CN110681395B - Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof - Google Patents
Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110681395B CN110681395B CN201910982765.2A CN201910982765A CN110681395B CN 110681395 B CN110681395 B CN 110681395B CN 201910982765 A CN201910982765 A CN 201910982765A CN 110681395 B CN110681395 B CN 110681395B
- Authority
- CN
- China
- Prior art keywords
- composite material
- doping
- preparation
- wcl
- size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 30
- 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 18
- 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 14
- 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 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 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
- 238000004626 scanning electron microscopy Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 230000000052 comparative effect Effects 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
- 229910052760 oxygen Inorganic materials 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
- 238000001878 scanning electron micrograph Methods 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 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
- 239000008204 material by function 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
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 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
Images
Classifications
-
- 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
- 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
-
- 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—
-
- 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
Abstract
The invention discloses Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and method for its production, the composite material being assembled from nanowires, cu + W doped in monoclinic system 18 O 49 In 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 the shape of the nanowires in the composite material. The preparation method comprises the following steps: 1) WCl 6 Dissolving in absolute ethyl alcohol; 2) Adding copper chloride to WCl 6 Mixing 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 Cu 2+ Reduction to Cu + Post-doped in W 18 O 49 In, cu is realized simultaneously + The doping and the regulation and control of the size and the shape of the nano-wire provide more choices for catalytic reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of chemical engineering, functional materials and photocatalytic materials, and particularly relates to Cu with adjustable shape and size + Doping of W 18 O 49 Composite materials and methods for making the same.
Background
With the advance of the modernization process, the industrial civilization is rapidly developed at the same timeThe environmental pollution and energy shortage problem become serious increasingly, so that the world is faced with a serious 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) 18 O 49 ) Is an n-type semiconductor, has a band gap ranging from 1.6 to 2.9eV, and has a high absorption coefficient. And, W 18 O 49 A 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 W 18 O 49 Has 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 W 18 O 49 Method for producing composite material, which can be carried out in W by simple operation 18 O 49 In 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 problem, the invention adopts the following technical scheme:
cu with adjustable appearance and size + Doping with W 18 O 49 Composite material assembled from nanowires, cu + W doped in monoclinic system 18 O 49 In the crystal lattice, cu accounts for 0.4-10% of the molar weight of W in terms of mole percent.
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 nanowire in the composite material has the length of 50-500 nm and the diameter of 25-40 nm.
The Cu with adjustable appearance and size + Doping of W 18 O 49 The preparation method of the composite material specifically comprises the following steps:
1) Mixing WCl 6 Dissolving in absolute ethyl alcohol;
2) Adding copper chloride into WCl obtained in step 1) 6 Mixing 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) 6 The 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 percentage 6 0.4 to 10 percent of the molar weight.
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: washed by water and absolute ethyl alcohol for 3 times respectively, and fully dried at the temperature of 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 W 18 O 49 Appearing as nanowires grown along the 010 crystal plane. When CuCl is present 2 When added into the system, the absolute ethyl alcohol has reducibility, cu 2+ Is reduced to Cu + ，Cu + And W 6+ W is easily replaced by the similar ionic radius 6+ Successful doping into W 18 O 49 In (b) when Cu + When the doping amount reaches a certain amount, the growth of the 010 crystal face direction is interrupted, and the nanowire is shortened, so that the shape and the size of the composite material can be simply and effectively regulated. Wherein, mainly expressed as Cu + Doping amount to W 18 O 49 The feature size of (2) has a large influence when Cu + When the doping amount is less than 2.5 percent, the length of the doped alloy is 500 to EA 1000nm nanowire; when the doping ratio reaches 5%, W 18 O 49 The size is obviously changed and gradually reduced along with the increase of the doping amount, and the structure is represented by 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 WCl 6 An alcoholysis reaction is carried out, and Cu is simultaneously present in the form of a reducing agent 2+ Reduction to Cu + The dual function of the method can provide reference for doping of metals with different valence states.
The beneficial results of the invention are:
1. the invention uses Cu + As W 18 O 49 Doping element, synthesis of Cu + Doping with W 18 O 49 Composite material and realizes simple and effective W treatment through doping amount change 18 O 49 The 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, high in stability, capable of meeting the actual production requirement and large in application potential, and the synthesized catalyst is of a uniform nanowire structure.
Drawings
FIG. 1 shows W obtained in comparative example 1 18 O 49 And Cu obtained in example 1 + Doping with W 18 O 49 An X-ray diffraction analysis (XRD) pattern of the composite;
FIG. 2 shows Cu obtained in example 1 + Doping with W 18 O 49 An 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 1 18 O 49 Scanning 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 of W 18 O 49 CompoundingSEM images (fig. a), TEM images (fig. b) and HRTEM (fig. c) of the materials;
FIG. 5 shows Cu obtained in example 2 + Doping with W 18 O 49 XRD pattern (panel a) and SEM pattern (panel b) of the composite material;
FIG. 6 shows Cu obtained in example 3 + Doping with W 18 O 49 XRD pattern (fig. a) and SEM pattern (fig. b) of the composite material;
FIG. 7 shows Cu obtained in example 4 + Doping with W 18 O 49 XRD 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 the accompanying drawings, the scope of the invention is not limited to the examples:
comparative example 1
Monomer W 18 O 49 The 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 W 18 O 49 A material.
FIG. 3 shows a monomer W obtained in this comparative example 18 O 49 SEM, TEM and HRTEM images of the material. FIG. (a) is an SEM photograph showing W synthesized in this comparative example 18 O 49 Is a nano linear structure with the length of 500-1000 nm; FIG. (b) the TEM image is consistent with the SEM image and shows the nano-wire shaped structure with the length of about 500-1000 nm and the diameter of about 30 nm; FIG. (c) HRTEM image showed that the crystal lattice spacing was 0.38nm and the crystal was grown along the 010 crystal plane.
Example 1
Cu + Doping with W 18 O 49 The 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, and performing ultrasonic dispersion to obtain uniform solutionPlacing the reaction solution into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, reacting for 12h at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu + Doping with W 18 O 49 The 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 W 18 O 49 XRD spectrum of the composite material. From FIG. 1, W can be seen 18 O 49 The 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 W 18 O 49 010 and 020 crystal planes, and diffraction peaks in the composite material correspond to W 18 O 49 The 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 W 6+ Relatively close in ionic radius, cu + (0.46)，W 6+ (0.41). In addition, no other impurity peaks appeared, indicating that monomer W of high purity was finally synthesized 18 O 49 And Cu doped W 18 O 49 A composite material.
FIG. 2 shows Cu obtained in this example + Doping with W 18 O 49 XPS spectra of the composites to further confirm the composition and valence state of the synthesized material. From the XPS spectrogram (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 state 18 O 49 In the composite material, the bonding energy corresponding to the Cu element (figure b) is Cu 2 O, i.e. Cu + (ii) a The binding energy position of W element (figure c) corresponds to W 5+ And W 6+ Corresponding to a defective state W 18 O 49 And the binding energy positions of the O element (figure d) correspond to surface oxygen and W-O bonds, respectively.
FIG. 4 shows Cu prepared in this example + Doping with W 18 O 49 SEM, TEM and HRTEM images of the composite material. FIG. A is a SEM image, as shown in the figureThe composite material synthesized in this example is a nanowire-like structure with a length of about 500 to 1000nm, comparable to the monomer W of the comparative example 18 O 49 The materials are similar. FIG. (b) TEM image is consistent with SEM image, which shows nanowire structure of 500-1000 nm. FIG. (c) HRTEM image showed that the crystal lattice spacing was 0.38nm and the crystal was grown along the 010 crystal plane.
Example 2
Cu + Doping with W 18 O 49 The 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 W 18 O 49 The 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) 18 O 49 The 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 W 18 O 49 A composite material. FIG. (b) SEM shows the synthesized Cu + Doping with W 18 O 49 The 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 of W 18 O 49 The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 30mL of absolute ethyl alcohol solution, adding 0.01mmol 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 12 hours at 200 ℃, naturally cooling to room temperature, centrifuging, washing, drying and cooling to obtain Cu + Doping with W 18 O 49 A composite material wherein Cu is 5 mol% based on W% (mole percent).
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) 18 O 49 The diffraction peak is consistent with the standard map JCPDS 71-2451, which indicates that Cu + Doping of W 18 O 49 And (4) successfully synthesizing the composite material. FIG. (b) SEM photograph showing synthesized Cu + Doping with W 18 O 49 The 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 W 18 O 49 The 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 W 18 O 49 A 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) 18 O 49 The diffraction peak of the compound is consistent with a standard spectrum JCPDS 71-2451. FIG. (b) SEM photograph shows the synthesized Cu + Doping with W 18 O 49 The composite material is in a nanometer short rod-shaped structure, and the length of the composite material is about 50-200 nm.
Example 5
Cu + Doping of W 18 O 49 The preparation method of the composite material comprises the following steps:
dissolving 0.2mmol of tungsten hexachloride into 25mL 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 W 18 O 49 A composite material.
Example 6
Cu + Doping with W 18 O 49 The 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 of W 18 O 49 A composite material.
Example 7
Cu + Doping with W 18 O 49 The 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 W 18 O 49 A composite material.
Example 7
Cu + Doping with W 18 O 49 The 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 of W 18 O 49 A composite material.
Claims (6)
1. Cu with adjustable shape and size + Doping of W 18 O 49 Composite material, characterized in that the composite material is assembled from nanowires, cu + Doped in monoclinic systemW of (2) 18 O 49 In the crystal lattice, cu accounts for 0.4 to 10 percent of the molar weight of W in terms of molar percentage; wherein: when Cu accounts for 0.4 to 2.5 percent of the molar weight of W in terms of mole percentage, the length of a nanowire in the composite material is 500 to 1000nm, and the diameter of the nanowire is 25 to 40nm; when Cu accounts for 2.5 to 10 percent of the molar weight of W, the length of the nanowire in the composite material is 50 to 500nm, and the diameter of the nanowire is 25 to 40nm.
2. The Cu with adjustable feature size of claim 1 + Doping of W 18 O 49 The preparation method of the composite material is characterized by comprising the following steps:
1) WCl 6 Dissolving in absolute ethyl alcohol;
2) Adding copper chloride into WCl obtained in step 1) 6 Mixing 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.
3. The method of claim 2, wherein the WCl in step 1) is prepared by 6 The mass volume ratio of the alcohol to the absolute ethyl alcohol is 1 to 8g/L.
4. The process according to claim 2, wherein the amount of cupric chloride added is WCl in mole percent 6 0.4 to 10% of the molar amount.
5. The preparation method according to claim 2, wherein the solvothermal reaction conditions in step 3) are: the reaction temperature is 160 to 200 ℃, and the reaction time is 8 to 12h.
6. The preparation method according to claim 2, 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 under the conditions of 50 to 80 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982765.2A CN110681395B (en) | 2019-10-16 | 2019-10-16 | Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910982765.2A CN110681395B (en) | 2019-10-16 | 2019-10-16 | Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110681395A CN110681395A (en) | 2020-01-14 |
| CN110681395B true CN110681395B (en) | 2022-10-21 |
Family
ID=69112896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910982765.2A Active CN110681395B (en) | 2019-10-16 | 2019-10-16 | Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110681395B (en) |
Families Citing this family (3)
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0722114A2 (en) * | 2007-10-23 | 2014-04-08 | Sumitomo Metal Mining Co | PROTECTIVE MATERIAL FOR SOLAR RADIATION FOR VEHICLE WINDOW AND VEHICLE WINDOW |
| CN105271420A (en) * | 2015-10-27 | 2016-01-27 | 陕西科技大学 | Method for preparing nanoscale granular W18O49 material |
| CN105749912A (en) * | 2016-03-14 | 2016-07-13 | 中国海洋大学 | Multi-morphology metal-doped W18O49 electrocatalyst and application thereof to hydrogen production by water electrolysis |
-
2019
- 2019-10-16 CN CN201910982765.2A patent/CN110681395B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0722114A2 (en) * | 2007-10-23 | 2014-04-08 | Sumitomo Metal Mining Co | PROTECTIVE MATERIAL FOR SOLAR RADIATION FOR VEHICLE WINDOW AND VEHICLE WINDOW |
| CN105271420A (en) * | 2015-10-27 | 2016-01-27 | 陕西科技大学 | Method for preparing nanoscale granular W18O49 material |
| CN105749912A (en) * | 2016-03-14 | 2016-07-13 | 中国海洋大学 | Multi-morphology metal-doped W18O49 electrocatalyst and application thereof to hydrogen production by water electrolysis |
Non-Patent Citations (4)
| Title |
|---|
| Ce-Doped bundled ultrafine diameter tungsten oxide nanowires with enhanced electrochromic performance;Kunyapat Thummavichai et al;《NANOSCALE》;20180131;第10卷(第10期);第4718-4726页 * |
| P-type conductivity and NO2 sensing properties for V-doped W18O49 nanowires at room temperature01;Qin Yu-Xiang et al;《ACTA PHYSICA SINICA》;20131031;第62卷(第20期);第208104页 * |
| Synthesis of transition metal-doped tungsten oxide nanostructures and their optical properties;Chang, Xueting et al;《MATERIALS LETTERS》;20110615;第65卷(第11期);第1710-1712页 * |
| 钒掺杂W18O49纳米线的室温p型电导与NO2敏感性能;秦玉香 等;《物理学报》;20131023;第1-7页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110681395A (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110681395B (en) | Cu with adjustable appearance and size + Doping with W 18 O 49 Composite material and preparation method thereof | |
| Xiang et al. | Bimetallic Pd-Ni core-shell nanoparticles as effective catalysts for the Suzuki reaction | |
| Huang et al. | 3D nanospherical CdxZn1− xS/reduced graphene oxide composites with superior photocatalytic activity and photocorrosion resistance | |
| CN106077695B (en) | A kind of preparation method of high-copper tungsten copper nano composite powder | |
| KR20100082609A (en) | Method for preparing metal compound powders | |
| CN109422294B (en) | Preparation method of size-controllable cobaltosic oxide nanoparticles | |
| Peng et al. | Synthesis, characterization and photocatalytic activity of Zn (OH) F hierarchical nanofibers prepared by a simple solution-based method | |
| CN108187699B (en) | BiOX-Bi4O5X2Heterojunction and preparation method and application thereof | |
| CN107433203B (en) | Z-Scheme composite system, preparation method and application | |
| CN111333117A (en) | Preparation of cupronickel type structure CuFeO2Method for preparing biochar composite material | |
| CN103877966A (en) | Preparation method of heterostructure photocatalyst | |
| CN108339562B (en) | Preparation method of iron ion doped carbon nitride nanotube and obtained product | |
| CN108212186B (en) | A kind of room temperature solid-state reaction prepares bismuth oxide-bismuthyl carbonate nano-complex method | |
| CN113600223B (en) | Fe (Fe) 2 P/nitrogen vacancy g-C 3 N 4 Preparation method and application of nanosheet photocatalyst | |
| CN108017086B (en) | Preparation method of bismuth oxycarbonate-graphene oxide nano compound | |
| CN108262051B (en) | Method for synthesizing cerium dioxide-bismuthyl carbonate nano composite by mechanical ball milling heat treatment two-step method | |
| CN110180523A (en) | A kind of non-metal porous carbon nanocatalyst and preparation method thereof | |
| CN114733540B (en) | Nanoscale carbon-coated Mo-Mo 2 Heterogeneous nanoparticle of C and preparation method and application thereof | |
| CN114210337B (en) | Nickel copper tungstate nano heterojunction particles, preparation method thereof and application of nickel copper tungstate nano heterojunction particles in catalytic hydrogen production | |
| CN114082972B (en) | Method for green preparation of Rh ultrathin nanosheets and low crystallinity nanoparticles | |
| CN1431146A (en) | Method for preparing powder of nano vanadium nitride in cubic phase | |
| CN101260564A (en) | Method for preparing micron/nano tungsten oxide crystal whisker/wire/bar | |
| CN114377709A (en) | Hydrothermal method for preparing CeO2/Ce(OH)CO3Method of heterojunction | |
| CN106694898A (en) | Method for preparing various-shape metal copper nano materials through low heat solid phase chemical reaction | |
| CN1191201C (en) | Preparation of nano copper chromite using microemulsion method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |