CN117899864A - Method for preparing copper-loaded black titanium dioxide at room temperature and copper-loaded black titanium dioxide - Google Patents
Method for preparing copper-loaded black titanium dioxide at room temperature and copper-loaded black titanium dioxide Download PDFInfo
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- CN117899864A CN117899864A CN202410295140.XA CN202410295140A CN117899864A CN 117899864 A CN117899864 A CN 117899864A CN 202410295140 A CN202410295140 A CN 202410295140A CN 117899864 A CN117899864 A CN 117899864A
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- titanium dioxide
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- black titanium
- room temperature
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 354
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 174
- 239000010949 copper Substances 0.000 title claims abstract description 140
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 26
- 229910052724 xenon Inorganic materials 0.000 claims description 25
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- 238000005303 weighing Methods 0.000 description 16
- 239000002105 nanoparticle Substances 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 12
- 229910001431 copper ion Inorganic materials 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 238000001132 ultrasonic dispersion Methods 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000001678 irradiating effect Effects 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001879 copper Chemical class 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002256 photodeposition Methods 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- 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
- B01J23/72—Copper
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of photocatalytic materials, and discloses a method for preparing copper-loaded black titanium dioxide at room temperature and the copper-loaded black titanium dioxide. S1, adding cupric salt and titanium dioxide into a solvent, and then mixing to obtain a mixed material; s2, carrying out illumination reaction on the mixed material under stirring, and then separating and purifying to obtain copper-loaded titanium dioxide; and S3, mixing the copper-loaded titanium dioxide with borohydride in a solvent system, and grinding to obtain the copper-loaded black titanium dioxide. The preparation method does not need high temperature, has simple process flow, and can obtain the copper-loaded black titanium dioxide with good light absorption and photocatalysis performances under normal-temperature grinding.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a method for preparing copper-loaded black titanium dioxide at room temperature and the copper-loaded black titanium dioxide.
Background
The traditional titanium dioxide photocatalytic material is white powder, can only absorb ultraviolet light and is excited to generate photo-generated charges, so that the effect of photocatalytic oxidation or photoelectric conversion is achieved, and most of energy sources in sunlight cannot be fully utilized. Compared with the common TiO 2 nano material, the black TiO 2 nano material has a unique crystal core/non-crystal core shell structure. The black TiO 2 nano material optimizes the electronic energy level structure of the TiO 2 by introducing lattice defects to improve the crystal structure, shortens the forbidden bandwidth, improves the optical performance, and expands the light response range from the ultraviolet region to the infrared region, so that the black TiO 2 nano material has wide application in the energy and environment fields.
However, the preparation of the black TiO 2 nanomaterial requires the participation of high temperature and high pressure and a reducing gas. The process is complex and dangerous, and is not suitable for large-scale preparation, and with the deep research, other methods such as chemical reduction, chemical oxidation, electrochemical reduction and the like are also proposed, but all have the problems of high preparation temperature and long preparation time. For example, chinese patent CN111573721a discloses a preparation method of black titanium dioxide, chinese patent CN110813280a discloses a black titanium dioxide photocatalyst with high dispersion platinum-loaded surface modification, a preparation method and application thereof, however, the preparation method of the black titanium dioxide needs high-temperature heating, and has the problems of high preparation temperature and long preparation time. In view of the above, how to ensure that a black TiO 2 nanomaterial with good light absorption and photocatalytic properties is obtained at a lower reaction temperature is a current urgent problem to be solved.
Disclosure of Invention
The application is used for solving the technical problem of higher preparation temperature of black titanium dioxide in the prior art.
Accordingly, a first object of the present invention is to provide a method for producing copper-supported black titanium dioxide at room temperature, which produces copper-supported black titanium dioxide having good light absorption and photocatalytic performance by a method of grinding only at room temperature without requiring a high temperature.
Specifically, a method for preparing copper-loaded black titanium dioxide at room temperature comprises the following steps:
s1, adding cupric salt and titanium dioxide into a solvent, and then mixing to obtain a mixed material;
s2, carrying out illumination reaction on the mixed material under stirring, and then separating and purifying to obtain copper-loaded titanium dioxide;
and S3, mixing the copper-loaded titanium dioxide with borohydride in a solvent system, and grinding to obtain the copper-loaded black titanium dioxide.
Further, the mass concentration of the cupric salt in the mixed material is 0.5-1.5g/L.
Further, in the mixed material, the mass concentration of the titanium dioxide is 5-20g/L.
Further, the mass ratio of the copper-loaded titanium dioxide to the borohydride is 1 (0.5-1.5).
Further, the grinding time is 15-45min.
Further, the photoreaction uses a 300W xenon lamp for 30-90min.
Further, the wavelength range of the xenon lamp is the full wavelength of the xenon lamp, and the current is 12-18A.
Further, the stirring speed is 500-1000r/min.
Further, the solvent comprises one or more of methanol, ethanol, propanol and isopropanol.
The technical mechanism is as follows:
(1) Copper-loaded titanium dioxide is prepared by a photo-deposition method, and copper-loaded titanium dioxide powder and NaBH 4 are mixed and ground (a small amount of water is added) to obtain copper-loaded black titanium dioxide.
(2) The borohydride has strong reducibility, the loaded copper nano particles (2-5 nm) can easily obtain oxygen, a new interface is generated at the contact position by the load, the new interface energy is high, the reaction is easy to occur, the strong reducibility of the borohydride damages the surface structure of titanium dioxide at the interface position in the grinding process, so that the oxygen is firstly transferred to the copper nano particles (CuO or CuO 2), oxygen vacancies are generated on the surface of the titanium dioxide to form black titanium dioxide, and then the residual borohydride reduces the oxide of copper back to Cu, so that the black titanium dioxide loaded by copper is finally obtained.
A second object of the present invention is to provide copper-loaded black titanium dioxide prepared by the method according to any one of the embodiments of the first object, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2 to 5nm.
The beneficial effects of the application are as follows:
The application provides a method for preparing copper-loaded black titanium dioxide at room temperature, which comprises the steps of firstly preparing copper-loaded titanium dioxide by using a photo-deposition method, then destroying the surface structure of the titanium dioxide in the grinding process by using borohydride with strong reducibility, leading oxygen to be transferred to copper nano particles, generating oxygen vacancies on the surface of the titanium dioxide to form black titanium dioxide, and reducing the oxide of copper back to Cu by using the residual borohydride to finally obtain the copper-loaded black titanium dioxide. The preparation method does not need high temperature, has simple process flow, and can obtain the copper-loaded black titanium dioxide with good light absorption and photocatalysis performances under normal-temperature grinding.
Drawings
Fig. 1 is a photograph of titanium dioxide (a), copper-supported titanium dioxide (b), copper-supported black titanium dioxide (c) provided in example 1 of the present application;
FIG. 2 is an XRD pattern for copper-loaded black titanium dioxide provided in example 1 of the present application;
FIG. 3 is a TEM image of copper-loaded black titanium dioxide provided in example 1 of the present application;
FIG. 4 is an EPR diagram of copper-loaded black titanium dioxide according to example 1 of the present application;
FIG. 5 is an ultraviolet-visible light absorption spectrum of copper-loaded black titanium dioxide provided in example 1 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
First, the present invention provides a method for preparing copper-loaded black titanium dioxide at room temperature, the method comprising the steps of:
s1, adding cupric salt and titanium dioxide into a solvent, and then mixing to obtain a mixed material;
In the invention, the mass concentration of the cupric salt in the mixed material is 0.5-1.5g/L.
In the invention, the mass concentration of the cupric salt in the mixed material is 1g/L.
In an embodiment of the invention, the amount of copper salt determines the concentration of copper ions in the solution, which affects the loading of copper particles on the surface of the final titanium dioxide. If the concentration is too high, after a certain limit is reached, the copper nano particles generated by reduction are attached to the surface of the titanium dioxide, so that the subsequent reaction is prevented; if the concentration is too small, the reaction is insufficient. The concentration is thus limited to a certain range.
In the present invention, the cupric salt includes one or more of cupric chloride, cupric sulfate and cupric nitrate.
In the embodiment of the invention, titanium dioxide is added into the solution rich in copper ions as a photocatalyst, and only copper ions participate in the reaction from the viewpoint of reduction principle, and only copper ions are needed to be rich in the solution, so that the copper salt can be one or more of copper chloride, copper sulfate and copper nitrate.
In the invention, the mass concentration of the titanium dioxide in the mixed material is 5-20g/L.
In the invention, the mass concentration of the titanium dioxide in the mixed material is 10g/L.
In embodiments of the invention, the mass concentration of titanium dioxide is dependent on the mass of material desired, while to some extent affecting the rate of reaction, too little photocatalyst may take more time to reduce copper ions.
In the invention, the solvent comprises one or more of methanol, ethanol, propanol and isopropanol.
In the invention, the solvent is a mixed solvent of ethanol and methanol, and the volume ratio of the ethanol to the methanol in the mixed solvent is (2-6): 1.
In the invention, the volume ratio of ethanol to methanol in the mixed solvent is 4:1.
In embodiments of the present invention, the type of solvent may be determined based on the solubility of the copper salt and the surface properties of the titanium dioxide. The solvent is selected to satisfy the following conditions: copper salts can be dissolved; the titanium dioxide powder can be uniformly dispersed in the solvent. Thus, alcohols may be selected as solvents in the present invention.
In the invention, the mixing comprises ultrasonic dispersion for 10-20min and stirring at a speed of 600-800r/min for 20-30min.
S2, carrying out illumination reaction on the mixed material under stirring, and then separating and purifying to obtain copper-loaded titanium dioxide;
In view of this, the present inventors found that the cupric salt was reduced to nano copper particles and adhered to the surface of the titanium dioxide powder by subjecting the mixture to a photoreaction under stirring.
In the invention, the stirring rotating speed is 500-1000r/min.
In the invention, the stirring rotating speed is 700r/min.
In the present invention, the photoreaction is performed using a 300W xenon lamp for 30-90min.
In the invention, the wavelength range of the xenon lamp is the full wavelength of the xenon lamp, and the current is 12-18A.
In the embodiment of the invention, the illumination time and intensity also influence the speed of the photocatalytic reaction, and too low light intensity or too short time can lead to insufficient reduction of copper ions, so that the load capacity is low and the raw material is wasted. When copper ions in the solution are basically reacted, the copper ions are useless for too long, and waste of resources is caused, so that the illumination time and intensity need to be controlled within proper ranges.
In the present invention, the purification includes washing and drying.
In view of this, the present inventors have found that copper-supported titanium dioxide is first prepared using a photo-deposition method, at which time a cupric salt is reduced to nano-copper particles and attached to the surface of the titanium dioxide powder, and the product is yellowish green powder in color.
And S3, mixing the copper-loaded titanium dioxide with borohydride in a solvent system, and grinding to obtain the copper-loaded black titanium dioxide.
In the invention, the mass ratio of the titanium dioxide loaded with copper to the borohydride is 1 (0.5-1.5).
In the invention, the mass ratio of the copper-loaded titanium dioxide to the borohydride is 1:1.
In the embodiment of the invention, the mass ratio of the borohydride to the titanium dioxide determines the reduction degree, and the proper mass ratio can ensure that particles of the borohydride and the titanium dioxide are fully contacted, so that the waste of the reducing agent (borohydride) is not caused while the reaction is ensured.
In the invention, the borohydride comprises one or more of sodium borohydride and potassium borohydride.
In the invention, the grinding time is 15-45min.
In the embodiment of the present invention, the polishing time determines whether or not the reaction is sufficient, and the polishing method can only react on the copper-supported titanium dioxide surface, and there is no more strong effect even when the reaction is completed and the polishing time needs to be controlled in a proper range.
In view of this, the present inventors found that in the prior art, borohydride and titanium dioxide were thoroughly mixed and calcined at 300 c, thereby obtaining copper-supported black titanium dioxide. The principle of the prior art is that NaBH 4 is used as a reducing agent to decompose and generate strong reducing gas (active hydrogen) at high temperature, so that the titanium dioxide has stronger oxidizing property, and the structure of the titanium dioxide surface is destroyed (oxygen is extracted) so as to generate defects (oxygen vacancies) on the surface. In the present application, however, copper-supported titanium dioxide powder and NaBH 4 were mixed and ground (small amount of water was added) to obtain copper-supported black titanium dioxide. The borohydride has strong reducibility, the loaded copper nano particles (2-5 nm) can easily obtain oxygen, a new interface is generated at the contact position by the load, the new interface energy is high, the reaction is easy to occur, the strong reducibility of the borohydride damages the surface structure of titanium dioxide at the interface position in the grinding process, so that the oxygen is firstly transferred to the copper nano particles (CuO or CuO 2), oxygen vacancies are generated on the surface of the titanium dioxide to form black titanium dioxide, and then the residual borohydride reduces the oxide of copper back to Cu, so that the black titanium dioxide loaded by copper is finally obtained.
The specific mechanism of the invention is summarized as follows: the preparation of copper-loaded titanium dioxide adopts a photo-deposition method, and is a method for catalyzing metal ions to reduce into nano particles by using a light source. The basic principle of the method is that copper ions are reduced into copper atoms under the action of a catalyst through the excitation action of a light source, and the copper ions are promoted to be gradually aggregated to form nano particles. The concrete description is as follows: under the action of light, active oxide and electron hole pairs on the surface of titanium dioxide can be excited to generate. Reactive oxides such as hydroxyl radicals (.oh) and superoxide radicals (.o2-), as well as electron-hole pairs, can participate in subsequent reduction reactions. The generated active oxide and electron-hole pairs participate in the reduction reaction of copper ions. The electron-hole pairs oxidize the reducing agent in the solution to reactive radicals, and the reactive oxides react with copper ions to reduce them to copper atoms. Copper atoms are aggregated to form nano particles attached to the surfaces of titanium dioxide particles through a reduction reaction. The surface of the titanium dioxide is conducive to the formation and stabilization of the nanoparticles, and the size and distribution of the nanoparticles can be regulated. The morphology, size and distribution of the copper nano particles can be controlled by regulating and controlling the components of the solution, the energy of the light source, the irradiation time and other conditions.
Second, the present invention provides copper-loaded black titanium dioxide having a particle diameter of 2 to 5nm.
In view of the above, the inventor discovers that the copper-loaded black titanium dioxide prepared by the method has good light absorption and photocatalysis performances, and can be applied to the technical fields of photocatalysis, lithium ion batteries, super capacitors, fuel cells, photoelectric sensors and the like.
< Example >
Example 1
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper chloride and 1g of titanium dioxide, and adding the mixture into a beaker filled with a mixed solvent of 80ml of ethanol and 20ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
S21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process (700 r/min), and washing and drying the beaker to obtain titanium dioxide loaded with copper;
S31, weighing and mixing sodium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep wet, grinding in a mortar for 30min, washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2nm. The obtained samples were subjected to XRD, EPR, TEM and light absorption performance analysis, and the results are shown in FIGS. 2 to 5.
Example 2
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 50mg of copper nitrate and 1g of titanium dioxide, and adding the mixture into a beaker filled with 100ml of ethanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
S21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process (700 r/min), and washing and drying the beaker to obtain titanium dioxide loaded with copper;
S31, weighing and mixing potassium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep wet, grinding in a mortar for 30min, and washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2nm.
Example 3
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 150mg of copper chloride and 1g of titanium dioxide, and adding the mixture into a beaker filled with a mixed solvent of 80ml of ethanol and 20ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process (800 r/min), and washing and drying the beaker to obtain copper-loaded titanium dioxide;
s31, weighing and mixing sodium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep wet, grinding in a mortar for 30min, washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 3nm.
Example 4
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper nitrate and 1.5g of titanium dioxide, and adding the mixture into a beaker filled with a mixed solvent of 80ml of ethanol and 20ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 18A), stirring the beaker in the whole process (700 r/min), and washing and drying the beaker to obtain titanium dioxide loaded with copper;
S31, weighing and mixing sodium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep wet, grinding in a mortar for 30min, washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 4nm.
Example 5
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper chloride and 1g of titanium dioxide, and adding the mixture into a beaker filled with a mixed solvent of 80ml of ethanol and 20ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process, and washing and drying the beaker to obtain copper-loaded titanium dioxide;
S31, weighing and mixing potassium borohydride with the mass of the copper-loaded titanium dioxide being 1:0.8, adding a small amount of deionized water to keep moist, grinding for 30min in a mortar, and washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 5nm.
Example 6
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper nitrate and 1g of titanium dioxide, and adding the mixture into a beaker filled with 100ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process, and washing and drying the beaker to obtain copper-loaded titanium dioxide;
S31, weighing and mixing sodium borohydride with the mass of the copper-loaded titanium dioxide of 1:1.2, adding a small amount of deionized water to keep moist, grinding for 30min in a mortar, and washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2nm.
Example 7
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper sulfate and 1g of titanium dioxide, and adding the mixture into a beaker filled with a mixed solvent of 80ml of ethanol and 20ml of methanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process, and washing and drying the beaker to obtain copper-loaded titanium dioxide;
S31, weighing and mixing sodium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep moist, grinding for 45min in a mortar, and washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2nm.
Example 8
The method for preparing copper-loaded black titanium dioxide at room temperature provided by the embodiment comprises the following steps:
S11, weighing 100mg of copper sulfate and 1g of titanium dioxide, and adding the mixture into a beaker filled with 100ml of propanol. Placing the beaker in an ultrasonic device for ultrasonic dispersion for 15 minutes, and stirring (700 r/min) under a stirrer to fully mix;
s21, irradiating the beaker under a 300W xenon lamp for one hour (the wavelength range is the full wavelength of the xenon lamp; the current is 15A), stirring the beaker in the whole process, and washing and drying the beaker to obtain copper-loaded titanium dioxide;
S31, weighing and mixing potassium borohydride with the mass of the copper-loaded titanium dioxide being 1:1, adding a small amount of deionized water to keep wet, grinding in a mortar for 15min, and washing and drying to obtain the copper-loaded black titanium dioxide, wherein the particle size of copper particles on the surface of the copper-loaded black titanium dioxide is 2nm.
Detailed description of the drawings 1-5:
fig. 1 is a photograph of titanium dioxide (a), copper-supported titanium dioxide (b), and copper-supported black titanium dioxide (c) provided in example 1 of the present application.
As can be seen from FIG. 1, the titanium dioxide is white, the copper-loaded titanium dioxide is yellow-green powder, the copper-loaded black titanium dioxide is black powder, and the experiment proves that the prepared copper-loaded black titanium dioxide is truly copper-loaded.
Fig. 2 is an XRD pattern of copper-loaded black titania provided in example 1 of the present application.
As can be seen from fig. 2, XRD results show that the peak intensity of the Cu-supported black titania prepared by this method is reduced, and the increase in peak intensity of Cu after grinding can be attributed to partial oxidation of copper during the preparation process and reduction thereof by the reducing agent during the grinding process. The decrease in peak intensity of titanium dioxide corresponds to the transmitted disordered layer, and is also a proof that the preparation of black titanium dioxide is successful, and the increase in peak intensity of Cu can be considered as a certain oxidation of the loaded copper before cleaning and reduction, and the reduction process reduces the oxide of copper back to copper.
Fig. 3 is a TEM image of copper-loaded black titania provided in example 1 of the present application.
As can be seen from fig. 3, d is the interplanar spacing, and specific crystal planes can be deduced from the results of TEM and XRD. When d=0.35 nm, the (101) crystal plane denoted as TiO 2; when d=0.21 nm, the (111) plane is expressed as Cu. The Cu-loaded black titanium dioxide prepared by the method is shown, cu nano particles are uniformly loaded on the surface of the black titanium dioxide, and a certain amorphous layer appears on the surface of the black titanium dioxide. Thus, it can be seen from the TEM results that significant copper nanoparticle loading occurs and a significant (1-2 nm) disordered layer appears at the edges, except for a thinner layer thickness.
Fig. 4 is an EPR diagram of copper-loaded black titanium dioxide provided in example 1 of the present application.
As can be seen from FIG. 4, EPR results indicate that the Cu-supported black titanium dioxide prepared by this method has a distinct peak of oxygen vacancies. Characterization of oxygen vacancies also showed peaks that supported copper nanoparticles and had distinct oxygen vacancies after milling reduction, demonstrating successful production of black titanium dioxide.
FIG. 5 is an ultraviolet-visible light absorption spectrum of copper-loaded black titanium dioxide provided in example 1 of the present application.
As can be seen from fig. 5, the copper-loaded black titanium dioxide (after grinding) has good ultraviolet light absorption performance compared with titanium dioxide (P25, representing a commercial grade titanium dioxide raw material) and copper-loaded titanium dioxide (before grinding).
In conclusion, the prepared sample accords with the characteristics of black titanium dioxide, and successfully prepares the black titanium dioxide.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing copper-loaded black titanium dioxide at room temperature, the method comprising the steps of:
s1, adding cupric salt and titanium dioxide into a solvent, and then mixing to obtain a mixed material;
s2, carrying out illumination reaction on the mixed material under stirring, and then separating and purifying to obtain copper-loaded titanium dioxide;
and S3, mixing the copper-loaded titanium dioxide with borohydride in a solvent system, and grinding to obtain the copper-loaded black titanium dioxide.
2. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the mass concentration of the cupric salt in the mixed material is 0.5-1.5g/L.
3. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the mass concentration of the titanium dioxide in the mixed material is 5-20g/L.
4. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the mass ratio of the copper-loaded titanium dioxide to the borohydride is 1 (0.5-1.5).
5. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the grinding time is 15-45min.
6. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the stirring speed is 500-1000r/min.
7. The method for preparing copper-loaded black titanium dioxide at room temperature according to claim 1, wherein the solvent comprises one or more of methanol, ethanol, propanol and isopropanol.
8. The method for producing copper-supported black titanium dioxide at room temperature according to any one of claims 1 to 7, wherein the photoreaction uses a 300W xenon lamp for 30 to 90 minutes.
9. The method for producing copper-supported black titanium dioxide at room temperature according to claim 8, wherein the wavelength range of the xenon lamp is the full wavelength of the xenon lamp, and the current is 12-18A.
10. Copper-loaded black titanium dioxide produced according to the method of any one of claims 1 to 9, characterized in that the surface copper particles of the copper-loaded black titanium dioxide have a particle size of 2-5nm.
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