CN114505076B - CoO/h-TiO 2 Method for preparing nano heterostructure - Google Patents

CoO/h-TiO 2 Method for preparing nano heterostructure Download PDF

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CN114505076B
CN114505076B CN202210210249.XA CN202210210249A CN114505076B CN 114505076 B CN114505076 B CN 114505076B CN 202210210249 A CN202210210249 A CN 202210210249A CN 114505076 B CN114505076 B CN 114505076B
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coo
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CN114505076A (en
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徐平
陈晓宇
韩喜江
张彬
杜耘辰
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Harbin Institute of Technology
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Abstract

CoO/h-TiO 2 The invention relates to a preparation method of a nano heterostructure, and relates to the field of preparation methods of semiconductor nano heterostructures. The invention aims to solve the problems of the prior h-TiO 2 The solar energy conversion efficiency of the base photocatalyst is low, and the base photocatalyst is too dependent on noble metal to improve the performance. The method comprises the following steps: preparing hydrogenated titanium dioxide nanosheets by a hydrothermal method and a calcination method, taking the nanosheets as a substrate, taking cobalt acetate as a divalent cobalt source, loading cobalt-based compound intermediates on the surfaces of the nanosheets by the hydrothermal method under alkaline conditions, and finally calcining the nanosheets under nitrogen conditions to obtain light green CoO/h-TiO 2 The nano heterostructure catalyst can be used for photolysis water hydrogen production reaction. In the form of h-TiO 2 As a substrate, a metal layer is formed,can effectively protect Co 2+ Is not oxidized to Co in hydrothermal process 3+ In the form of TiO 2 Is a substrate, co 2+ Will be oxidized to Co 3+ The preparation process also provides a new idea for synthesizing low-price cobalt oxide. CoO/h-TiO prepared by the invention 2 The nano heterostructure has excellent photocatalytic hydrogen production performance and can be used in the field of catalysis.

Description

CoO/h-TiO 2 Method for preparing nano heterostructure
Technical Field
The invention relates to the field of semiconductor nano heterostructure preparation methods.
Background
With the continuous consumption of fossil energy, development of clean energy which is rich in reserves and renewable is urgent. Photocatalytic water splitting to produce hydrogen is one of the most effective methods for solving energy and environmental problems at present. Titanium dioxide (TiO) 2 ) The catalyst is environment-friendly and has stable chemical properties, so that the catalyst is widely applied to the field of photocatalysis. But TiO 2 The large band gap (3.0-3.2 eV) limits the absorption and utilization of solar uv light by about 5%. Thus, regulating TiO 2 The morphology, lattice defects and crystal phase type of (c) are particularly important for improving the light absorption capacity and photocatalytic performance thereof. However, most of the literature currently reports about titanium dioxide hydride (h-TiO 2 ) Application in photocatalytic performance has been rarely reported in h-TiO 2 The role of the intermediate oxygen vacancies in further modification thereof, thus exploring the h-TiO 2 The regulating action of the oxygen vacancy on the valence state of the cocatalyst further loaded on the surface of the catalyst can be used for designing and synthesizing h-TiO 2 The base heterojunction plays an important role. Cobalt oxide (CoO) is also a good photocatalyst, but CoO is easily oxidized to higher-valence tricobalt tetraoxide (Co 3 O 4 ) Affecting its catalytic activity, so preparing CoO with high catalytic activity and stable performance is also a problem to be studied. In addition, the h-TiO is generally to be promoted 2 The photocatalytic activity of (2) depends on a noble metal promoter, which increases the preparation cost and is not suitable for practical application. To sum upDesign and development of CoO/h-TiO 2 The cheap, environment-friendly and efficient photocatalyst has guiding significance in synthesis and is a great breakthrough in the field of photocatalysis.
Disclosure of Invention
The invention aims to solve the problems of the prior h-TiO 2 The technical problems of low solar energy conversion efficiency and too much dependence on noble metal to improve performance of the base photocatalyst are solved, and a CoO/h-TiO is provided 2 A method for preparing nano heterostructures.
CoO/h-TiO 2 The preparation method of the nano heterostructure is characterized by comprising the following steps of:
stirring tetrabutyl titanate and hydrofluoric acid uniformly, and transferring the stirred tetrabutyl titanate and hydrofluoric acid into a polytetrafluoroethylene reaction kettle for solvothermal reaction; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 Calcining at elevated temperature under mixed atmosphere, wherein H 2 The volume percentage content of (2) is 5%, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4-10 h, and then the mixture is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
preparing a sodium hydroxide solution by adopting sodium hydroxide and deionized water, and preparing a cobalt acetate solution by adopting cobalt acetate tetrahydrate and deionized water;
step four, the h-TiO obtained in the step two is treated 2 Dispersing the nano-sheets into deionized water, uniformly dispersing by ultrasonic, adding the cobalt acetate solution and the sodium hydroxide solution obtained in the step three, stirring, and transferring into a reaction kettle for hydrothermal reaction; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Calcining under the condition that the calcining temperature is controlled to be 600 ℃ and the calcining time is controlled to be 4-10 h, thus obtaining CoO/h-TiO 2 Nano heterostructures.
CoO/h-TiO is prepared according to the mole ratio of Co to Ti 2 The nano heterostructure is named CoO/h-TiO 2 -x (x is the molar ratio of Co to Ti)
If the calcining atmosphere in the second step is air, tiO is obtained 2 A nanosheet; h-TiO in step four 2 Substitution of nanoplatelets for TiO 2 Nanosheets to give intermediate supported TiO 2 Nanoplatelets, based on molar ratio of Co to Ti, coO/TiO 2 The nano heterostructure is named Co 3 O 4 /TiO 2 -x (x is the molar ratio of Co to Ti).
The beneficial effects of the invention are as follows:
the invention utilizes the h-TiO 2 Oxygen vacancies in the cobalt acetate solution inhibit Co 2+ Oxidized by oxygen in hydrothermal reaction to Co 3+ Finally, calcining under the protection of nitrogen to successfully prepare the CoO/h-TiO with excellent performance 2 Nano heterostructure, successfully demonstrated h-TiO 2 Oxygen vacancies in (C) can be found in the para-h-TiO 2 And plays a role in the further modification process.
CoO/h-TiO obtained by the invention 2 The nano heterostructure has good visible light response performance, a p-n heterojunction is formed at the contact position of the nano heterostructure and the nano heterostructure, a built-in space electric field is formed at the interface, the separation of electrons and holes is more effectively promoted, and the maximum hydrogen production rate can reach 2.595 mmol.g under the condition that noble metal is not used as a cocatalyst -1 ·h -1 And has excellent cycle stability and can be repeatedly used.
The material prepared by the invention can effectively utilize visible light under the condition of no noble metal as a cocatalyst, improves the solar energy conversion efficiency, improves the separation efficiency of photogenerated carriers, reduces the preparation cost and provides a new reference for the design of high-efficiency photocatalysts.
CoO/h-TiO prepared by the invention 2 The nano heterostructure has excellent photocatalytic hydrogen production performance, can be used in the field of catalysis, and has certain practical application value.
Drawings
FIG. 1 shows h-TiO as prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -an optical photograph of a 1 nm heterostructure; wherein a is TiO 2 Nanosheets, b is Co 3 O 4 /TiO 2 -1 nanometer heterostructure, c is h-TiO 2 Nanosheets, d is CoO/h-TiO 2 -1 nanometer heterostructure;
FIG. 2 shows the h-TiO composition prepared in example one step two 2 Atomic force microscope photographs of nanoplatelets;
FIG. 3 is the h-TiO of FIG. 2 2 A thickness test chart of nanoplatelets, wherein the reference numerals correspond to those of fig. 2;
FIG. 4 shows h-TiO as prepared in example one 2 Nanoplatelets and CoO/h-TiO 2 -nitrogen adsorption profile for a 1 nm heterostructure;
FIG. 5 shows h-TiO as prepared in example one 2 Nanoplatelets and CoO/h-TiO 2 -a specific surface area and pore size contrast plot of a 1 nm heterostructure;
FIG. 6 a shows the h-TiO composition prepared in example one 2 Transmission electron microscopy (100 nm) of the nanoplatelets, b-plot is h-TiO prepared in example one 2 Transmission electron microscopy (20 nm) of the nanoplatelets, c is the h-TiO prepared in example one 2 High-power transmission electron microscope (HRTEM) image of nano sheet, d image is h-TiO prepared in example one 2 AFM image of nanosheets, e-image, example one preparation of CoO/h-TiO 2 TEM image of 1 nm heterostructure, f image for example one preparation of CoO/h-TiO 2 HRTEM diagram of 1 nm heterostructure, g-diagram example one example of CoO/h-TiO preparation 2 HRTEM diagram of 1 nm heterostructure, h diagram for example one preparation of CoO/h-TiO 2 Fourier transform pattern diagram of-1 nm heterostructure, i-diagram is example one of preparing CoO/h-TiO 2 EDS surface scanning spectrum of-1 nanometer heterostructure, j graph is preparation of CoO/h-TiO in embodiment I 2 EDS surface scanning energy spectrum (Ti) of-1 nanometer heterostructure, and k graph is prepared CoO/h-TiO in embodiment I 2 EDS plane of-1 nm heterostructureThe energy spectrum (O) is a graph of the first example of the preparation of CoO/h-TiO 2 -EDS face sweep spectrum (Co) of 1 nm heterostructure;
FIG. 7 a is a diagram of TiO prepared in example two 2 TEM image of the nanoplatelets, b image is TiO prepared in example two 2 HRTEM image of nanosheets, c image Co prepared in example two 3 O 4 /TiO 2 TEM image of 1 nm heterostructure, d image Co prepared in example two 3 O 4 /TiO 2 HRTEM diagram of 1 nm heterostructure, e-diagram Co prepared in example two 3 O 4 /TiO 2 HRTEM diagram of 1 nm heterostructure, f diagram Co prepared in example two 3 O 4 /TiO 2 -a fourier transform pattern diagram of a 1 nm heterostructure;
FIG. 8 is Co prepared in example two 3 O 4 /TiO 2 -EDS surface-scan spectrum of a 1 nm heterostructure, wherein figure a is HAADF, figure b is O element, figure c is Ti element, and figure d is Co element;
FIG. 9 is a schematic diagram of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -XRD spectrum of 1 nm heterostructure;
FIG. 10 shows h-TiO as prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -Raman profile of 1 nm heterostructure;
FIG. 11 is a schematic illustration of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -a partial magnified view of Raman spectra of 1 nm heterostructures;
FIG. 12 is a cobalt intermediate supported h-TiO prepared in step four of the example 2 Nanosheets and cobalt intermediate supported TiO prepared in example two and four steps 2 XPS peak-splitting fitting graph of Co 2p of nano sheet, wherein graph a is negative cobalt intermediate prepared in step two and step four of exampleSupported TiO 2 Nanosheets, b-chart of example one step four cobalt intermediate supported h-TiO 2 A nanosheet;
FIG. 13A is a graph showing CoO/h-TiO prepared in example one 2 XPS full spectrum of-1 nanometer heterostructure, b graph is h-TiO prepared in example one 2 XPS spectrum of Ti 2p of nano-sheet, c graph is h-TiO prepared in example one 2 XPS spectrum of O1 s of nano-sheet, d graph of H-TiO prepared in example I 2 Nanoplatelets and TiO prepared in example two 2 XPS (X-ray Spectrum) contrast spectrum of Ti 2p of nano-sheet, and e-graph of H-TiO prepared in example I 2 Nanoplatelets and CoO/h-TiO 2 XPS contrast spectrum of Ti 2p of-1 nanometer heterostructure, f graph is TiO prepared in example two 2 Nanoplatelets and Co 3 O 4 /TiO 2 -XPS contrast profile of Ti 2p of 1 nm heterostructure;
FIG. 14A is a graph showing CoO/h-TiO prepared in example one 2 -1 nm heterostructure and Co prepared in example two 3 O 4 /TiO 2 XPS contrast plot of Co 2p of-1 nm heterostructure, b plot is CoO/h-TiO prepared in example one 2 XPS peak-splitting fitting map of-1 nm heterostructure Co 2p, c map of Co prepared in example two 3 O 4 /TiO 2 XPS peak-splitting fitting graph of Co 2p of-1 nanometer heterostructure, d graph is h-TiO prepared in example I 2 Nanoplatelets and CoO/h-TiO 2 -EPR profile of a 1 nm heterostructure;
FIG. 15A is a graph of CoO/h-TiO with different Co to Ti molar ratios 2 Ultraviolet absorption spectrum diagram of nano heterostructure, b diagram is CoO/h-TiO with different Co to Ti mole ratios 2 Band gap diagram of nano heterostructure;
FIG. 16 a is a diagram of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 Ultraviolet absorption spectrum of-1 nm heterostructure, b diagram is h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 nm heterostructure bandgap diagram, c-diagram h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 PL fluorescence spectrum of-1 nm heterostructure, d graph is h-TiO prepared in example 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -transient fluorescence lifetime diagram of 1 nm heterostructure;
FIG. 17A is a graph of CoO/h-TiO with different Co to Ti molar ratios 2 Hydrogen production performance diagram of nano heterostructure, b diagram is Co with different Co to Ti molar ratios 3 O 4 /TiO 2 The hydrogen production performance diagram of the nano heterostructure, c is CoO/h-TiO 2 -1 nm heterostructure and Co 3 O 4 /TiO 2 -1 nm heterostructure hydrogen production cycle stability diagram, d diagram is CoO/h-TiO 2 -1 nm heterostructure and Co 3 O 4 /TiO 2 -a hydrogen production performance map of a 1 nm heterostructure under light irradiation of different wavelengths;
FIG. 18 is a graph of CoO/h-TiO for varying Co to Ti molar ratios 2 Hydrogen production cycle stability diagram of nano heterostructure under full spectrum irradiation, wherein 1 represents CoO/h-TiO 2 -1,2 represents CoO/h-TiO 2 -0.5,3 represents CoO/h-TiO 2 -2,4 represents CoO/h-TiO 2 -3,5 represents CoO/h-TiO 2 -4,6 represents h-TiO 2 ；
FIG. 19 is a CoO/h-TiO prepared in example one 2 -XPS spectra of Co 2p of 1 nm heterostructure photocatalyst after reaction;
FIG. 20A shows h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 nm heterostructure photocurrent versus time graph, b graph h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 Impedance spectrum of 1 nanometer heterostructure under light adding and no light adding condition, c graph is h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -Mott-Schottky profile of 1 nm heterostructure in the absence of added light;
FIG. 21 is a h-TiO prepared in example one 2 Nanoplatelets, tiO prepared in example two 2 Nanoplatelets, commercial CoO nanoparticles, commercial Co 3 O 4 UPS plots of nanoparticles;
FIG. 22 is the commercial Co of FIG. 21 3 O 4 A partial magnified view of the nanoparticle; FIG. 23 is a TiO 2 prepared in example two of FIG. 21 2 A partial magnified view of the nanoplatelets; FIG. 24 is an enlarged view of a portion of the commercial CoO nanoparticle of FIG. 21; FIG. 25 is a schematic illustration of h-TiO 1 prepared according to example one of FIG. 21 2 A partial magnified view of the nanoplatelets;
FIG. 26A is a graph of ultraviolet absorbance spectra of commercial CoO nanoparticles, b is a band gap graph of commercial CoO nanoparticles, c is a graph of commercial Co 3 O 4 Ultraviolet absorbance spectrum of nanoparticle, d plot is commercial Co 3 O 4 Band gap diagram of nanoparticles;
FIG. 27 is a CoO/h-TiO prepared according to the present invention 2 Schematic of the catalytic mechanism of nano heterostructure photocatalyst;
FIG. 28 is a CoO/h-TiO prepared in example III 2 -transmission electron microscopy of 4 nm heterostructures.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: the embodiment is a CoO/h-TiO 2 The preparation method of the nano heterostructure comprises the following steps:
stirring tetrabutyl titanate and hydrofluoric acid uniformly, and transferring the stirred tetrabutyl titanate and hydrofluoric acid into a polytetrafluoroethylene reaction kettle for solvothermal reaction; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 Calcining at elevated temperature under mixed atmosphere, wherein H 2 The volume percentage content of (2) is 5%, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4-10 h, and then the mixture is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
preparing a sodium hydroxide solution by adopting sodium hydroxide and deionized water, and preparing a cobalt acetate solution by adopting cobalt acetate tetrahydrate and deionized water;
step four, the h-TiO obtained in the step two is treated 2 Dispersing the nano-sheets into deionized water, uniformly dispersing by ultrasonic, adding the cobalt acetate solution and the sodium hydroxide solution obtained in the step three, stirring, and transferring into a reaction kettle for hydrothermal reaction; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Calcining under the condition that the calcining temperature is controlled to be 600 ℃ and the calcining time is controlled to be 4-10 h, thus obtaining CoO/h-TiO 2 Nano heterostructures.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the dosage of tetrabutyl titanate in the first step is 1-5 mL, and the dosage of hydrofluoric acid is 0.16-0.8 mL. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: the solvothermal reaction temperature in the first step is 140-200 ℃ and the reaction time is 12-24 h. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the concentration of the sodium hydroxide solution in the step one is 0.1mol/L. The other is the same as in one of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and step two, controlling the temperature rising rate to be 2-10 ℃/min. The others are the same as in one to one fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: and in the third step, the concentration of the sodium hydroxide solution is 0.5mol/L, and the concentration of the cobalt acetate solution is 1.0mol/L. The others are the same as in one of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: step four, 60mg of h-TiO 2 The nanoplatelets are dispersed in 30mL deionized water. The others are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and step four, adding a cobalt acetate solution and a sodium hydroxide solution according to the molar ratio of cobalt acetate tetrahydrate to sodium hydroxide of 1:2.5. The other is the same as in one of the first to seventh embodiments.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: and step four, adding a cobalt acetate solution with the volume of 10-75 mu L. The others are the same as in one to eight embodiments.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: controlling the hydrothermal reaction temperature to be 140-200 ℃ and the reaction time to be 8-16 h. The others are the same as in one of the embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the embodiment is a CoO/h-TiO 2 The preparation method of the nano heterostructure is characterized by comprising the following steps of:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
Step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 In the mixed atmosphere, the heating rate is controlled to be 2 ℃/min, and the calcination is carried out by heating, wherein H 2 The volume percentage of the catalyst is 5 percent, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4 hours, and then the catalyst is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 60mg of the h-TiO obtained in the step two is treated 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 19 mu L of the cobalt acetate solution obtained in the step three and 0.1mL of sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 180 ℃, and controlling the reaction time to be 12h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4 hours, so as to obtain CoO/h-TiO 2 -1 nm heterostructure.
Embodiment two:
this example is Co 3 O 4 /TiO 2 -1 nanometer heterostructure preparation method, characterized in that it is carried out according to the following steps:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is calcined in the air atmosphere at a temperature rising rate of 2 ℃/min, a temperature rising temperature is controlled to be 600 ℃, a calcining time is controlled to be 4 hours, and then the titanium dioxide powder is naturally cooled to room temperature to obtain TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 60mg of the TiO obtained in the step two 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 19 mu L of the cobalt acetate solution obtained in the step three and 0.1mL of sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 180 ℃, and controlling the reaction time to be 12h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain TiO loaded by cobalt intermediate 2 A nanosheet;
step five, the TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4h, so that Co is obtained 3 O 4 /TiO 2 -1 nm heterostructure.
FIG. 1 shows h-TiO as prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -an optical photograph of a 1 nm heterostructure; wherein a is TiO 2 Nanosheets, b is Co 3 O 4 /TiO 2 -1 nanometer heterostructure, c is h-TiO 2 Nanosheets, d is CoO/h-TiO 2 -1 nm heterostructure.
FIG. 2 shows the h-TiO composition prepared in example one step two 2 Atomic force microscope photographs of nanoplatelets;
FIG. 3 is the h-TiO of FIG. 2 2 A thickness test chart of nanoplatelets, wherein the reference numerals correspond to those of fig. 2;
FIG. 4 shows h-TiO as prepared in example one 2 Nanoplatelets and CoO/h-TiO 2 -nitrogen adsorption profile for a 1 nm heterostructure;
FIG. 5 shows h-TiO as prepared in example one 2 Nanoplatelets and CoO/h-TiO 2 -a specific surface area and pore size contrast plot of a 1 nm heterostructure; from the figure, it can be seen that CoO/h-TiO 2 -1 nm heterostructure with ultra-thin h-TiO for specific surface area and pore size 2 The nano-sheets are reduced, and the CoO nano-particles tend to be loaded on ultrathin h-TiO 2 The pores of the nano-sheet.
FIG. 6 a shows the h-TiO composition prepared in example one 2 Transmission electron microscopy (100 nm) of the nanoplatelets, b-plot is h-TiO prepared in example one 2 Transmission electron microscopy (20 nm) of the nanoplatelets, c is the h-TiO prepared in example one 2 High-power transmission electron microscope (HRTEM) image of nano sheet, d image is h-TiO prepared in example one 2 AFM image of nanosheets, e-image, example one preparation of CoO/h-TiO 2 TEM image of 1 nm heterostructure, f image for example one preparation of CoO/h-TiO 2 HRTEM diagram of 1 nm heterostructure, g-diagram example one example of CoO/h-TiO preparation 2 HRTEM diagram of 1 nm heterostructure, h diagram for example one preparation of CoO/h-TiO 2 Fourier transform pattern diagram of-1 nm heterostructure, i-diagram is example one of preparing CoO/h-TiO 2 EDS surface scanning spectrum of-1 nanometer heterostructure, j graph is preparation of CoO/h-TiO in embodiment I 2 EDS surface scanning energy spectrum (Ti) of-1 nanometer heterostructure, and k graph is prepared CoO/h-TiO in embodiment I 2 EDS surface scanning energy spectrum (O) of-1 nanometer heterostructure, and l graph is prepared by preparing CoO/h-TiO in example I 2 EDS surface scanning Spectrometry (Co) of the 1 nm heterostructure. From the figure, it can be seen that h-TiO 2 The main growth crystal face of the nano-sheet is a (101) crystal face, the interplanar distance is 0.352nm, the main growth crystal face of the CoO nano-particle is a (200) crystal face, the interplanar distance is 0.213nm, and the CoO nano-particle is successfully loaded on h-TiO as can be seen from a Fourier transformation pattern diagram and an EDS (electronic data System) surface energy scanning spectrum 2 Is a surface of the substrate.
FIG. 7 a is a diagram of TiO prepared in example two 2 TEM image of the nanoplatelets, b image is TiO prepared in example two 2 HRTEM image of nanosheets, c image Co prepared in example two 3 O 4 /TiO 2 TEM image of 1 nm heterostructure, d image Co prepared in example two 3 O 4 /TiO 2 HRTEM diagram of 1 nm heterostructure, e-diagram Co prepared in example two 3 O 4 /TiO 2 HRTEM diagram of 1 nm heterostructure, f diagram Co prepared in example two 3 O 4 /TiO 2 -a fourier transform pattern diagram of a 1 nm heterostructure;
FIG. 8 is Co prepared in example two 3 O 4 /TiO 2 -EDS surface-scan spectrum of a 1 nm heterostructure, wherein figure a is HAADF, figure b is O element, figure c is Ti element, and figure d is Co element;
it can be seen that TiO 2 The main growth crystal face of the nano-sheet is (101) crystal face, the inter-crystal face distance is 0.353nm, and TiO is used 2 When the nano-sheet is used as a substrate, under the same preparation condition, the type of cobalt oxide loaded is Co 3 O 4 The main growth crystal face is (311) crystal face, the interplanar distance is 0.242nm, and Co can be known by combining the Fourier transformation result and the energy spectrum scanning graph 3 O 4 /TiO 2 The-1 nm heterostructure was successfully prepared.
FIG. 9 is a schematic diagram of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -XRD spectrum of 1 nm heterostructure;
FIG. 10 shows h-TiO as prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -Raman profile of 1 nm heterostructure;
FIG. 11 is a schematic illustration of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 nanometer isoA partial magnified view of Raman spectrum of the plasma structure;
as shown in FIGS. 9 to 11, it can be found that h-TiO 2 Nanoplatelets and TiO 2 The nanoplatelets are all matched with anatase titanium dioxide. XRD diffraction peaks at 2θ=25.3, 36.9, 37.8, 38.6, 48.1, 53.9 and 55.1 ° correspond to anatase TiO, respectively 2 The (101), (103), (004), (112), (200), (105) and (211) crystal planes of titanium dioxide having raman peak positions corresponding to 144, 395, 516 and 637cm -1 Where, contrast h-TiO 2 With TiO 2 Is found by the peak position of h-TiO 2 XRD and raman characteristic peaks of (b) are compared with those of TiO 2 All have a slight shift due to the H-TiO after hydrogenation modification 2 Generates oxygen vacancies and forms Ti 3+ This is caused by self-doping, which also allows the same method of loading cobalt oxide to be used, respectively with TiO 2 And h-TiO 2 For different reasons for the product at the time of the substrate. Due to CoO and Co 3 O 4 The diffraction intensity was weak because the loading amount was small, and the characteristic peak was not clearly observed from the graph.
FIG. 12 is a cobalt intermediate supported h-TiO prepared in step four of the example 2 Nanosheets and cobalt intermediate supported TiO prepared in example two and four steps 2 XPS peak-splitting fitting graph of Co 2p of nano sheet, wherein graph a is TiO loaded by cobalt intermediate prepared in the second step of the embodiment 2 Nanosheets, b-chart of example one step four cobalt intermediate supported h-TiO 2 A nanosheet; the results show that the catalyst is expressed as TiO 2 When the nanosheets are used as a substrate, co appears 3+ Characteristic peak of 2p, in the form of h-TiO 2 When the nanosheets are the substrate, co is not detected 3+ Characteristic peak of 2 p. This is due to the fact that TiO 2 When the nano sheet is taken as a substrate, under the action of dissolved oxygen and alkaline environment in water in the hydrothermal process, co is taken as a cobalt source 2+ Partially oxidized to Co 3+ When using h-TiO 2 When the porous ceramic is a substrate, oxygen vacancies exist on the surface of the porous ceramic, and dissolved oxygen in water preferentially occupies h-TiO under the conditions of high temperature and high pressure 2 Oxygen vacancies in (a), which play a role in protecting Co 2+ Is not oxidized, so Co is not generated 3+ . Thus, when h-TiO is used respectively 2 And TiO 2 When the nanosheets are substrates, the cobalt oxide is supported by the same method, and when the loading is low, the cobalt intermediate has different manifestations.
FIG. 13A is a graph showing CoO/h-TiO prepared in example one 2 XPS full spectrum of-1 nanometer heterostructure, b graph is h-TiO prepared in example one 2 XPS spectrum of Ti2p of nano-sheet, c graph is h-TiO prepared in example one 2 XPS spectrum of O1s of nano-sheet, d graph of H-TiO prepared in example I 2 Nanoplatelets and TiO prepared in example two 2 XPS (X-ray Spectrum) contrast spectrum of Ti2p of nano-sheet, and e-graph of H-TiO prepared in example I 2 Nanoplatelets and CoO/h-TiO 2 XPS contrast spectrum of Ti2p of-1 nanometer heterostructure, f graph is TiO prepared in example two 2 Nanoplatelets and Co 3 O 4 /TiO 2 -XPS contrast profile of Ti2p of 1 nm heterostructure; as can be seen from the figure, ti2p 3/2 And Ti2p 1/2 At 458.7 and 464.8eV is CoO/H-TiO 2 -1 Ti in nanocomposite 4+ The other two peaks at 457.6 and 463.4eV are Ti 3+ Is Ti2p of (2) 3/2 And Ti2p 1/2 Characteristic peak positions. h-TiO 2 The O1s peak of the nano-sheet can be divided into three characteristic peaks of 529.9, 530.9 and 532.2eV, which correspond to Ti-O-Ti bond and oxygen vacancy (V) O ) And Ti-OH bonds, which means after the hydrotreating at h-TiO 2 More surface oxygen defects and hydroxyl groups are formed on the surface of the nanoplatelets. Comparative h-TiO 2 、CoO/h-TiO 2 -1 and TiO 2 、Co 3 O 4 /TiO 2 The characteristic peak shift of Ti2p in-1, after loading cobalt oxide, the characteristic peak of Ti2p is obviously shifted to the low binding energy direction, further proving CoO/h-TiO 2 -1 and Co 3 O 4 /TiO 2 Successful preparation of 1 nm heterostructures.
FIG. 14A is a graph showing CoO/h-TiO prepared in example one 2 -1 nm heterostructure and Co prepared in example two 3 O 4 /TiO 2 XPS contrast plot of Co 2p for a-1 nm heterostructure, b plot is realExample one prepared CoO/h-TiO 2 XPS peak-splitting fitting map of-1 nm heterostructure Co 2p, c map of Co prepared in example two 3 O 4 /TiO 2 XPS peak-splitting fitting graph of Co 2p of-1 nanometer heterostructure, d graph is h-TiO prepared in example I 2 Nanoplatelets and CoO/h-TiO 2 -EPR profile of a 1 nm heterostructure; as shown in the figure, in CoO/h-TiO 2 In the-1 nm heterostructure, the peaks at 796.6eV and 780.7eV are Co, respectively 2+ 2p 1/2 And Co 2+ 2p 3/2 Characteristic peaks, which means when used in the form of h-TiO 2 The cobalt oxide supported on the substrate is present as CoO. Co again 3 O 4 /TiO 2 In the-1 nm heterostructure, co corresponds to 795.1eV and 779.3eV, respectively 3+ 2p 1/2 And Co 3+ 2p 3/2 Characteristic peaks at 796.8eV and 780.9eV are Co respectively 2+ 2p 1/2 And Co 2+ 2p 3/2 Characteristic peaks, when expressed in TiO 2 Co as cobalt oxide supported on a substrate 3 O 4 Is present in the form of (c). From the EPR test results, h-TiO 2 And CoO/h-TiO 2 -1 signal peaks appear at g=2.004 due to the presence of oxygen vacancies at CoO/h-TiO 2 The intensity of the signal peak at the position in the-1 heterostructure is relatively pure h-TiO 2 The nanosheets are weak, illustrating the presence of h-TiO during the cobalt oxide loading process 2 The oxygen vacancies of the nanoplatelets have an influence such that CoO/h-TiO 2 Concentration of oxygen vacancies in the-1 nm heterostructure is purer h-TiO 2 The concentration of oxygen vacancies in the nanoplatelets decreases. Due to the existence of oxygen vacancies, the charge transmission is promoted and the recombination efficiency of photo-generated carriers is reduced, so that CoO/h-TiO 2 The photocatalytic activity of the-1 heterostructure is improved.
FIG. 15A is a graph of CoO/h-TiO with different Co to Ti molar ratios 2 Ultraviolet absorption spectrum diagram of nano heterostructure, b diagram is CoO/h-TiO with different Co to Ti mole ratios 2 Band gap diagram of nano heterostructure; as shown in the graph, it is understood that when the cobalt oxide loading amount was increased from 0.5% to 1%, the light absorption in the visible light region was gradually increased, the band gap width was gradually decreased, and the loading was increasedWhen the amount is increased from 2% to 4%, the visible light absorption capacity and band gap of the catalyst gradually decrease and increase, which indicates that excessive cobalt oxide loading can block the absorption of light by the titanium dioxide in the heterostructure.
FIG. 16 a is a diagram of h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 Ultraviolet absorption spectrum of-1 nm heterostructure, b diagram is h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 nm heterostructure bandgap diagram, c-diagram h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 PL fluorescence spectrum of-1 nm heterostructure, d graph is h-TiO prepared in example 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -transient fluorescence lifetime diagram of 1 nm heterostructure; as can be seen, the loading of cobalt oxide nanoparticles can reduce CoO/h-TiO 2 -1 nm heterostructure and Co 3 O 4 /TiO 2 -1 nanometer heterostructure relative to h-TiO 2 Nanoplatelets and TiO 2 Band gap of the nanoplatelets, and due to CoO/h-TiO 2 -1 nm Ti in heterostructure 3+ The effect of self-doping and oxygen vacancy further increases the light absorption range, improves the utilization rate of sunlight, and further improves the hydrogen production performance by photolysis of water. As can be seen from the PL spectrum and fluorescence lifetime analysis, coO/h-TiO 2 -1 nm heterostructure ratio Co 3 O 4 /TiO 2 The photo-generated carriers of the-1 nanometer heterostructure have higher separation efficiency and longer service life, and the photo-generated electrons and hydrogen ions react more at the same time to generate hydrogen, so that the photo-catalytic activity is easier to be improved.
To verify the photocatalytic hydrogen production activity of the photocatalyst, cobalt was then separately reactedOxide-supported CoO/h-TiO 2 Nano heterostructure and Co 3 O 4 /TiO 2 The nano heterostructure performs hydrogen production performance test, cyclic stability test and hydrogen production performance test under different wavelength light irradiation,
FIG. 17A is a graph of CoO/h-TiO with different Co to Ti molar ratios 2 Hydrogen production performance diagram of nano heterostructure, b diagram is Co with different Co to Ti molar ratios 3 O 4 /TiO 2 The hydrogen production performance diagram of the nano heterostructure, c is CoO/h-TiO 2 -1 nm heterostructure and Co 3 O 4 /TiO 2 -1-Hydrogen production cycle stability diagram of a nano-heterostructure, wherein 1 represents CoO/h-TiO 2 -1 nanometer heterostructure, 2 stands for Co 3 O 4 /TiO 2 -1 nm heterostructure d-graph CoO/h-TiO 2 -1 nm heterostructure and Co 3 O 4 /TiO 2 -1 graph of hydrogen production performance of a nano-heterostructure under light irradiation of different wavelengths, wherein 1 represents CoO/h-TiO 2 -1 nanometer heterostructure, 2 stands for Co 3 O 4 /TiO 2 -1 nm heterostructure.
FIG. 18 is a graph of CoO/h-TiO for varying Co to Ti molar ratios 2 A hydrogen production cycle stability diagram of the nano heterostructure under full spectrum irradiation;
as can be seen from FIGS. 17 and 18, when h-TiO is used 2 When the nanosheet is taken as a substrate, the theoretical loading of CoO is 1%, and the CoO/h-TiO is 2 The highest hydrogen production rate of the heterostructure can reach 2.595 mmol.g -1 ·h -1 The method comprises the steps of carrying out a first treatment on the surface of the When TiO is used 2 Nanosheets as substrates, co 3 O 4 At 1% theoretical loading of Co 3 O 4 /TiO 2 The photocatalytic hydrogen production activity of the heterostructure is higher than that of CoO/h-TiO 2 Slightly worse heterostructure, highest hydrogen production rate of 1.349 mmol.g -1 ·h -1 But are all far higher than pure h-TiO under the same test conditions 2 (0.012mmol·g -1 ·h -1 ) And TiO 2 Nanometer sheet (0.005 mmol.g) -1 ·h -1 ) Hydrogen production rate of (a) is provided. The hydrogen production performance under single-wavelength illumination also accords with CoO/h-TiO 2 Catalytic performance of nano heterostructure is superior to Co 3 O 4 /TiO 2 Nano heterostructure, fully explaining CoO/h-TiO 2 The nano heterostructure has good catalytic performance. CoO/h-TiO 2 Heterostructure and Co 3 O 4 /TiO 2 The heterostructure can still keep good photocatalytic activity after being subjected to a cycle stability test for 20 hours, and has high photocatalytic stability.
FIG. 19 is a CoO/h-TiO prepared in example one 2 XPS spectrum of Co 2p after reaction of-1 nanometer heterostructure photocatalyst, it can be known that CoO/h-TiO 2 The nano heterostructure has good light stability, and can keep the valence state of Co unchanged in the photocatalysis reaction process.
FIG. 20A shows h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 nm heterostructure photocurrent versus time graph, b graph h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -1 impedance spectrum of nano heterostructure under light and no light, wherein 1 represents CoO/h-TiO 2 -1-light,2 represents Co 3 O 4 /TiO 2 -1-light,3 represents h-TiO 2 Light,4 represents TiO 2 Light,5 stands for CoO/h-TiO 2 -1-dark,6 represents Co 3 O 4 /TiO 2 -1-dark,7 represents h-TiO 2 Dark,8 represents TiO 2 The dark, c-plot is the h-TiO prepared in example one 2 Nanoplatelets, coO/h-TiO 2 -1 nanometer heterostructure, tiO prepared in example two 2 Nanoplatelets, co 3 O 4 /TiO 2 -Mott-Schottky profile of 1 nm heterostructure in the absence of added light; as can be seen from the figure, coO/h-TiO 2 The photocurrent intensity of the-1 nm heterostructure is highest, the electrochemical alternating current impedance is smallest, the carrier density is largest, and the CoO/h-TiO is fully explained 2 -1 nm heterostructure vs Co 3 O 4 /TiO 2 -1 nm heterostructure and h-TiO 2 And TiO 2 The nano-sheet has good photocatalysis performance.
To analyze CoO/h-TiO 2 Catalytic mechanism of nano heterostructure for CoO and h-TiO 2 UPS test was performed and h-TiO was calculated 2 Work functions of (-4.04 eV) and CoO (-3.39 eV);
FIG. 21 is a h-TiO prepared in example one 2 Nanoplatelets, tiO prepared in example two 2 Nanoplatelets, commercial CoO nanoparticles, commercial Co 3 O 4 UPS plots of nanoparticles;
FIG. 22 is the commercial Co of FIG. 21 3 O 4 A partial magnified view of the nanoparticle; FIG. 23 is a TiO 2 prepared in example two of FIG. 21 2 A partial magnified view of the nanoplatelets; FIG. 24 is an enlarged view of a portion of the commercial CoO nanoparticle of FIG. 21; FIG. 25 is a schematic illustration of h-TiO 1 prepared according to example one of FIG. 21 2 A partial magnified view of the nanoplatelets;
FIG. 26A is a graph of ultraviolet absorbance spectra of commercial CoO nanoparticles, b is a band gap graph of commercial CoO nanoparticles, c is a graph of commercial Co 3 O 4 Ultraviolet absorbance spectrum of nanoparticle, d plot is commercial Co 3 O 4 Band gap diagram of nanoparticles;
FIG. 27 is a CoO/h-TiO prepared according to the present invention 2 Schematic of the catalytic mechanism of nano heterostructure photocatalyst;
h-TiO as shown in FIGS. 15 and 26 in combination 2 And the CoO band gap, give a catalytic mechanism diagram as shown in FIG. 27. Since CoO is a p-type semiconductor, h-TiO 2 Is an n-type semiconductor, a space electric field is formed before the n-type semiconductor and the n-type semiconductor promote carrier migration, and the work function of CoO is smaller than that of h-TiO 2 The electrons flow from the conduction band of CoO to h-TiO 2 And the conduction band and the reduction reaction generate hydrogen, and the flow direction of the holes is opposite. Co (Co) 3 O 4 /TiO 2 The catalytic mechanism of the nano-heterostructure is the same.
Embodiment III:
the embodiment is a CoO/h-TiO 2 The preparation method of the nano heterostructure is characterized by comprising the following steps ofThe method comprises the following steps:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 In the mixed atmosphere, the heating rate is controlled to be 2 ℃/min, and the calcination is carried out by heating, wherein H 2 The volume percentage of the catalyst is 5 percent, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4 hours, and then the catalyst is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 150mg of the h-TiO obtained in the step two 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 75 mu L of the cobalt acetate solution obtained in the step three and 0.4mL of sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 200 ℃, and controlling the reaction time to be 10h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4 hours, so as to obtain CoO/h-TiO 2 -4 nm heterostructures.
FIG. 28 is a CoO/h-TiO prepared in example III 2 -transmission electron microscopy of 4 nm heterostructures.
Embodiment four:
the embodiment is a CoO/h-TiO 2 Nanometer scaleThe preparation method of the heterostructure is characterized by comprising the following steps of:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 In the mixed atmosphere, the heating rate is controlled to be 2 ℃/min, and the calcination is carried out by heating, wherein H 2 The volume percentage of the catalyst is 5 percent, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4 hours, and then the catalyst is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 150mg of the h-TiO obtained in the step two 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 10 mu L of the cobalt acetate solution obtained in the step three and 0.05mL of the sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 200 ℃, and controlling the reaction time to be 10h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4 hours, so as to obtain CoO/h-TiO 2 -0.5 nm heterostructure.
Fifth embodiment:
the embodiment is a CoO/h-TiO 2 The preparation method of nano heterostructure is characterized by comprising the following stepsRow:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
Step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 In the mixed atmosphere, the heating rate is controlled to be 2 ℃/min, and the calcination is carried out by heating, wherein H 2 The volume percentage of the catalyst is 5 percent, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4 hours, and then the catalyst is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 150mg of the h-TiO obtained in the step two 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 37 mu L of the cobalt acetate solution obtained in the step three and 0.2mL of sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 200 ℃, and controlling the reaction time to be 10h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4 hours, so as to obtain CoO/h-TiO 2 -2 nm heterostructures.
Example six:
the embodiment is a CoO/h-TiO 2 The preparation method of the nano heterostructure is characterized by comprising the following steps of:
uniformly stirring 5mL of tetrabutyl titanate and 0.8mL of hydrofluoric acid, transferring into a polytetrafluoroethylene reaction kettle, performing solvothermal reaction, and controlling the solvothermal reaction temperature to be 200 ℃ and the reaction time to be 24 hours; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution with the concentration of 0.1mol/L, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 In the mixed atmosphere, the heating rate is controlled to be 2 ℃/min, and the calcination is carried out by heating, wherein H 2 The volume percentage of the catalyst is 5 percent, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4 hours, and then the catalyst is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
step three, preparing 0.5mol/L sodium hydroxide solution by adopting ultrasonic dissolution of 0.1g sodium hydroxide and deionized water, and preparing 1.0mol/L cobalt acetate solution by adopting ultrasonic dissolution of 0.2491g cobalt acetate tetrahydrate and deionized water;
step four, 150mg of the h-TiO obtained in the step two 2 Dispersing the nano-sheets into 30mL of deionized water, performing ultrasonic dispersion for 30min, adding 56 mu L of the cobalt acetate solution obtained in the step three and 0.3mL of the sodium hydroxide solution, stirring for 30min, transferring into a 50mL reaction kettle, performing hydrothermal reaction, controlling the hydrothermal reaction temperature to be 200 ℃, and controlling the reaction time to be 10h; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying at 60 ℃ to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Under the condition that the heating rate is controlled to be 2 ℃/min, the temperature is increased to calcine, the calcination temperature is controlled to be 600 ℃, and the calcination time is controlled to be 4 hours, so as to obtain CoO/h-TiO 2 -3 nm heterostructures.

Claims (10)

1. CoO/h-TiO 2 The preparation method of the nano heterostructure is characterized by comprising the following steps of:
stirring tetrabutyl titanate and hydrofluoric acid uniformly, and transferring the stirred tetrabutyl titanate and hydrofluoric acid into a polytetrafluoroethylene reaction kettle for solvothermal reaction; then cooling to room temperature, washing off residual surface fluoride ions by using a sodium hydroxide solution, washing by using deionized water and absolute ethyl alcohol in sequence, and drying to obtain titanium dioxide powder;
step two, the titanium dioxide powder obtained in the step one is treated with Ar and H 2 Calcining at elevated temperature under mixed atmosphere, wherein H 2 The volume percentage content of (2) is 5%, the calcination temperature is controlled to be 600 ℃, the calcination time is controlled to be 4-10 h, and then the mixture is naturally cooled to room temperature to obtain h-TiO 2 A nanosheet;
preparing a sodium hydroxide solution by adopting sodium hydroxide and deionized water, and preparing a cobalt acetate solution by adopting cobalt acetate tetrahydrate and deionized water;
step four, the h-TiO obtained in the step two is treated 2 Dispersing the nano-sheets into deionized water, uniformly dispersing by ultrasonic, adding the cobalt acetate solution and the sodium hydroxide solution obtained in the step three, stirring, and transferring into a reaction kettle for hydrothermal reaction; cooling to room temperature after the reaction, sequentially adopting water and absolute ethyl alcohol to carry out centrifugal washing, and carrying out vacuum drying to obtain the cobalt intermediate loaded h-TiO 2 A nanosheet;
step five, the h-TiO obtained in the step four is treated 2 Nanoplatelets, at N 2 Calcining under the condition that the calcining temperature is controlled to be 600 ℃ and the calcining time is controlled to be 4-10 h, thus obtaining CoO/h-TiO 2 Nano heterostructures.
2. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized in that the dosage of tetrabutyl titanate in the first step is 1-5 mL, and the dosage of hydrofluoric acid is 0.16-0.8 mL.
3. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized in that the solvothermal reaction temperature in the first step is 140-200 ℃ and the reaction time is 12-24 h.
4. A CoO/h-TiO according to claim 1 2 Preparation of nano heterostructuresThe method is characterized in that the concentration of the sodium hydroxide solution in the step one is 0.1mol/L.
5. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized in that the heating rate is controlled to be 2-10 ℃/min in the second step.
6. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized in that the concentration of the sodium hydroxide solution in the step three is 0.5mol/L, and the concentration of the cobalt acetate solution is 1.0mol/L.
7. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized by comprising the step four of preparing 60mg of h-TiO 2 The nanoplatelets are dispersed in 30mL deionized water.
8. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized by comprising the step four of adding a cobalt acetate solution and a sodium hydroxide solution according to the molar ratio of cobalt acetate tetrahydrate to sodium hydroxide of 1:2.5.
9. A CoO/h-TiO according to claim 8 2 The preparation method of the nano heterostructure is characterized in that the volume of the cobalt acetate solution added in the fourth step is 10-75 mu L.
10. A CoO/h-TiO according to claim 1 2 The preparation method of the nano heterostructure is characterized in that the hydrothermal reaction temperature is controlled to be 140-200 ℃ and the reaction time is controlled to be 8-16 h.
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