CN114289010B - TiO (titanium dioxide) 2 -SnO 2 Composite photocatalyst, preparation method and application thereof - Google Patents
TiO (titanium dioxide) 2 -SnO 2 Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 28
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- 238000002360 preparation method Methods 0.000 title abstract description 16
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- 239000004408 titanium dioxide Substances 0.000 title description 12
- 239000002071 nanotube Substances 0.000 claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 229910010442 TiO2-SnO2 Inorganic materials 0.000 claims 2
- 229910010257 TiO2—SnO2 Inorganic materials 0.000 claims 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 38
- 239000003054 catalyst Substances 0.000 abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention discloses a TiO 2 ‑SnO 2 A composite photocatalyst, a preparation method and application thereof belong to the technical field of photocatalysis. It comprises TiO 2 Nanotubes and SnO 2 Nanoparticles of SnO 2 Nanoparticle support on TiO 2 At the mouth of the nanotube, where SnO 2 Is physically and/or chemically bonded to TiO 2 The surface of the pipe orifice of the nanotube grows. The photocatalyst of the invention can effectively promote the separation of photon-generated carriers, thereby effectively improving the photocatalytic reduction of CO by the catalyst 2 Is not limited to the above-described embodiments.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and in particular relates to TiO 2 -SnO 2 A composite photocatalyst, a preparation method and application thereof.
Background
The three major fossil energy sources of coal, petroleum and natural gas belong to non-renewable resources and occupy more than 80% of the total energy, and are used as promoters of economic development and social progress, which cause serious energy crisis in the process of gradual consumption, and simultaneously generate a large amount of CO in the combustion process along with fossil fuel 2 The carbon balance in the natural environment is destroyed, and the global air temperature is increased due to the greenhouse effect caused by the carbon balance. Thus, CO under dual pressures of energy and environment 2 Is eliminated by (a)Is particularly important. Currently, CO 2 Carbon capture and sealing can be used for centralized collection of CO generated by large power plants 2 To CO 2 Techniques for conversion to hydrocarbons, including biological, thermochemical, electrochemical, and photocatalytic conversion, may be used to effect CO 2 Reduced emissions, and renewable energy.
Wherein the photocatalytic reduction of CO is applied 2 Technology, i.e. CO by solar energy 2 The conversion into hydrocarbon can realize stable carbon circulation process, and the solar energy is used as renewable resource to make the technology more economical. TiO (titanium dioxide) 2 As a photocatalysis material which is earlier in research and wider in application at present, the material has the characteristics of high chemical stability, no toxicity, low cost, easy obtainment and the like, but due to TiO 2 Is a low energy conversion efficiency due to the wide bandgap (Eg. Apprxeq.3.0 eV). Research shows that by designing the heterogeneous structure photocatalytic material, the band gap of the semiconductor is optimized to collect sunlight, and the effective separation of photoexcited electron-hole pairs is inhibited, so that the catalytic performance of the semiconductor is improved.
Through searching, chinese patent 201010215619.6 discloses a mesoporous metal oxide/macroporous titanium dioxide nanotube array composite photocatalyst and a preparation method thereof. The catalyst takes a macroporous titanium dioxide nanotube array vertically attached to a metal titanium plate as a carrier, mesoporous metal oxide is filled in the carrier, and the filling degree is 10-100% V/V. According to the patent, the mesoporous metal oxide is introduced, meanwhile, the titanium dioxide nanotube array structure is reserved, the specific surface area of the nanotube array is increased, the influence of other non-porous oxides filled on the pollutant adsorption and reaction area is reduced, the separation effect of the photogenerated electron-hole pairs of the system is improved through the combination of the titanium dioxide and the other mesoporous metal oxides, the spectral response range of the titanium dioxide is expanded, and the effective collection of sunlight is facilitated. However, the applicant has found that the composite photocatalyst has certain limitation, and the composite photocatalyst only has certain degradation effect on organic matters in solution under the photocatalysis effect, and has certain degradation effect on reducing CO 2 And do not function well.
Thus, at presentThere is a need to design a device that can effectively reduce CO by photocatalysis 2 Catalyst material of (2) or a process for its preparation to reduce CO 2 And the emission amount provides renewable energy sources.
Disclosure of Invention
1. Problems to be solved
For the reduction of CO by the photocatalysis material or the composite material pair in the prior art 2 The invention provides a TiO with low efficiency 2 -SnO 2 Composite photocatalyst, and preparation method and application thereof; by forming a metal oxide layer on TiO 2 Designing TiO at specific locations on nanotubes 2 And SnO 2 The heterostructure between the two can effectively promote the separation of photon-generated carriers, thereby solving the problem of reduction of CO by the existing photocatalysis material 2 Is relatively inefficient.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a TiO of the invention 2 -SnO 2 A composite photocatalyst comprising TiO 2 Nanotubes and SnO 2 Nanoparticles of SnO 2 Nanoparticle support on TiO 2 At the mouth of the nanotube, where SnO 2 Is physically and/or chemically bonded to TiO 2 The surface of the pipe orifice of the nanotube grows.
Preferably, the composite photocatalyst is a catalyst prepared by mixing TiO 2 Nanotubes as cathode material in Sn 4+ Electrodepositing in a solution to obtain; during electrodeposition, the TiO 2 The nanotube gradually decreases in potential along its length and becomes lowest at one of the nozzles. During the electrodeposition process, an electrodeposited voltage can be applied to the TiO 2 At the two ends of the nanotube, one of the ends has the lowest potential, so Sn 4+ Will be deposited on TiO preferentially 2 At the orifice of the nanotube, tiO thus formed 2 -SnO 2 Heterostructures will also be located at the orifice and thus be more exposed to light while being TiO-based 2 The tubular structure of the nanotubes also facilitates the guiding of CO 2 Reduction takes place at the pipe orifice, thereby promoting the photocatalytic reduction of CO 2 Is not limited to the above-described embodiments.
Preferably, the electric current of the electrodeposition is 5 mA-100 mA, sn 4+ The concentration in the solution is 0.01mol/L to 0.1mol/L.
The invention relates to a preparation method of a composite photocatalyst, which is TiO as described in the invention 2 -SnO 2 A composite photocatalyst is characterized in that TiO is prepared firstly 2 Nanotube and TiO 2 The nano tube is used as a cathode and a conductive anode to be put into SnCl 4 And (3) performing electrodeposition in the solution, and drying to obtain the composite photocatalyst.
Preferably, the specific preparation steps are:
(1) Cleaning a pure titanium foil, and then placing the pure titanium foil into ethylene glycol electrolyte for anodic oxidation;
(2) Cleaning and drying the material obtained by the reaction in the step (1), and then placing the material in a muffle furnace for roasting to obtain TiO 2 A nanotube;
(3) TiO obtained in step (2) 2 The nano tube is used as a cathode, the Pt electrode is used as an anode, and 0.03mol/L to 0.1mol/L of SnCl is used as the anode 4 Electrodepositing in the solution, wherein the current is 8 mA-80 mA;
(4) Cleaning the material obtained in the step (3), and then putting the cleaned material into an oven for drying to obtain TiO 2 -SnO 2 A composite photocatalyst.
Preferably, in the step (1), the electrolyte is 0.1 to 1.0wt% NH 4 F, the solution comprises ethylene glycol and water, wherein the ratio of the ethylene glycol to the water is 10:1-100:1; the temperature of the electrolyte is 35-60 ℃, the direct current voltage is 30-80V, and the electrolysis time is 10-60 min.
Preferably, in the step (2), the roasting temperature is 350-450 ℃, the time is 90-140 min, and the heating rate is 1-10 ℃/min.
Preferably, in the step (3), snCl 4 The solution also contains a refiner, the refiner comprises 0.1 mol/L-1.0 mol/L hexadecyl trimethyl ammonium bromide, and the temperature of the solution is 30-80 ℃.
Preferably, in the step (4), the drying temperature is 90-110 ℃ and the time is 8-12 h.
The invention relates to application of a composite photocatalyst, which is TiO as described in the invention 2 -SnO 2 Composite photocatalyst, and application of the composite photocatalyst in photocatalytic reduction of CO 2 。
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) A TiO of the invention 2 -SnO 2 Composite photocatalyst, tiO 2 Nanotubes and SnO 2 The nano particles have a heterostructure therebetween, and the heterostructure is positioned in the TiO 2 The pipe orifice of the nano-tube can effectively promote the separation of photon-generated carriers, thereby effectively improving the photocatalytic reduction of CO by the catalyst 2 Is higher than the pure TiO 2 The photocatalyst is 6 times higher.
(2) The preparation method of the composite photocatalyst of the invention orderly and controllably prepares SnO by electrodeposition 2 Loaded on TiO 2 The orifice of the nano material is more beneficial to the separation of photo-generated carriers after illumination in the subsequent photocatalytic reaction process, the preparation process is simple, and the raw materials required in the preparation process are cheap and easy to obtain, thus having better industrial application prospect.
Drawings
FIG. 1 shows pure phase TiO 2 (a) And a TiO of the present invention 2 -SnO 2 SEM profile of the composite photocatalyst: (b) example 1, (c) example 2, (d) example 3;
FIG. 2 shows a TiO according to the invention 2 -SnO 2 HR-TEM spectrum of the composite photocatalyst;
FIG. 3 shows a TiO according to the invention 2 -SnO 2 XPS spectrogram of Ti2p, sn3d and O1s orbits of the composite photocatalyst;
FIG. 4 is a pure phase TiO 2 Photocatalytic reduction of CO with the composite photocatalyst synthesized in accordance with 3 embodiments of the present invention 2 Comparison of efficiency.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which features of the invention are identified by reference numerals. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. It will be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the invention described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention is further described below in connection with specific embodiments.
Example 1
The present embodiment provides a TiO 2 -SnO 2 The preparation method of the composite photocatalyst comprises the following steps:
(1) Ultrasonically cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein the electrolyte is NH of 0.2wt% 4 F, solution, wherein the solvent comprises glycol and water mixture in a ratio of 20:1, the water temperature is 50 ℃, the direct current voltage is 40V, and the electrolysis time is 40min.
(2) Cleaning and drying the material obtained by the reaction in the step (1), and then placing the material in a muffle furnace for roasting at the temperatureHeating at 350deg.C for 140min at a heating rate of 5deg.C/min to obtain TiO 2 A nanotube.
(3) TiO obtained in the step (2) 2 Nano tube as cathode material, pt electrode as anode material, 0.03mol/L SnCl 4 Electrodepositing in solution, adding 0.2mol/L cetyltrimethylammonium bromide (CTMAB) as refiner, water temperature being 40 deg.C, and current being 8mA.
(4) Further cleaning, and drying in an oven at 105 ℃ for 8 hours to obtain TiO 2 -SnO 2 A composite photocatalyst.
Finally, the TiO is 2 -SnO 2 Application of composite photocatalyst in photocatalytic reduction of CO 2 During the process, the embodiment reduces CO 2 CH generation in the process 4 The rate change of (c) is recorded in fig. 4.
Example 2
The present embodiment provides a TiO 2 -SnO 2 The preparation method of the composite photocatalyst comprises the following steps:
(1) Ultrasonically cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein the electrolyte is NH of 0.3wt% 4 F, solution, wherein the solvent comprises glycol and water mixture in a ratio of 50:1, the water temperature is 45 ℃, the direct current voltage is 50V, and the electrolysis time is 30min.
(2) Cleaning and drying the material obtained by the reaction in the step (1), and then placing the material in a muffle furnace for roasting at 400 ℃ for 120min at a heating rate of 2 ℃/min to obtain TiO 2 A nanotube.
(3) TiO obtained in the step (2) 2 The nano tube is used as a cathode material, the Pt electrode is used as an anode material, and 0.05mol/L SnCl is used as an anode material 4 Electrodepositing in solution, adding 0.5mol/L cetyltrimethylammonium bromide (CTMAB) as refiner, water temperature being 50deg.C, and current being 40mA.
(4) Further cleaning, and drying in a 100 ℃ oven for 12 hours to obtain TiO 2 -SnO 2 A composite photocatalyst.
Finally, the TiO is 2 -SnO 2 Application of composite photocatalyst in photocatalytic reduction of CO 2 During the process, the embodiment reduces CO 2 CH generation in the process 4 The rate change of (c) is recorded in fig. 4.
FIG. 2 shows the TiO composition prepared in this example 2 -SnO 2 HR-TEM spectrum of composite photocatalyst, and TiO characterized in the spectrum 2 -SnO 2 The interplanar spacing of the composite photocatalyst was 0.35nm and 0.33nm, respectively, due to the TiO 2 (110) And SnO 2 (110)。
FIG. 3 shows the TiO of this example 2 -SnO 2 XPS spectra of Ti2p, sn3d and O1s orbitals of the composite photocatalyst, and FIG. 3 (a) is the prepared TiO 2 -SnO 2 The full scan spectrum of the composite photocatalyst shows that Ti, O and Sn elements exist, and FIG. 3 (b) is an XPS spectrum of Ti2p, with two peaks at 463.8eV and 458.2eV respectively corresponding to Ti2p respectively 1/2 And Ti2p 3/2 Indicating that the valence of Ti is +4, FIG. 3 (c) is an XPS spectrum of Sn3d, sn3d 5/2 The peak is at 486.1eV, sn3d 3/2 The peak was located at 494.6eV, indicating that the valence state of Sn was +4, and FIG. 3 (d) is a high resolution XPS spectrum of the main peak of O1s, which can be fitted to two chemical states, the peaks at 529.3eV and 530.8eV being attributed to O, respectively Ti-O And O Sn-O 。
By the method of TiO of this example 2 -SnO 2 Characterization of HR-TEM spectrum and XPS spectrum of the composite photocatalyst shows that TiO 2 Nanotubes and SnO 2 The nanoparticles are effectively compounded.
Example 3
The present embodiment provides a TiO 2 -SnO 2 The preparation method of the composite photocatalyst comprises the following steps:
(1) Ultrasonically cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein the electrolyte is NH of 0.8wt% 4 F, solution, wherein the solvent comprises ethylene glycol and water mixture in a ratio of 80:1, the water temperature is 40 ℃, the direct current voltage is 60V, and the electrolysis time is 20min.
(2) Cleaning and drying the material obtained by the reaction in the step (1), and then placing the material in a muffle furnace for roasting at the temperature of 450 ℃ for 90min at the heating rate of 1 ℃/min to obtain the TiO 2 A nanotube.
(3) TiO obtained in the step (2) 2 Nano tube as cathode material, pt electrode as anode material, 0.1mol/L SnCl 4 Electrodepositing in solution, adding 0.8mol/L cetyltrimethylammonium bromide (CTMAB) as refiner, water temperature being 60 deg.C, current being 80mA.
(4) Further cleaning, and drying in a 95 ℃ oven for 10 hours to obtain TiO 2 -SnO 2 A composite photocatalyst.
Finally, the TiO is 2 -SnO 2 Application of composite photocatalyst in photocatalytic reduction of CO 2 During the process, the embodiment reduces CO 2 CH generation in the process 4 The rate change of (c) is recorded in fig. 4.
Comparative example 1
This comparative example provides a TiO 2 The photocatalyst was prepared in substantially the same manner as in example 1, with the main difference that:
1) SnO without steps (3) and (4) 2 A deposition step of directly adding TiO 2 Photocatalyst for photocatalytic reduction of CO 2 And (3) a process.
Comparative example in CO reduction 2 CH generation in the process 4 The rate change of (c) is recorded in fig. 4.
Comparative example 2
The comparative example provides a composite mesoporous tin oxide/macroporous titanium dioxide nanotube array composite photocatalyst, which is prepared according to the method disclosed in Chinese patent 201010215619.6, and the main difference between the comparative example and the example 1 is that:
1) Mesoporous SnO 2 Nano material is filled in TiO 2 In nanotubes, not at the orifice.
The preparation method of the photocatalyst comprises the following steps:
using a macroporous titanium dioxide array with the aperture of about 70 nanometers prepared by anodic oxidation as a carrier, wherein the mass ratio of water to ethanol in an alcohol-water mixed solvent is 1:1, the mesoporous structure template agent is cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB), and the mass ratio of the CTAB to the alcohol-water mixed solvent is 0.01:1, the metal precursor is stannic chloride, and the mass ratio of the metal precursor to the alcohol-water mixed solvent is 0.1:6.5, regulating the pH value of the system to be 1, stirring uniformly to obtain a mixed solution, immersing the macroporous titanium dioxide array in the mixed solution, lifting for 20 times, taking out, placing the mixed solution at the temperature of 10 ℃ and the humidity of 50%, volatilizing and self-assembling the solvent for 48 hours, placing the obtained material in a muffle furnace, heating to 600 ℃ at the speed of 3 ℃/min, and preserving the heat for 2 hours to obtain the composite mesoporous tin oxide/macroporous titanium dioxide nanotube array composite photocatalyst with the filling degree of 30%.
Finally, the composite photocatalyst in this comparative example was applied to photocatalytic reduction of CO 2 Process, the catalyst is used for reducing CO 2 At 6h of the process, 5. Mu. Mol/g are produced cata CH of (2) 4 。
FIG. 4 shows the pure phase TiO of comparative example 1 2 And TiO prepared in examples 1 to 3 2 -SnO 2 Photocatalytic reduction of CO with composite photocatalyst 2 The effect diagram is characterized in that the specific test conditions are as follows: the evaluation device is a closed stainless steel reaction kettle with the volume of 100mL, the light source is a xenon lamp with the weight of 300W, firstly, the reactor is cleaned and dried, and 2.0. 2.0mLH is added into the reactor 2 O, adding stirring magneton, putting the synthesized catalyst in reactor, and introducing high-purity CO 2 Gas (99.999%). During the photocatalytic reaction, 0.4mL of gas was withdrawn from the reaction vessel at 1 hour intervals for detection, and the data obtained were plotted in fig. 4 for comparison of performance. As can be seen from FIG. 4, the TiO of the present invention 2 -SnO 2 Compared with pure phase TiO, the composite photocatalyst 2 Exhibit high activity, wherein the TiO prepared in example 2 2 -SnO 2 The composite photocatalyst (40 mA) has optimal photocatalytic performance, and is compared with pure phase TiO 2 The photocatalytic reduction efficiency is improved to 6 times, and the composite photocatalyst shows extremely strong photocatalytic activity and meets the requirements of photocatalyst materials. In addition, the composite photocatalyst prepared in comparative example 2 was useful for photocatalytic reduction of CO 2 The efficiency is far lower than that of the embodiment 2, and the technical scheme of the invention has certain advantages.
To explore the reason for the excellent photocatalyst performance of example 2, the applicant prepared pure phase TiO from comparative example 1 2 And TiO prepared in examples 1 to 3 2 -SnO 2 Comparing SEM spectra of composite photocatalyst, FIG. 1 (a) shows the prepared pure phase TiO 2 In a nano-tubular structure and highly ordered, FIG. 1 (b) shows smaller size SnO 2 Nanoparticle in TiO 2 The nanotube openings are concentrated, and FIG. 1 (c) shows SnO due to the lower deposition current (8 mA) 2 Nanoparticle aggregation on TiO 2 At the nanotube openings, and of suitable size and number (40 mA), FIG. 1 (d) shows that higher deposition current results in SnO 2 The nano particles are mutually combined to completely cover TiO 2 Nanotube surface (80 mA). Therefore, it is presumed that the SnO is caused by the low deposition current flow 2 Insufficient TiO formation is achieved with low amounts of nanoparticles deposited 2 -SnO 2 A heterostructure; while the deposition current is too high, resulting in SnO 2 The deposition amount of nano particles is more, and TiO is prepared 2 Sealing the pipe orifice of the nano-tube to make CO 2 Cannot be combined with TiO 2 -SnO 2 Heterostructures are in effective contact and thus the photocatalysts produced in example 1 and example 3 are less photocatalytic than example 2.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the invention described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. Where a rate, voltage, current, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1-50 should be understood to include any number, combination of numbers, or subranges of numbers selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all fractional values between the integers described above, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
Claims (6)
1. The application of the composite photocatalyst is characterized in that the composite photocatalyst is used for photocatalytic reduction of CO2, wherein the composite photocatalyst is a TiO2-SnO2 composite photocatalyst and comprises TiO2 nanotubes and SnO2 nano particles, the SnO2 nano particles are loaded at the pipe orifice of the TiO2 nanotubes, and the SnO2 grows on the surface of the pipe orifice of the TiO2 nanotubes by a chemical method;
the composite photocatalyst is prepared by the following steps:
(1) Cleaning a pure titanium foil, and then placing the pure titanium foil into ethylene glycol electrolyte for anodic oxidation;
(2) Cleaning and drying the material obtained by the reaction in the step (1), and then placing the material in a muffle furnace for roasting to obtain the TiO2 nanotube;
(3) Taking the TiO2 nanotube obtained in the step (2) as a cathode and a Pt electrode as an anode, and performing electrodeposition in 0.03-0.1 mol/L SnCl4 solution, wherein the current is 40-80 mA;
(4) And (3) cleaning the material obtained in the step (3), and then putting the cleaned material into an oven for drying to obtain the TiO2-SnO2 composite photocatalyst.
2. The use of a composite photocatalyst according to claim 1, wherein the potential of the TiO2 nanotubes decreases gradually in the length direction thereof and becomes lowest at one of the nozzles during electrodeposition.
3. The use of a composite photocatalyst according to claim 1 or 2, wherein in the step (1), the electrolyte is 0.1wt% to 1.0wt% NH4F solution, the solvent comprises ethylene glycol and water, and the ratio of ethylene glycol to water is 10:1 to 100:1; the temperature of the electrolyte is 35-60 ℃, the direct current voltage is 30-80V, and the electrolysis time is 10-60 min.
4. The use of a composite photocatalyst according to claim 1 or 2, wherein in the step (2), the baking temperature is 350 ℃ to 450 ℃, the time is 90min to 140min, and the heating rate is 1 ℃/min to 10 ℃/min.
5. The use of a composite photocatalyst according to claim 1 or 2, wherein in step (3), snCl 4 The solution also containsThe refiner comprises 0.1 mol/L-1.0 mol/L hexadecyl trimethyl ammonium bromide, and the solution temperature is 30-80 ℃.
6. The use of a composite photocatalyst according to claim 1 or 2, wherein in the step (4), the drying temperature is 90 ℃ to 110 ℃ and the time is 8h to 12h.
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| CN101884915A (en) * | 2010-06-29 | 2010-11-17 | 上海大学 | Mesoporous metal oxide/macroporous titanium dioxide nanotube array composite photochemical catalyst and preparation method thereof |
| CN102151561A (en) * | 2011-01-22 | 2011-08-17 | 浙江理工大学 | Photocatalyst consisting of carbon nanotubes loaded with titanium dioxide and preparation method thereof |
| CN102240550A (en) * | 2011-05-12 | 2011-11-16 | 南开大学 | Low-concentration copper-doped titanium dioxide nanotube photocatalyst and preparation method thereof |
| CN112791724A (en) * | 2021-01-11 | 2021-05-14 | 桂林理工大学 | Nanotube photocatalytic bactericide, and preparation method and application thereof |
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| CN101884915A (en) * | 2010-06-29 | 2010-11-17 | 上海大学 | Mesoporous metal oxide/macroporous titanium dioxide nanotube array composite photochemical catalyst and preparation method thereof |
| CN102151561A (en) * | 2011-01-22 | 2011-08-17 | 浙江理工大学 | Photocatalyst consisting of carbon nanotubes loaded with titanium dioxide and preparation method thereof |
| CN102240550A (en) * | 2011-05-12 | 2011-11-16 | 南开大学 | Low-concentration copper-doped titanium dioxide nanotube photocatalyst and preparation method thereof |
| CN112791724A (en) * | 2021-01-11 | 2021-05-14 | 桂林理工大学 | Nanotube photocatalytic bactericide, and preparation method and application thereof |
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