CN113181914A - Transition metal in-situ doped TiO2Catalyst, preparation method and application - Google Patents

Transition metal in-situ doped TiO2Catalyst, preparation method and application Download PDF

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CN113181914A
CN113181914A CN202110410323.8A CN202110410323A CN113181914A CN 113181914 A CN113181914 A CN 113181914A CN 202110410323 A CN202110410323 A CN 202110410323A CN 113181914 A CN113181914 A CN 113181914A
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tio
transition metal
catalyst
nitrate
situ
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CN113181914B (en
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张鹏
杨晓燕
李静茹
王佳任
尹良科
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Tianjin Polytechnic University
Shangqiu Normal University
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Tianjin Polytechnic University
Shangqiu Normal University
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Abstract

The invention relates to transition metal in-situ doped TiO2Catalyst, preparation method and application. With H2Ti3O7Ion exchange is carried out in a transition metal cation aqueous solution to obtain MxH2‑ xTi3O7Calcining the precursor at high temperature to obtain H2‑xTi3O7Conversion to TiO2Base body, M exchangedn+Then the TiO is doped in situ in the form of transition metal monoatomic or polyatomic atoms2To prepare M-TiO doped with transition metal atoms on the atom layer in situ2A material. The preparation method has the advantages of simple process route, simple and convenient operation, high dispersion degree of doped ions, good uniformity, simple required equipment and easy amplification production, and the prepared transition metal in-situ doped M-TiO2Catalyst material in waterThe method has good application prospect in the fields of treatment, catalytic oxidation, energy storage, sensing and the like.

Description

Transition metal in-situ doped TiO2Catalyst, preparation method and application
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to transition metal in-situ doped TiO2Catalyst, preparation method and application.
Background
TiO2The material is a common industrial raw material, has low price, no toxicity, no pollution, high temperature resistance, acid and alkali resistance, stable chemical property and strong action force with metal, and is an ideal catalyst carrier material.
Furthermore, TiO2The material has also been found to have good photoelectrochemical properties and may be used as a photocatalyst exhibiting good catalytic activity in a number of chemical reactions. But pure TiO2The photocatalyst has two defects, so that the photocatalyst cannot be really applied to industrial photocatalytic production until now: (1) TiO 22The intrinsic forbidden band width of (3.2eV) is too large to be excited by ultraviolet light and not to respond to visible light. The absorption efficiency of the ultraviolet light is too low because the ultraviolet component in the sunlight is only 3 to 5%, which limits TiO2A major difficulty with photocatalytic applications; (2) pure TiO2The fluorescence efficiency of the material is low, and the surface is excited by the light to generate photo-generated electrons (e)-) Will react with the photo-generated holes (h) in a very short time+) Recombination releases energy, resulting in pure TiO2The photocatalytic activity of the material is greatly limited. Research shows that in TiO2The introduction of metal atoms into the crystal structure will be in TiO2A new transition level is created in the bandgap of the semiconductor. The introduction of the transition energy level leads to TiO on the one hand2The band gap of (2) is narrowed, and the excitation can be carried out by visible light. On the other hand, the transition energy level can effectively transfer photon-generated electrons or holes, accelerate the separation of photon-generated carriers and improve TiO2Quantum efficiency and photocatalytic activity. Thus preparing metal-doped TiO2Photocatalyst for realizing TiO2Ideal solution for industrial photocatalytic application of the material.
There are many kinds of TiO at present2The supported metal or metal oxide catalyst is developed and successfully applied to a plurality of catalytic reactions, and the catalytic activity of the catalyst has great influence on the properties of the supported metal or metal oxide, such as size, dispersity and loading capacity. Research finds that the particle size of metal or metal oxide is reduced to nano-scale or even atomic level, so that the utilization efficiency, the catalytic efficiency and the economical efficiency of the catalyst can be greatly improved, and how to prepare metal doped/loaded TiO with atomic level2The catalyst is the key to realizing the industrial production of the catalyst.
There are many experimental schemes proposed to prepare metal-doped M-TiO2Catalysts, but the existing methods suffer from the following drawbacks to varying degrees: (1) the experimental scheme involves strong acid with high risk (such as concentrated sulfuric acid, concentrated nitric acid, hydrofluoric acid, etc.) or expensive reagents. (2) Uses drastic preparation methods (such as plasma bombardment, laser method and the like), is not suitable for large-scale production, and the doped metal atoms are not uniformly distributed and are not suitable for M-TiO2The overall performance of the catalyst is greatly affected. (3) Many of the M-TiO produced2The regulation and control space of a plurality of key parameters such as the types, doping amount, existing forms and the like of metal elements in the catalyst is small, and the regulation and application range of the catalytic performance of the catalyst is greatly limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the H-shaped material with simple operation and low cost2Ti3O7Constructing in-situ transition metal doped M-TiO as raw material2The catalyst obtained by the method has the advantages of stable structure, controllable property, high catalytic efficiency and good applicability in catalytic oxidation and photocatalytic reaction.
The method comprises the following specific steps:
transition metal in-situ doped TiO2The preparation method of the catalyst comprises the following steps:
(1) preparing a precursor: mix 3.88X 10-3mol of starting materials H2Ti3O7UltrasoundUniformly dispersing into 50-300 mL of transition metal salt solution with the concentration of 0.01-0.5 mol/L, continuously magnetically stirring at room temperature for not less than 18h, filtering, and drying at the temperature of not more than 100 ℃ to obtain MxH2-xTi3O7A precursor;
(2) high-temperature calcination: mixing M in step (1)xH2-xTi3O7Putting the precursor into a tube furnace, calcining at a high temperature of 600-900 ℃ in a certain atmosphere, heating at a rate of 1-10 ℃/min for 1-4 h to obtain the transition metal in-situ doped M-TiO2A catalyst;
m is transition metal element, x is atomic ratio, and x is more than 0 and less than 1.
Preferably, the transition metal salt is zinc acetate, bismuth nitrate, manganese nitrate, cadmium nitrate, cerium nitrate, lanthanum nitrate, yttrium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate, silver nitrate, palladium nitrate, platinum nitrate, gold chloride or ruthenium chloride.
Preferably, the stirring time is 24 h.
Preferably, the atmosphere of the calcination treatment is air, oxygen, nitrogen, argon, hydrogen or ammonia.
Transition metal in-situ doped TiO2M-TiO obtained by preparation method of catalyst2A catalyst.
Preferably, the transition metal atoms are embedded in the catalyst lattice.
Transition metal in-situ doped TiO2M-TiO obtained by preparation method of catalyst2The application of the catalyst in catalytic oxidation.
Transition metal in-situ doped TiO2M-TiO obtained by preparation method of catalyst2The application of the catalyst in photocatalysis.
The invention has the beneficial effects that:
(1) the method has wide application range, and can be applied to different transition metal salt solutions to prepare different transition metal atom-doped M-TiO2A catalyst;
(2) the raw materials are cheap and easy to obtain, the preparation method is simple and safe, the experimental conditions are easy to control, the production cost is low, and the method is suitable for large-scale industrial production;
(3) the transition metal atoms can be uniformly dispersed in TiO2In the crystal lattice, the transition metal atom is in contact with the base TiO2The interaction of (A) is strong;
(4)M-TiO2the material has better integral structure uniformity and stable structure, so the M-TiO prepared by the method2The material is very suitable for various catalytic reactions such as catalytic oxidation, photocatalysis and the like, and can control the M-TiO by regulating and controlling the conditions such as the type, the loading capacity, the form and the like of transition metal2The purpose of the catalytic activity of the catalyst.
Drawings
FIG. 1 shows Cu atom-doped Cu-TiO according to the present invention2Scanning electron microscope photographs of the nanorods;
FIG. 2 shows Cu atom-doped Cu-TiO according to the present invention2XRD pattern of the nanorods;
FIG. 3 shows Cu atom-doped Cu-TiO according to the present invention2Transmission electron microscope photo of the nano rod;
FIG. 4 shows Ag atom-doped Ag-TiO according to the present invention2XRD spectrogram of the nanorod;
FIG. 5 shows the TiO doped with Fe, Co and Ni atoms according to the invention2Graph of catalyst conversion in catalytic nitromethylmorpholine oxide (NMM) reaction.
Detailed Description
Example 1
0.1g of H is weighed2Ti3O7Adding the raw materials into 40mL of cuprous chloride aqueous solution with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Cu in solution+Ion exchange reaches balance, and Cu with complete exchange is obtained by filteringxH2- xTi3O7The sample (x is atomic ratio, x is more than 0 and less than 1), washed alternately by deionized water and ethanol, and dried in an oven at 80 DEG COvernight. Cu to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 700 ℃ from room temperature at a speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the brown Cu atom in-situ doped Cu-TiO2The XRD pattern of the catalyst and the obtained material is shown in figure 1, and it can be seen that the doping of copper atom does not change TiO2The crystal structure of the catalyst can be observed under an electron microscope, and the catalyst crystal grains are rod-shaped and uniform in size.
Example 2
0.1g of H is weighed2Ti3O7Adding the raw materials into 50mL of zinc acetate aqueous solution with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Zn in solution2+Ion exchange reaches balance, and Zn with complete exchange is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Zn to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 800 ℃ from room temperature at a speed of 10 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the gray black Zn atom in-situ doped Zn-TiO2A catalyst.
Example 3
0.5g of H are weighed2Ti3O7Adding the raw materials into 100mL of silver nitrate aqueous solution with the concentration of 0.05mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 22H to obtain H2Ti3O7H in (1)+Ions and Ag in solution+Ion exchange reaches balance, and the Ag with complete exchange is obtained by filteringxH2- xTi3O7Sample (x is original)Sub ratio, x is more than 0 and less than 1), washing with deionized water and ethanol alternately, and drying in an oven at 75 ℃ overnight. Drying the AgxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 750 ℃ from room temperature at a speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting grayish blue Ag atoms in-situ doped Ag-TiO2A catalyst.
Example 4
0.1g of H is weighed2Ti3O7Adding the raw materials into 50mL of aqueous solution of ferric chloride with the concentration of 0.05mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Fe in solution3+The ion exchange reaches the balance, and the Fe which is completely exchanged is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried overnight in an oven at 60 ℃. Fe to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 750 ℃ from room temperature at the speed of 3 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the light yellow Fe atom in-situ doped Fe-TiO2A catalyst.
Example 5
0.1g of H is weighed2Ti3O7Adding the raw materials into 100mL of cobalt acetate aqueous solution with the concentration of 0.2mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Co in solution2+The ion exchange reaches the balance, and the Co completely exchanged is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Will dryDry CoxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 900 ℃ from room temperature at the speed of 8 ℃/min, keeping the temperature for 4 hours, naturally cooling to room temperature, and collecting the light green Co atom in-situ doped Co-TiO2A catalyst.
Example 6
0.02g of H is weighed2Ti3O7Adding the raw materials into 40mL of aqueous solution of cerium nitrate with the concentration of 0.15mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Ce in solution3+The ion exchange reaches the balance, and the Ce which is completely exchanged is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 70 ℃ overnight. To-be-dried CexH2-xTi3O7Calcining the sample in a tube furnace, introducing argon, heating to 650 ℃ from room temperature at the speed of 1 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, and collecting the Ce-TiO doped with Ce atoms in situ2A catalyst.
Example 7
0.1g of H is weighed2Ti3O7Adding the raw materials into 40mL of nickel acetate aqueous solution with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Ni in solution2+Ion exchange reaches balance, and Ni with complete exchange is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried overnight in an oven at 75 ℃. Ni to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, and thenHeating to 700 ℃ from room temperature at the speed of 6 ℃/min, keeping the temperature for 2h, naturally cooling to room temperature, and collecting the yellowish Ni atom in-situ doped Ni-TiO2A catalyst.
Example 8
0.2g of H are weighed2Ti3O7Adding the raw materials into 400mL of palladium chloride aqueous solution with the concentration of 0.01mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Pd in solution2+Ion exchange reaches balance, and the Pd with complete exchange is obtained by filtrationxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Pd to be driedxH2-xTi3O7The sample is put into a tube furnace for calcination, air is introduced, then the temperature is raised to 600 ℃ from room temperature at the speed of 5 ℃/min, the temperature is kept constant for 2h, and then the sample is naturally cooled to the room temperature. After the high-temperature reaction is finished completely, collecting the obtained Pd atoms in-situ doped Pd-TiO2A catalyst.
Example 9
0.1g of H is weighed2Ti3O7Adding the raw materials into 60mL of lanthanum nitrate aqueous solution with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and La in solution3+Ion exchange reaches balance, and filtration is carried out to obtain La with complete exchangexH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. La to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing hydrogen, heating to 800 ℃ from room temperature at a speed of 10 ℃/min, keeping the temperature for 3h, and thenNaturally cooling to room temperature, and collecting the La-TiO doped with La atoms in situ2A catalyst.
Example 10
0.5g of H are weighed2Ti3O7Adding the raw materials into 100mL of aqueous solution of manganese nitrate with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Mn in solution2+Ion exchange reaches balance, and Mn with complete exchange is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Mn to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 900 ℃ from room temperature at the speed of 3 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, and collecting the yellow-green Mn atom in-situ doped Mn-TiO2A catalyst.
Example 11
0.1g of H is weighed2Ti3O7Adding the raw materials into 50mL of aqueous solution of chloroauric acid with the concentration of 0.01mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Au in solution3+Ion exchange reaches balance, and Au with complete exchange is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Au to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 600 ℃ from room temperature at the speed of 5 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature, and collecting the Au-TiO doped with Au atoms in situ2A catalyst.
Example 12
0.1g of H is weighed2Ti3O7Adding the raw materials into 300mL of chloroplatinic acid aqueous solution with the concentration of 0.01mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Pt in solution4+Ion exchange reaches balance, and filtration is carried out to obtain Pt with complete exchangexH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Drying PtxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 750 ℃ from room temperature at a speed of 4 ℃/min, keeping the temperature for 4 hours, naturally cooling to room temperature, and collecting the Pt-TiO doped with Pt atoms in situ2A catalyst.
Example 13
0.1g of H is weighed2Ti3O7Adding the raw materials into 100mL of yttrium nitrate aqueous solution with the concentration of 0.2mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Y in solution3+Ion exchange reaches balance, and filtering to obtain completely exchanged YxH2Ti3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Drying YxH2Ti3O7Calcining the sample in a tube furnace, introducing oxygen, heating to 900 ℃ from room temperature at the speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the Y-TiO doped with Y atoms in situ2A catalyst.
Example 14
0.1g of H is weighed2Ti3O7Raw materials, adding them under the assistance of ultrasoundAdding into 80mL of indium nitrate water solution with the concentration of 0.05mol/L, and continuing to perform ultrasonic treatment for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and In solution3+Ion exchange reaches balance, and completely exchanged In is obtained by filtrationxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Drying InxH2-xTi3O7Calcining the sample In a tube furnace, introducing nitrogen, heating to 800 ℃ from room temperature at the speed of 10 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, and collecting In-situ doped In-TiO of In atoms2A material.
Example 15
0.1g of H is weighed2Ti3O7Adding the raw materials into 50mL of aqueous solution of ruthenium chloride with the concentration of 0.01mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Ru in solution3+Ion exchange reaches balance, and filtration is carried out to obtain Ru with complete exchangexH2-xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Ru to be driedxH2-xTi3O7The sample is put into a tube furnace for calcination, air is introduced, then the temperature is raised to 600 ℃ from room temperature at the speed of 3 ℃/min, the temperature is kept constant for 3h, and then the sample is naturally cooled to the room temperature. After the high-temperature reaction is finished completely, collecting the Ru atoms in-situ doped Ru-TiO2A catalyst.
Example 16
0.2g of H are weighed2Ti3O7Adding the raw materials into 100mL of aqueous solution of cadmium nitrate with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Cd in solution3+Ion exchange reaches balance, and Cd completely exchanged is obtained by filteringxH2- xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Cd to be driedxH2-xTi3O7Calcining the sample in a tube furnace, introducing air, heating to 700 ℃ from room temperature at a speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the Cd-TiO doped with Cd atoms in situ2A catalyst.
Example 17
0.1g of H is weighed2Ti3O7Adding the raw materials into 50mL of 0.1mol/L bismuth nitrate aqueous solution (adding a proper amount of nitric acid to dissolve the bismuth nitrate) under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. Continuously magnetically stirring the suspension at room temperature for 24H to obtain H2Ti3O7H in (1)+Ions and Bi in solution3+Ion exchange reaches balance, and Bi with complete exchange is obtained by filtrationxH2-xTi3O7Samples (x is atomic ratio, 0 < x < 1) were washed alternately with deionized water and ethanol and dried in an oven at 80 ℃ overnight. Drying BixH2-xTi3O7Calcining the sample in a tube furnace, introducing ammonia gas, heating to 900 ℃ from room temperature at the speed of 10 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, and collecting the Bi-TiO doped with Bi atoms in situ2A catalyst.
Found by research that H2Ti3O7The raw material and transition metal cation are subjected to long-time ion exchange, dried under mild conditions, calcined at high temperature, and subjected to H2Ti3O7Conversion to TiO2While the transition metal atoms exchanged on the surface are left in the TiO2In the crystal lattice, form a single atom or multiple atomsSub-doped M-TiO2A material. Increasing the concentration of the transition metal salt allows exchange to MxH2-xTi3O7The transition metal ion carrying capacity on the precursor is improved, and the precursor is doped with TiO after being calcined at high temperature2The content of transition metal atoms in the alloy is increased. If the exchanged transition metal atoms continue to increase, TiO2Not only doped transition metal atoms are generated in the structure, but also transition metal or transition metal oxide particles are generated on the surface, and the M-TiO which is loaded by particles and doped with atoms is prepared2A material. Since this method is through uniformly exchanging MxH2-xTi3O7The precursor is prepared in situ at high temperature, so that the obtained M-TiO2The dispersibility of the doped transition metal in the material is higher. The transition metal being embedded into TiO at the atomic level2In the crystal lattice, the transition metal atom is in contact with the base TiO2The interaction of (3) is stronger. M-TiO2The material has better integral structure uniformity and stable structure, so the M-TiO prepared by the method2The material is very suitable for various catalytic reactions such as catalytic oxidation, photocatalysis and the like, and can control the M-TiO by regulating and controlling the conditions such as the type, the loading capacity, the form and the like of transition metal2The purpose of the catalytic activity of the catalyst.
Example 18
0.1g of TiO was weighed2Adding the mixture into 40mL of cuprous chloride aqueous solution with the concentration of 0.1mol/L under the assistance of ultrasound, and continuing to perform ultrasound for 5-10min to obtain uniformly dispersed suspension. The suspension was magnetically stirred for 24h at room temperature, filtered to give a solid sample, washed alternately with deionized water and ethanol, and dried in an oven at 80 ℃ overnight. Putting the dried sample into a tubular furnace for calcination, introducing air, heating to 700 ℃ from room temperature at a speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting the obtained CuO-loaded CuO/TiO2A catalyst.
Example 19
0.1g of TiO was weighed2Adding the mixture into 40mL of aqueous solution under the assistance of ultrasound, continuing ultrasound for 5-10min,obtain a uniformly dispersed suspension. The suspension was magnetically stirred continuously for 24h at room temperature, and then the solid sample was removed and dried in an oven at 80 ℃ overnight. Putting the dried sample into a tube furnace for calcination, introducing air, heating to 700 ℃ from room temperature at a speed of 5 ℃/min, keeping the temperature for 2 hours, naturally cooling to room temperature, and collecting white TiO2A catalyst.
Example 20
Photocatalytic reaction
The catalysts, numbered I, II and III, prepared according to the methods of example 1, example 18 and example 19, are used in reactions for degrading toxic pollutants (tetracycline) in water under the irradiation of visible light, the dosage of the catalyst is 0.1g, and the catalyst is ultrasonically dispersed in 400mL of tetracycline aqueous solution with the concentration of 20 mg/L. After stirring for 0.5 hour in the dark, a 300W Xe lamp was turned on to provide visible light to start the photocatalytic reaction. In the reaction process, a fan is used for cooling the lamp source and the reactor, so that the whole reaction system is kept at room temperature all the time, and the reaction time is 2 hours. The catalytic results for the different samples obtained are shown in the table below.
Figure BDA0003023932380000131
Example 21
Catalytic oxidation reaction
0.02g of the catalyst obtained in examples 4, 5 and 7 was added to 10g of N-methylmorpholine (NMM), the temperature was maintained at 28 ℃ and after stirring was complete, 15g H was added dropwise2O2Starting from the time after the first addition, when H2O2After all additions the temperature was raised to 35 ℃ until the reaction was complete. Taking a sample every 20min, diluting, detecting the content of reactant N-methylmorpholine and product N-methylmorpholine oxide (NMMO) in the solution by using a liquid chromatograph to obtain TiO doped with Fe, Co and Ni atoms2The conversion rate chart of the catalyst for catalyzing the reaction of oxidizing the Nitromethylmorpholine (NMM) shows that the conversion rate of the nitromethylmorpholine reaches over 80 percent after the reaction is carried out for 60 min.
The inventionThe method has strong universality, and can be suitable for preparing M-TiO doped with different transition metal atoms by using different transition metal salt solutions2A catalyst. The transition metal doped M-TiO prepared by the invention2The preparation method of the material is simple, convenient and safe, has lower production cost, is easy to operate, regulate and control, and is suitable for industrial production and application.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (8)

1. Transition metal in-situ doped TiO2The preparation method of the catalyst is characterized by comprising the following steps:
(1) preparing a precursor: mix 3.88X 10-3mol of starting materials H2Ti3O7Uniformly dispersing the mixture into 50-300 mL of transition metal salt solution with the concentration of 0.01-0.5 mol/L by ultrasonic, continuously stirring the mixture by magnetic force at room temperature for not less than 18h, filtering the mixture, and drying the filtered mixture at the temperature of not more than 100 ℃ to obtain MxH2-xTi3O7A precursor;
(2) high-temperature calcination: mixing M in step (1)xH2-xTi3O7Putting the precursor into a tube furnace, calcining at a high temperature of 600-900 ℃ in a certain atmosphere, heating at a rate of 1-10 ℃/min for 1-4 h to obtain the transition metal in-situ doped M-TiO2A catalyst;
m is transition metal element, x is atomic ratio, and x is more than 0 and less than 1.
2. The in-situ transition metal doped TiO of claim 12The preparation method of the catalyst is characterized in that the transition metal salt is zinc acetate, bismuth nitrate, manganese nitrate, cadmium nitrate, cerium nitrate, lanthanum nitrate, yttrium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate and nitrateSilver acid, palladium nitrate, platinum nitrate, gold chloride or ruthenium chloride.
3. The in-situ transition metal doped TiO of claim 12The preparation method of the catalyst is characterized in that the stirring time is 24 hours.
4. The in-situ transition metal doped TiO of claim 12The preparation method of the catalyst is characterized in that the atmosphere of the calcination treatment is air, oxygen, nitrogen, argon, hydrogen or ammonia.
5. The in-situ TiO doped transition metal of any one of claims 1 to 42M-TiO obtained by preparation method of catalyst2A catalyst.
6. M-TiO according to claim 52A catalyst, characterized in that the transition metal atoms are embedded in the catalyst lattice.
7. The in-situ transition metal doped TiO of claim 52M-TiO obtained by preparation method of catalyst2The application of the catalyst in catalytic oxidation.
8. The in-situ transition metal doped TiO of claim 52M-TiO obtained by preparation method of catalyst2The application of the catalyst in photocatalysis.
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