CN114289010A - TiO 22-SnO2Composite photocatalyst and preparation method and application thereof - Google Patents
TiO 22-SnO2Composite photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114289010A CN114289010A CN202210020793.8A CN202210020793A CN114289010A CN 114289010 A CN114289010 A CN 114289010A CN 202210020793 A CN202210020793 A CN 202210020793A CN 114289010 A CN114289010 A CN 114289010A
- Authority
- CN
- China
- Prior art keywords
- tio
- composite photocatalyst
- sno
- nanotube
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 66
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002071 nanotube Substances 0.000 claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910010442 TiO2-SnO2 Inorganic materials 0.000 claims description 15
- 229910010257 TiO2—SnO2 Inorganic materials 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 14
- 230000008569 process Effects 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
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910020923 Sn-O Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- -1 biological Chemical class 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a TiO 22‑SnO2A composite photocatalyst and a preparation method and application thereof, belonging to the technical field of photocatalysis. It comprises TiO2Nanotubes and SnO2Nanoparticles of said SnO2Nanoparticles on TiO2At the mouth of the nanotube, wherein SnO2Is carried out on TiO by physical and/or chemical means2Growing the nanotube on the surface of the nanotube opening. The photocatalyst can effectively promote the separation of photon-generated carriers, thereby effectively improving the photocatalytic reduction of CO by the catalyst2The efficiency of (c).
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to TiO2-SnO2A composite photocatalyst and a preparation method and application thereof.
Background
Coal, petroleum and natural gas, which are non-renewable resources and account for more than 80% of the total energy, are used as promoters for economic development and social progress, which cause serious energy crisis in the process of gradual consumption and simultaneously generate a large amount of CO along with fossil fuels in the combustion process2The carbon balance in the natural environment is destroyed, and the greenhouse effect caused by the carbon balance causes the global temperature to rise. Thus, under the dual pressure of energy and environment, CO2The elimination of (a) is particularly important. At present, CO2The fixed carbon capture and sequestration can be used for intensively collecting CO generated by a large-scale power plant2To thereby convert CO into2Techniques for conversion to hydrocarbons, including biological, thermochemical, electrochemical, and photocatalytic conversions, can effect CO2Reduction in emissions, and provision of renewable energy.
Wherein the CO is reduced by photocatalysis2Technique, i.e. CO generation by solar energy2The conversion into hydrocarbons can realize a stable carbon cycle process, and the solar energy as a renewable resource makes the technology more economical. TiO 22As a photocatalytic material which is earlier researched and widely applied at present, the material has the properties of high chemical stability, no toxicity, low cost, easy obtainment and the like, but because of TiO2The wide band gap (Eg. apprxeq.3.0 eV) results in low energy conversion efficiency. Research shows that by designing the heterogeneous structure photocatalytic material, the band gap of the semiconductor is optimized to collect sunlight, and effective separation of light-excited electron-hole pairs is inhibited, so that the catalytic performance of the semiconductor is improved.
Through retrieval, the Chinese patent invention 201010215619.6 discloses a mesoporous metal oxide/macroporous titanium dioxide nanotube array composite photocatalyst and a preparation method thereof. The catalystThe method comprises the following steps of taking a macroporous titanium dioxide nanotube array vertically attached to a metal titanium plate as a carrier, wherein mesoporous metal oxide is filled in the macroporous titanium dioxide nanotube array, and the filling degree of the mesoporous metal oxide is 10-100% V/V. According to the preparation method, the titanium dioxide nanotube array structure is kept while the mesoporous metal oxide is introduced, the specific surface area of the nanotube array is increased, the influence of filling other non-porous oxides on pollutant adsorption and reaction area is reduced, the separation effect of photo-generated electron-hole pairs of the system is improved by compounding the titanium dioxide and 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 finds that the composite photocatalyst has certain limitation, and the composite photocatalyst only has certain degradation effect on organic matters in a solution under the photocatalysis effect and can reduce CO2It does not work well.
Therefore, there is a need to design a catalyst capable of efficiently photocatalytic reduction of CO2To reduce CO or a process for preparing the same2And (4) discharging amount and providing renewable energy.
Disclosure of Invention
1. Problems to be solved
Aiming at reducing CO by using photocatalytic material or composite material in the prior art2The invention provides a TiO compound2-SnO2A composite photocatalyst and a preparation method and application thereof; by reaction on TiO2Designing TiO at specific positions on nanotube2And SnO2The heterostructure between the two can effectively promote the separation of photon-generated carriers, thereby solving the problem that the existing photocatalytic material reduces CO2The efficiency of (2) is low.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a TiO2-SnO2A composite photocatalyst comprising TiO2Nanotubes and SnO2Nanoparticles of said SnO2Nanoparticles on TiO2At the mouth of the nanotube, wherein SnO2Is carried out on TiO by physical and/or chemical means2Growing the nanotube on the surface of the nanotube opening.
Preferably, the composite photocatalyst is prepared by mixing TiO2Nanotube as cathode material in Sn4+Electrodepositing in solution to obtain the product; in the electrodeposition process, the TiO2The potential of the nanotubes decreases gradually along their length and reaches a minimum at one of the nozzles. In the electrodeposition process, an electrodeposition voltage may be applied to the TiO2The electrical potential at the two ends of the nanotube is lowest, so that Sn4+Will be preferentially deposited on TiO2At the mouth of the nanotube, TiO thus formed2-SnO2The heterostructure will also be located at the mouth of the tube, making it easier to be exposed to light, and is based on TiO2The tubular structure of the nanotubes also more readily conducts CO2Reduction takes place at the orifice of the tube, thereby promoting the photocatalytic reduction of CO2The efficiency of (c).
Preferably, the electric current of the electrodeposition is 5 mA-100 mA, Sn4+The concentration of the solution is 0.01 mol/L-0.1 mol/L.
The preparation method of the composite photocatalyst is characterized in that the composite photocatalyst is TiO2-SnO2The composite photocatalyst is characterized in that TiO is prepared firstly2Nanotube and TiO 22The nanotube is used as cathode and conductive anode and SnCl is put in4And carrying out electrodeposition in the solution, and drying to obtain the composite photocatalyst.
Preferably, the specific preparation steps are as follows:
(1) cleaning a pure titanium foil, and then putting the cleaned pure titanium foil into ethylene glycol electrolyte for anodic oxidation;
(2) cleaning and drying the material obtained in the step (1), and then placing the material in a muffle furnace for roasting to obtain TiO2A nanotube;
(3) TiO obtained in the step (2)2Nano tube as cathode, Pt electrode as anode, SnCl at 0.03-0.1 mol/L4Carrying out electrodeposition in the solution, wherein the current is 8 mA-80 mA;
(4) cleaning the material obtained in the step (3), and then putting the material into an oven for drying to obtain TiO2-SnO2A composite photocatalyst is provided.
Preferably, in the step (1), the electrolyte is 0.1 wt% to 1.0 wt% of NH4The solvent of the solution F comprises ethylene glycol and water, and 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), SnCl4The solution also contains a refiner, the refiner comprises 0.1 mol/L-1.0 mol/L cetyl 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 drying time is 8-12 h.
The invention discloses application of a composite photocatalyst, and the composite photocatalyst is TiO disclosed in the invention2-SnO2Composite photocatalyst, and application of composite photocatalyst in photocatalytic reduction of CO2。
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a TiO2-SnO2Composite photocatalyst, TiO2Nanotubes and SnO2The nano particles have a heterostructure between them, and the heterostructure is located in the TiO2The 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 catalyst2Efficiency of methane formation rate compared to TiO alone2The photocatalyst is 6 times higher.
(2) The preparation method of the composite photocatalyst comprises the step of carrying out electrodeposition on SnO in an orderly and controllable manner2Supported on TiO2The pipe 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, the raw materials required in the preparation process are cheap and easy to obtain, and the industrial application is betterAnd (4) foreground.
Drawings
FIG. 1 is pure phase TiO2(a) And a TiO of the invention2-SnO2SEM spectrogram of the composite photocatalyst: (b) example 1, (c) example 2, (d) example 3;
FIG. 2 shows a TiO compound of the present invention2-SnO2HR-TEM spectrogram of the composite photocatalyst;
FIG. 3 shows a TiO compound of the present invention2-SnO2XPS spectra of Ti2p, Sn3d and O1s orbitals of the composite photocatalyst;
FIG. 4 is pure phase TiO2And the photocatalytic reduction of CO by the composite photocatalyst synthesized by 3 embodiments of the invention2Comparison of the 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 the invention may be practiced, and 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 presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of 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; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention is further described with reference to specific examples.
Example 1
This example provides a TiO2-SnO2The preparation method of the composite photocatalyst comprises the following steps:
(1) ultrasonic cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein electrolyte is 0.2 wt% of NH4And F, a solvent comprises a mixture of ethylene glycol and water in a ratio of 20:1, the water temperature is 50 ℃, the direct current voltage is 40V, and the electrolysis time is 40 min.
(2) Cleaning and drying the material obtained in the step (1), and then placing the material in a muffle furnace for roasting at 350 ℃, the heating time is 140min, and the heating rate is 5 ℃/min to obtain TiO2A nanotube.
(3) TiO obtained in the step (2)2Nano tube as cathode material, Pt electrode as anode material, SnCl at 0.03mol/L4The solution is subjected to electrodeposition, 0.2mol/L hexadecyl trimethyl ammonium bromide (CTMAB) is added into the solution as a refiner, the water temperature is 40 ℃, and the current is 8 mA.
(4) Further washing, drying in a drying oven at 105 ℃ for 8h to obtain TiO2-SnO2A composite photocatalyst is provided.
Finally, the TiO is reacted2-SnO2Application of composite photocatalyst in photocatalytic reduction of CO2Process, this example is in the reduction of CO2In the process CH is generated4The rate change of (2) is recorded in fig. 4.
Example 2
This example provides a TiO2-SnO2The preparation method of the composite photocatalyst comprises the following steps:
(1) ultrasonic cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein electrolyte is 0.3 wt% of NH4Solution F, solvent comprises mixture of ethylene glycol and water at a ratio of 50:1, water temperature is 45 deg.C, and DC voltage is50V, and the electrolysis time is 30 min.
(2) Cleaning and drying the material obtained in the step (1), and then placing the material in a muffle furnace for roasting at the temperature of 400 ℃, the heating time of 120min and the heating rate of 2 ℃/min to obtain TiO2A nanotube.
(3) TiO obtained in the step (2)2Nano tube as cathode material, Pt electrode as anode material, SnCl at 0.05mol/L4The solution is subjected to electrodeposition, 0.5mol/L hexadecyl trimethyl ammonium bromide (CTMAB) is added into the solution as a refiner, the water temperature is 50 ℃, and the current is 40 mA.
(4) Further washing, drying in an oven at 100 ℃ for 12h to obtain TiO2-SnO2A composite photocatalyst is provided.
Finally, the TiO is reacted2-SnO2Application of composite photocatalyst in photocatalytic reduction of CO2Process, this example is in the reduction of CO2In the process CH is generated4The rate change of (2) is recorded in fig. 4.
FIG. 2 shows TiO prepared in this example2-SnO2HR-TEM spectrogram of the composite photocatalyst, and TiO characterized in the chart2-SnO2The interplanar spacing of the composite photocatalyst is 0.35nm and 0.33nm respectively, which is attributed to TiO2(110) And SnO2(110)。
FIG. 3 shows TiO prepared in this example2-SnO2XPS spectrum of Ti2p, Sn3d, O1s orbitals of the composite photocatalyst, FIG. 3(a) is prepared TiO2-SnO2The full scanning spectrum of the composite photocatalyst shows that Ti, O and Sn elements exist, FIG. 3(b) is an XPS spectrum of Ti2p, and two peaks are respectively located at 463.8eV and 458.2eV and respectively correspond to the Ti2p1/2And Ti2p3/2Indicates that the valence of Ti is +4, FIG. 3(c) is an XPS spectrum of Sn3d, Sn3d5/2Peak at 486.1eV, Sn3d3/2The peak is at 494.6eV, indicating the valence of Sn is +4, FIG. 3(d) is a high resolution XPS spectrum of the main peak O1s, two chemical states can be fitted, the peaks at 529.3eV and 530.8eV being attributed to O, respectivelyTi-OAnd OSn-O。
By applying TiO to this example2-SnO2The characterization of HR-TEM spectrum and XPS spectrum of the composite photocatalyst shows that the TiO is2Nanotubes and SnO2The nanoparticles are effectively compounded.
Example 3
This example provides a TiO2-SnO2The preparation method of the composite photocatalyst comprises the following steps:
(1) ultrasonic cleaning pure titanium foil with thickness of 0.1mm in ethanol and acetone in sequence, wherein electrolyte is 0.8 wt% of NH4And F, a solvent comprises a mixture of ethylene glycol and water in a ratio of 80:1, the water temperature is 40 ℃, the direct current voltage is 60V, and the electrolysis time is 20 min.
(2) Cleaning and drying the material obtained in the step (1), and then placing the material in a muffle furnace for roasting at the temperature of 450 ℃, the heating time of 90min and the heating rate of 1 ℃/min to obtain TiO2A nanotube.
(3) TiO obtained in the step (2)2Nano tube as cathode material, Pt electrode as anode material, SnCl at 0.1mol/L4The solution is subjected to electrodeposition, 0.8mol/L hexadecyl trimethyl ammonium bromide (CTMAB) is added into the solution as a refiner, the water temperature is 60 ℃, and the current is 80 mA.
(4) Further cleaning, drying in an oven at 95 ℃ for 10h to obtain TiO2-SnO2A composite photocatalyst is provided.
Finally, the TiO is reacted2-SnO2Application of composite photocatalyst in photocatalytic reduction of CO2Process, this example is in the reduction of CO2In the process CH is generated4The rate change of (2) is recorded in fig. 4.
Comparative example 1
This comparative example provides a TiO2The preparation method of the photocatalyst is basically the same as that of the photocatalyst in the embodiment 1, and the main differences are that:
1) SnO not subjected to steps (3) and (4)2A deposition step of directly depositing TiO2Photocatalyst for photocatalytic reduction of CO2And (6) carrying out the process.
This comparative example is in the reduction of CO2In the process CH is generated4The rate change of (2) 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 the Chinese invention patent 201010215619.6, and the main difference between the comparative example and the example 1 is as follows:
1) mesoporous SnO2The nano material is filled in the TiO2In 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: the mesoporous structure template agent is a 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 tin tetrachloride, and the mass ratio of the metal precursor to the alcohol-water mixed solvent is 0.1: 6.5, adjusting the pH value of the system to be 1, uniformly stirring to obtain a mixed solution, dipping the macroporous titanium dioxide array in the mixed solution, pulling for 20 times, taking out, placing at the temperature of 10 ℃ and the humidity of 50%, volatilizing the solvent, self-assembling for 48 hours, placing the obtained material in a muffle furnace, heating to 600 ℃ at the temperature of 3 ℃/min, and preserving heat for 2 hours to obtain the composite photocatalyst of the composite mesoporous tin oxide/macroporous titanium dioxide nanotube array with the filling degree of 30%.
Finally, the composite photocatalyst in the comparative example is applied to photocatalytic reduction of CO2Process for the reduction of CO by the catalyst2Process 6h gave 5. mu. mol/gcataCH (A) of4。
FIG. 4 shows pure phase TiO prepared in comparative example 12And TiO prepared in examples 1 to 32-SnO2Photocatalytic reduction of CO by composite photocatalyst2Effect diagram, the specific test conditions are: the evaluation device is a sealed stainless steel reaction kettle with the volume of 100mL and a xenon lamp with the light source of 300W, the reactor is firstly cleaned and dried, and 2.0mLH is added into the reactor2O, adding stirring magneton, putting the resultant catalyst in reactor, and introducing high-purity CO2Gas (99.999%). During the photocatalytic reaction, each time0.4mL of gas was withdrawn from the autoclave at 1h intervals for detection, and the data are plotted in FIG. 4 for comparison of performance. As can be seen from FIG. 4, TiO prepared by the present invention2-SnO2The composite photocatalyst is compared with pure-phase TiO2All show higher activity, wherein the TiO prepared in example 22-SnO2The composite photocatalyst (40mA) has optimal photocatalytic performance and is compared with pure-phase TiO2The 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 is used for photocatalytic reduction of CO2The efficiency is far lower than that of the embodiment 2, and the technical scheme of the invention has certain superiority.
To investigate the reason why the photocatalyst of example 2 is excellent in performance, the applicant prepared the pure phase TiO prepared in comparative example 12And TiO prepared in examples 1 to 32-SnO2SEM spectrograms of the composite photocatalyst are compared, and FIG. 1(a) shows the prepared pure-phase TiO2Is in a nano-tubular structure and highly ordered, and FIG. 1(b) shows a smaller-sized SnO2Nanoparticles in TiO2Aggregation at the nanotube opening, due to the lower deposition current (8mA), FIG. 1(c) shows SnO2Nanoparticles aggregated in TiO2The nanotubes are open and the size and number are appropriate (40mA), and FIG. 1(d) shows that higher deposition current leads to SnO2Nanoparticles bound to each other completely covering the TiO2Nanotube surface (80 mA). Therefore, it is presumed that the deposition current is too low, resulting in SnO2Insufficient formation of TiO at a low deposition amount of the nanoparticles2-SnO2A heterostructure; while too high a deposition current results in SnO2Depositing more nano particles, and adding TiO2Sealing the opening of the nanotube to make CO2Can not react with TiO2-SnO2The heterostructures are in effective contact, so the photocatalysts prepared in examples 1 and 3 have lower photocatalytic efficiency than those prepared in example 2.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based 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, including definitions, will control. When a rate, voltage, current, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined 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 to 50 should be understood to include any number, combination of numbers, or subrange 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, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may 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 (10)
1. TiO 22-SnO2A composite photocatalyst, characterized in that it comprises TiO2Nanotubes and SnO2Nanoparticles of said SnO2Nanoparticles on TiO2At the mouth of the nanotube, wherein SnO2Is carried out on TiO by physical and/or chemical means2Growing the nanotube on the surface of the nanotube opening.
2. A TiO according to claim 12-SnO2The composite photocatalyst is characterized in that TiO is used as the composite photocatalyst2Nanotube as cathode material in Sn4+Electrodepositing in solution to obtain the product; in the electrodeposition process, the TiO2The potential of the nanotubes decreases gradually along their length and reaches a minimum at one of the nozzles.
3. A TiO according to claim 22-SnO2The composite photocatalyst is characterized in that the electric current of the electrodeposition is 5 mA-100 mA, and Sn4+The concentration of the solution is 0.01 mol/L-0.1 mol/L.
4. A preparation method of a composite photocatalyst, wherein the composite photocatalyst is the TiO as claimed in any one of claims 1 to 32-SnO2The composite photocatalyst is characterized in that TiO is prepared firstly2Nanotube and TiO 22The nanotube is used as cathode and conductive anode and SnCl is put in4And carrying out electrodeposition in the solution, and drying to obtain the composite photocatalyst.
5. The preparation method of the composite photocatalyst, as claimed in claim 4, is characterized by comprising the following specific preparation steps:
(1) cleaning a pure titanium foil, and then putting the cleaned pure titanium foil into ethylene glycol electrolyte for anodic oxidation;
(2) cleaning and drying the material obtained in the step (1), and then placing the material in a muffle furnace for roasting to obtain TiO2A nanotube;
(3) TiO obtained in the step (2)2Nano tube as cathode, Pt electrode as anode, SnCl at 0.03-0.1 mol/L4Carrying out electrodeposition in the solution, wherein the current is 8 mA-80 mA;
(4) cleaning the material obtained in the step (3), and then putting the material into an oven for drying to obtain TiO2-SnO2A composite photocatalyst is provided.
6. The method for preparing a composite photocatalyst as claimed in claim 5, wherein in step (1), the electrolyte is 0.1 wt% to 1.0 wt% of NH4The solvent of the solution F comprises ethylene glycol and water, and 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.
7. The method for preparing a composite photocatalyst as claimed in claim 5, wherein in the step (2), the calcination temperature is 350 ℃ to 450 ℃, the time is 90min to 140min, and the temperature rise rate is 1 ℃/min to 10 ℃/min.
8. The method for preparing a composite photocatalyst as claimed in claim 5, wherein in the step (3), SnCl is used4The solution also contains a refiner, the refiner comprises 0.1 mol/L-1.0 mol/L cetyl trimethyl ammonium bromide, and the temperature of the solution is 30-80 ℃.
9. The method for preparing a composite photocatalyst as claimed in claim 5, wherein in the step (4), the drying temperature is 90 ℃ to 110 ℃ and the drying time is 8h to 12 h.
10. Use of a composite photocatalyst as claimed in any one of claims 1 to 3, which is TiO2-SnO2The composite photocatalyst is characterized in that the composite photocatalyst is used for photocatalytic reduction of CO2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210020793.8A CN114289010B (en) | 2022-01-10 | 2022-01-10 | TiO (titanium dioxide) 2 -SnO 2 Composite photocatalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210020793.8A CN114289010B (en) | 2022-01-10 | 2022-01-10 | TiO (titanium dioxide) 2 -SnO 2 Composite photocatalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114289010A true CN114289010A (en) | 2022-04-08 |
| CN114289010B CN114289010B (en) | 2024-04-12 |
Family
ID=80974608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210020793.8A Active CN114289010B (en) | 2022-01-10 | 2022-01-10 | TiO (titanium dioxide) 2 -SnO 2 Composite photocatalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114289010B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-01-10 CN CN202210020793.8A patent/CN114289010B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114289010B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bafaqeer et al. | Indirect Z-scheme assembly of 2D ZnV2O6/RGO/g-C3N4 nanosheets with RGO/pCN as solid-state electron mediators toward visible-light-enhanced CO2 reduction | |
| Buller et al. | Nanostructure in energy conversion | |
| CN104988533B (en) | TiO2/BiVO4Light anode material and preparation method thereof | |
| CN102517601B (en) | Method for preparing Cu2O/TiO2 nano-tube array electrode with grapheme assembled on surface | |
| CN103991903B (en) | A kind of preparation method of mixed phase titanium dioxide nanosheet photocatalyst | |
| CN108671955B (en) | Composite catalyst for photolysis of aquatic hydrogen and preparation method thereof | |
| CN105688945A (en) | Composite photo-catalyst with molybdenum disulfide (MoS2) nanosheet/cadmium sulfide (CdS) nanowire core-shell structure | |
| Li et al. | Enhanced visible light photocatalytic hydrogenation of CO2 into methane over a Pd/Ce-TiO2 nanocomposition | |
| Luo et al. | Cu-MOF assisted synthesis of CuS/CdS (H)/CdS (C): Enhanced photocatalytic hydrogen production under visible light | |
| WO2022144043A1 (en) | Preparation method for heterojunction of mof-derived zinc oxide and titanium dioxide composite, and use in photoelectric water splitting | |
| CN113058617B (en) | Photocatalyst and preparation method and application thereof | |
| CN101786005A (en) | Method for preparing cadmium sulfide-titanium dioxide nano-tube composite catalyst | |
| CN104588040A (en) | Photocatalyst and preparation method thereof | |
| CN116139867B (en) | MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof | |
| Wang et al. | When MoS 2 meets TiO 2: facile synthesis strategies, hybrid nanostructures, synergistic properties, and photocatalytic applications | |
| CN111041508A (en) | Cobaltosic oxide array/titanium mesh water decomposition oxygen generation electrode and preparation method thereof | |
| CN106622198B (en) | A kind of composite nanostructure titanium dioxide optical catalyst and preparation method thereof | |
| Lai et al. | The ZnO–Au-Titanium oxide nanotubes (TiNTs) composites photocatalysts for CO2 reduction application | |
| CN106637285A (en) | Cu2O quantum dot-modified titanium dioxide nano-tube photoelectrode and preparation and application thereof | |
| Tahir et al. | Tailoring metal/support interaction in 0D TiO2 NPs/MPs embedded 2D MAX composite with boosted interfacial charge carrier separation for stimulating photocatalytic H2 production | |
| CN110560172A (en) | Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof | |
| CN107488864B (en) | The preparation method of the optoelectronic pole of zinc supported nickel cobalt subcarbonate | |
| CN105568309A (en) | Preparation method for photoelectrode of photoelectrochemical cell | |
| CN102527421A (en) | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof | |
| CN112023948A (en) | Photocatalyst for efficiently decomposing water to produce hydrogen by photocatalysis and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |