful doping into W18O49In (b) when Cu+When the doping amount reaches a certain amountThe growth of the 010 crystal face direction is interrupted, the nano wire is shortened, and the regulation and control of the shape and the size of the composite material can be simply and effectively realized. Wherein, mainly expressed as Cu+Doping amount to W18O49The feature size of (2) has a large influence when Cu+When the doping amount is less than 2.5%, the dimension of the nano-wire is not remarkably changed and the nano-wire is 500-1000 nm long; when the doping ratio reaches 5%, W18O49The dimension is obviously changed and gradually reduced along with the increase of the doping amount, and the structure is a short rod-shaped structure with the length of about 50-500 nm. In the synthetic method, absolute ethyl alcohol is used as a solvent and WCl6An alcoholysis reaction is carried out, and Cu is simultaneously present in the form of a reducing agent2+Reduction to Cu+The dual function of the method can provide reference for doping metals with different valence states.
The beneficial results of the invention are:
1. the invention uses Cu+As W18O49Doping element, synthesis of Cu+Doping with W18O49Composite material and simple and effective W pair through doping amount variation18O49The regulation and control of the shape and the size provide more choices for catalytic reaction, and can be applied to the fields of photocatalysis, electrocatalysis, gas sensitivity and the like.
2. The preparation method disclosed by the invention is simple in preparation process, convenient to operate, green and environment-friendly in production process, the synthesized catalyst is of a uniform nanowire structure in appearance, high in stability, and capable of meeting the actual production requirements and having a large application potential.
Drawings
FIG. 1 shows W obtained in comparative example 118O49And Cu obtained in example 1+Doping with W18O49An X-ray diffraction analysis (XRD) pattern of the composite;
FIG. 2 shows Cu obtained in example 1+Doping with W18O49An X-ray photoelectron spectroscopy (XPS) graph of the composite material, wherein the graph (a) is an XPS elemental analysis total spectrum, the graph (b) is an elemental Cu2p high-resolution XPS graph, the graph (c) is an O1s high-resolution XPS graph, and the graph (d) is a W4f high-resolution XPS graph;
FIG. 3 shows W obtained in comparative example 118O49Scanning Electron Microscopy (SEM) (fig. a), Transmission Electron Microscopy (TEM) (fig. b), and High Resolution Transmission Electron Microscopy (HRTEM) (fig. c).
FIG. 4 shows Cu obtained in example 1+Doping with W18O49SEM images (fig. a), TEM images (fig. b), and HRTEM (fig. c) of the composite material;
FIG. 5 shows Cu obtained in example 2+Doping with W18O49XRD pattern (panel a) and SEM pattern (panel b) of the composite material;
FIG. 6 shows Cu obtained in example 3+Doping with W18O49XRD pattern (panel a) and SEM pattern (panel b) of the composite material;
FIG. 7 shows Cu obtained in example 4+Doping with W18O49XRD pattern (panel a) and SEM pattern (panel b) of the composite material.
Detailed Description
The invention will be further described with reference to examples and drawings, to which the scope of the invention is not limited, but rather by the examples:
comparative example 1
Monomer W18O49The preparation method of the material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain a monomer W18O49A material.
FIG. 3 shows a monomer W obtained in this comparative example18O49SEM, TEM and HRTEM images of the material. FIG. (a) is an SEM photograph showing W synthesized in this comparative example18O49Is a nano linear structure with the length of about 500-1000 nm; FIG. (b) is a TEM image consistent with an SEM image showing nanowire-like structures about 500-1000 nm long and about 30nm in diameter; the HRTEM image in FIG. (c) shows that the lattice spacing is 0.38nm and the crystal grows along the 010 crystal plane.
Example 1
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.005mmol of copper chloride into the solution, uniformly dispersing by ultrasonic wave, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49The composite material, wherein Cu accounts for 2.5% of the molar weight of W in terms of mole percentage.
FIG. 1 shows Cu obtained in this example+Doping with W18O49XRD spectrum of the composite material. From FIG. 1, W can be seen18O49The diffraction peak of the standard spectrum JCPDS 71-2451 is consistent with that of the standard spectrum JCPDS, and the two standard diffraction peaks are positioned at 24 degrees and 47 degrees and are respectively W18O49010 and 020 crystal planes, and diffraction peaks in the composite material correspond to W18O49The peaks corresponding to 010 crystal planes and 020 crystal planes in the XRD spectrum of the Cu-doped composite material are not obviously shifted in the standard spectrum JCPDS 71-2451 probably because the Cu+And W6+Relatively close in ionic radius, Cu+(0.46)，W6+(0.41). In addition, no other impurity peaks appeared, indicating that monomer W of high purity was finally synthesized18O49And Cu doped W18O49A composite material.
FIG. 2 shows Cu obtained in this example+Doping with W18O49XPS spectra of the composites to further confirm the composition and valence state of the synthesized material. From the XPS total spectrum (a), it can be seen that the composite material synthesized in this example is composed of four elements, i.e., Cu, O, W, and C, where C is an element carbon introduced during the test, and the result further determines the elemental composition of the composite material. The Cu doped W synthesized in this example was analyzed by single element valence state18O49In the composite material, the bonding energy corresponding to the Cu element (figure b) is Cu2O, i.e. Cu+(ii) a The binding energy positions of the W elements (graph c) correspond to W5+And W6+Corresponding to a defective state W18O49And the binding energy sites of the O element (FIG. d) correspond to surface oxygen and W-O bonds, respectively.
FIG. 4 shows Cu prepared in this example+Doping with W18O49SEM, TEM and HRTEM images of the composite material. FIG. A is a SEM image showing that the composite material synthesized in the present example is a nanowire-like structure having a length of about 500 to 1000nm, and the monomer W of the comparative example18O49The materials are similar. The TEM image and the SEM image of the image (b) are consistent, and the nano-wire structure is represented by 500-1000 nm. FIG. (c) is a HRTEM image showing 0.38nm lattice spacing and growth along the 010 plane.
Example 2
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.002mmol of copper chloride into the solution, performing ultrasonic dispersion uniformly, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49The composite material, wherein Cu accounts for 1% of W mole amount according to mole percentage.
FIG. 5 is the XRD pattern and SEM pattern of the composite material synthesized in this example, as shown by W in the figure (a)18O49The diffraction peak is consistent with the standard map JCPDS 71-2451, and no other impurity peak appears, which indicates that the synthesized high-purity Cu+Doping with W18O49A composite material. FIG. (b) SEM picture shows synthesized Cu+Doping with W18O49The composite material is in a nano linear structure, and the length of the composite material is 0.5-1.0 um.
Example 3
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
0.2mmol of tungsten hexachloride was dissolved in 30mL of an anhydrous ethanol solution, and 0.01mmol of copper chloride was added to the above solutionUltrasonically dispersing the solution uniformly, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12 hours at the temperature of 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49The composite material wherein Cu is present in a molar percentage of 5% (mole percentage) of the molar amount of W.
FIG. 6 is an XRD pattern and SEM pattern of the composite material synthesized in this example, wherein W is shown in the figure (a)18O49The diffraction peak is consistent with the standard map JCPDS 71-2451, which indicates that Cu+Doping with W18O49And (4) successfully synthesizing the composite material. FIG. (b) SEM photograph showing synthesized Cu+Doping with W18O49The composite material is of a nano rod-shaped structure, and the length of the composite material is about 200-300 nm.
Example 4
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.02mmol of copper chloride into the solution, uniformly dispersing by ultrasonic wave, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49A composite material wherein Cu is present in a molar percentage of 10% (mole percentage) of the molar amount of W.
FIG. 7 is an XRD pattern and SEM pattern of the composite material synthesized in this example, wherein W is shown in the figure (a)18O49The diffraction peak of the compound is consistent with a standard spectrum JCPDS 71-2451. FIG. (b) SEM photograph showing synthesized Cu+Doping with W18O49The composite material is in a nano short rod-shaped structure, and the length of the composite material is about 50-200 nm.
Example 5
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride in 25mL of absolute ethanol solutionAdding 0.005mmol of copper chloride into the solution, uniformly dispersing by ultrasonic, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49A composite material.
Example 6
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.5mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.005mmol of copper chloride into the solution, uniformly dispersing by ultrasonic wave, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49A composite material.
Example 7
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.005mmol of copper chloride into the solution, uniformly dispersing by ultrasonic wave, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 12h at 160 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49A composite material.
Example 7
Cu+Doping with W18O49The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.005mmol of copper chloride into the solution, uniformly dispersing by ultrasonic wave, placing the reaction solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 8h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu+Doping with W18O49A composite material.
Claims (7)
1. Cu with adjustable appearance and size+Doping with W18O49Composite material, characterized in that the composite material is assembled from nanowires, Cu+W doped in monoclinic system18O49In the crystal lattice, Cu accounts for 0.4-10% of the molar weight of W in terms of mole percentage.
2. The topographically dimensionally adjustable Cu of claim 1+Doping with W18O49The composite material is characterized in that when Cu accounts for 0.4-2.5% of the molar weight of W in terms of mole percentage, the length of a nanowire in the composite material is 500-1000 nm, and the diameter of the nanowire is 25-40 nm; when Cu accounts for 2.5-10% of the molar weight of W, the length of the nanowire in the composite material is 50-500 nm, and the diameter of the nanowire is 25-40 nm.
3. The Cu with adjustable feature size of claim 1+Doping with W18O49The preparation method of the composite material is characterized by comprising the following steps:
1) mixing WCl6Dissolving in absolute ethyl alcohol;
2) adding copper chloride to WCl obtained in step 1)6Mixing in ethanol solution;
3) carrying out solvothermal reaction on the mixed solution in the step 2), naturally cooling to room temperature after the reaction is finished, and carrying out post-treatment to obtain the composite material.
4. The method of claim 3, wherein the WCl in step 1)6The mass volume ratio of the alcohol to the absolute ethyl alcohol is 1-8 g/L.
5. The process according to claim 3, wherein the amount of cupric chloride added is WCl in mol percent60.4 to 10% by mole.
6. The preparation method according to claim 3, wherein the solvothermal condition in the step 3) is a reaction temperature of 160-200 ℃ and a reaction time of 8-12 h.
7. The preparation method according to claim 3, wherein the post-treatment conditions of step 3) are as follows: washing with water and absolute ethyl alcohol for 3 times respectively, and fully drying at 50-80 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112138680A (en) * | 2020-09-15 | 2020-12-29 | 青岛亿恩方能源环保科技有限公司 | Gold nanoparticle/iron-doped tungsten oxide catalyst for removing formaldehyde at room temperature and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138649A (en) * | 2020-09-15 | 2020-12-29 | 青岛亿恩方能源环保科技有限公司 | Carbon dioxide thermal catalyst based on transition metal ion doped tungsten oxide and preparation method and application thereof |
| CN112138680A (en) * | 2020-09-15 | 2020-12-29 | 青岛亿恩方能源环保科技有限公司 | Gold nanoparticle/iron-doped tungsten oxide catalyst for removing formaldehyde at room temperature and preparation method and application thereof |
| CN112138680B (en) * | 2020-09-15 | 2023-03-10 | 青岛亿恩方能源环保科技有限公司 | Gold nanoparticle/iron-doped tungsten oxide catalyst for removing formaldehyde at room temperature and preparation method and application thereof |
| CN113058589A (en) * | 2021-03-31 | 2021-07-02 | 桂林理工大学 | Ce-doped W18O49Nanowire photocatalyst and preparation method thereof |
| CN115161005A (en) * | 2022-07-27 | 2022-10-11 | 武汉理工大学 | W with quick photochromic characteristic 18 O 49 Base nano material and preparation method and application thereof |
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