CN114768782A - TiO 22Homogeneous heterogeneous phase nano material and preparation method and application thereof - Google Patents
TiO 22Homogeneous heterogeneous phase nano material and preparation method and application thereof Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 104
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000000243 solution Substances 0.000 claims abstract description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 claims abstract description 43
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052593 corundum Inorganic materials 0.000 claims description 27
- 239000010431 corundum Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000011949 solid catalyst Substances 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 230000005540 biological transmission Effects 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000009647 facial growth Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 230000012010 growth Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000006557 surface reaction Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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Abstract
The invention discloses a TiO 22A homogeneous heterogeneous phase nano material and a preparation method and application thereof are disclosed, wherein the preparation method comprises the following steps: s1, placing titanium tetraisopropoxide and a concentrated hydrochloric acid solution in a sealed container, introducing protective gas, and stirring to uniformly mix the materials; s2, transferring the mixture into a hydrothermal kettle for hydrothermal reaction, and cooling after the reaction is finished; s3, washing the obtained product with NaOH solution, ethanol and deionized water respectively to obtain white solid precipitate; s4, drying the white precipitate in vacuum, grinding, and placing in a muffle furnace for annealing reactionNaturally cooling to room temperature after the reaction is finished to obtain the TiO2The homogeneous heterogeneous phase nanometer material contains a zero-dimensional-one-dimensional symbiotic structure coexisting with zero-dimensional particles and one-dimensional edge rods, wherein the zero-dimensional particles are in an anatase phase, and the one-dimensional edge rods are in a rutile phase. TiO prepared by the invention2The homogeneous heterogeneous junction has excellent photocatalytic performance and shows good application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic nano materials, and particularly relates to TiO (titanium dioxide)2A homogeneous heterogeneous phase nano material, a preparation method thereof and application thereof in hydrogen production by photocatalytic water decomposition.
Background
Hydrogen is a future energy source, and is expected to play a great role in realizing the national energy strategy of 'carbon neutralization' and 'carbon peaking', and solving the energy crisis and environmental pollution caused by consumption of fossil energy. Among various hydrogen preparation modes, the technology for preparing hydrogen by utilizing solar photocatalytic water splitting is the cleanest and most environment-friendly hydrogen preparation and renewable energy utilization mode. Since two Japanese scientists reported the technology for the first time in 1972, the technology for producing hydrogen by decomposing water through photocatalysis has made great progress after development of half a century. However, the efficiency of photocatalytic hydrogen production by water decomposition is still low at present due to the complexity of photocatalytic technology, and the demand of industrial application is far from being met.
On one hand, compared with electrocatalysis and thermocatalysis, the driving force for decomposing water by photocatalysis is insufficient, so that the dynamic behavior of the carrier separation and charge transmission processes is very slow, and the internal recombination is serious. On the other hand, due to the limitations of material preparation technologies and processes and the lack of deep recognition of the active surface reaction kinetics mechanism, most of the reported photocatalytic nanomaterials have low intrinsic surface activity and many defects, so that the carrier recombination is serious. For example, TiO was first studied by researchers2The photocatalytic activity of the photocatalytic nano material is greatly improved after decades of development, but the photocatalytic nano material is limited by inherent defects of the photocatalytic nano material, the band gap width is large (3.0-3.2eV, the carrier recombination is serious, and the overall activity of the photocatalysis is still low.
Researches find that the construction of hetero (homojunction) junction is an effective way for accelerating the separation of carriers and improving the activity of photocatalytic water decomposition. In the present stage, for TiO, in the aspect of constructing heterojunction2Of photocatalytic materialModifying the heterojunction formed, e.g. TiO2/g-C3N4，TiO2/CdS，TiO2/WO3Isoheterojunctions, although having improved performance, have not achieved commercial standards and, due to the complexity of the added components, have increased the amount of TiO2The difficulty and cost of the application. In the construction of homogeneous (heterogeneous) junctions, the more mature commercial titanium dioxide of type P25, produced by the gas phase process, is available from degussa, germany. The composite material is of an anatase and rutile phase composite structure, and the mass ratio of the composite material is 80/20. However, most of the synthesis methods of P25 are TiCl4The hydrogen flame burns, volatile corrosive gas is generated in the production process, and the danger is high. The TiO reported in the literature at present2Most of other types of homojunction synthesis methods are particle phase composite structures, most of the synthesis methods are two-step methods, defects are easily formed at interfaces, charge transmission is hindered, the process is complex, and the commercial requirements cannot be met.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a 'one-step method' for preparing TiO2A homogeneous heterogeneous nano material, a preparation method thereof and the TiO2The homogeneous heterogeneous phase is applied to photocatalytic water splitting to prepare hydrogen.
The technical scheme of the invention is as follows:
the invention provides a TiO2The preparation method of the homogeneous heterogeneous phase nano material comprises the following steps:
s1, placing titanium tetraisopropoxide and a concentrated hydrochloric acid solution in a sealed container, introducing protective gas, and stirring to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a hydrothermal kettle for hydrothermal reaction at the reaction temperature of 160-240 ℃ for 12-48h, and cooling after the reaction is finished;
s3, washing the product obtained in the step S2 with NaOH solution, ethanol and deionized water respectively to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven, grinding, transferring to a corundum crucible, and mixingPlacing the mixture in a muffle furnace for annealing reaction, and naturally cooling the mixture to room temperature after the reaction is finished to obtain TiO2Homogeneous heterogeneous phase nanometer material.
Preferably, the volume ratio of the titanium tetraisopropoxide to the concentrated hydrochloric acid solution in the step S1 is 10-30:3-6, and the shielding gas is one or a mixture of argon and nitrogen.
Preferably, in step S3, centrifugal washing is respectively performed with NaOH solution, ethanol and deionized water for three times, wherein the concentration of the NaOH solution is 5 mol/L; the centrifugal speed is 5000r/min, and the time of each centrifugation is 5 min.
Preferably, the drying temperature in the step S4 is 80 ℃, and the drying time is 10 h; the annealing reaction temperature is 450 ℃, the time is 3h, and the heating rate is 5 ℃/min.
The invention also provides TiO2The heterogeneous-homogeneous-phase nano material is prepared by the preparation method, and the TiO is2The homogeneous heterogeneous phase nanometer material contains a zero-dimensional-one-dimensional symbiotic structure coexisting with zero-dimensional particles and one-dimensional edge rods, wherein the zero-dimensional particles are in an anatase phase, and the one-dimensional edge rods are in a rutile phase.
Preferably, the particle size of the granular anatase is 10-20nm, the thickness of the prismatic rutile is 50-200nm, and the length is 200-1000 nm.
The invention also provides the TiO2The application of the homogeneous and heterogeneous junction nano material in hydrogen production by photocatalytic water decomposition.
The invention also provides a method for preparing hydrogen by photocatalytic water decomposition, which comprises the following steps: adding water, methanol and a solid catalyst to a photocatalytic reactor, wherein the solid catalyst is the TiO according to claim 52And (3) the heterogeneous nano material is subjected to homogeneous phase combination, air in the reactor is exhausted before reaction, a Pt source is added, and a xenon lamp is used for simulating sunlight irradiation during reaction.
Preferably, before the reaction, argon is used for purging for 15-20min, and air in the reactor is discharged; during reaction, a 300W xenon lamp is used for simulating sunlight to irradiate the supported cocatalyst Pt for 10-60min and then continuously irradiate for 5 h.
Preferably, the Pt source adopts a chloroplatinic acid solution, the concentration of the chloroplatinic acid solution is 0.1-10mg/mL, the mass of Pt is 0.1-10% of the total mass of the solid catalyst, the volume ratio of methanol to water is 0.1-0.3:1, and the ratio of the mass of the solid catalyst to the total volume of the methanol and the water is 10-200mg/80-220 mL.
The invention has the beneficial effects that:
(1) compared with the traditional two-step synthesis method, the invention controls the phase change kinetic process by controlling the thermodynamic process of crystal nucleation, particularly controls the supersaturation degree and the size effect in a growth unit, synthesizes two-phase symbiotic heterogeneous homogenous phases by a one-step method, and realizes the continuous adjustment of the proportion of two different phases of anatase and rutile;
(2) compared with a single modification mode that the traditional photocatalytic material accelerates the transmission of interface charges by constructing a heterojunction, the method simultaneously regulates and controls the saturation degree and the crystal orientation growth kinetic process in the crystal growth process, simultaneously realizes homojunction construction and active surface growth regulation and control, realizes the optimization of surface reaction kinetics while accelerating the transmission of interface charges by a built-in electric field in the homojunction construction, realizes the matching coupling of a second process and a third process of photocatalysis, namely a photochemical process and an electrochemical process, and finally realizes the improvement of the water decomposition efficiency of photocatalysis;
(3)TiO2the traditional homojunction is mostly in a 'zero-dimension-zero-dimension' particle phase composite structure, the charge transmission mode is a II-type heterojunction matching mode, and the TiO prepared by the invention2The homojunction is a zero-dimensional-one-dimensional symbiotic structure, and the charge transmission of the structure is calculated by a K-M equation, a Mott-Schottky test and DFT, and follows a Z-type body system charge transmission model: not only increases and accelerates the kinetics of interface charge transmission, but also preserves the energy potential of oxidation-reduction potential without energy loss in the charge transmission process.
Drawings
The invention is further described with reference to the following figures and examples:
FIG. 1 shows TiO prepared according to the present invention2A morphology structure chart of a homogeneous heterogeneous phase;
FIG. 2 shows TiO prepared by the present invention2Homogeneous heterogeneous phase structure and element distribution diagram;
FIG. 3 is a drawing of the present inventionPrepared TiO2Crystal structure diagram of the iso-phase;
FIG. 4 shows TiO prepared according to the present invention2A homogeneous heterogeneous phase photocatalytic hydrogen production performance diagram;
FIG. 5 shows TiO prepared according to the present invention2The band matching and charge transfer mechanism of the homogeneous-heterogeneous phase.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
This example provides a TiO2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 3mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring the white precipitate into a corundum crucible, placing the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phaseAnd (3) nano materials.
Example 2
This example provides a TiO2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 4mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, putting the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 3
This example provides a TiO2The preparation method of the homogeneous heterogeneous phase nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 5mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, putting the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 4
This example provides a TiO compound2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 3mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 200 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, putting the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 5
This example provides a TiO2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, a hydrochloric acid solution as a solvent and a crystal face growth control agent, wherein the hydrochloric acid solution is commercially available concentrated hydrochloric acid, the mass fraction of the hydrochloric acid solution is 35-37%, placing 15mL of titanium tetraisopropoxide and 3mL of the hydrochloric acid solution into a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix all the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 220 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring the white precipitate into a corundum crucible, placing the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 6
This example provides a TiO compound2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 3mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 240 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, whiteningDrying the color precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring into a corundum crucible, placing the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h at the heating rate of 5 ℃/min, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nanometer material.
Example 7
This example provides a TiO compound2The preparation method of the heterogeneous phase-change nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 5mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 160 ℃ for 36 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, putting the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 8
This example provides a TiO2The preparation method of the homogeneous heterogeneous phase nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, a hydrochloric acid solution as a solvent and a crystal face growth control agent, wherein the hydrochloric acid solution is commercially available concentrated hydrochloric acid, the mass fraction of the hydrochloric acid solution is 35-37%, placing 15mL of titanium tetraisopropoxide and 5mL of the hydrochloric acid solution into a sealed reaction glass bottle, introducing argon, and stirring for 10 minutes to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 180 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, putting the corundum crucible and the corundum crucible together in a muffle furnace for annealing reaction at 450 ℃ for 3h, and naturally cooling to room temperature after the reaction is finished to obtain the TiO2Homogeneous heterogeneous phase nano material.
Example 9
This example provides a TiO compound2The preparation method of the homogeneous heterogeneous phase nano material comprises the following steps:
s1, taking titanium tetraisopropoxide as a titanium source, taking a hydrochloric acid solution as a solvent and a crystal face growth control agent, taking a hydrochloric acid solution as a commercial concentrated hydrochloric acid, wherein the mass fraction is 35-37%, placing 15mL of titanium tetraisopropoxide and 4mL of the hydrochloric acid solution in a sealed reaction glass bottle, introducing argon, and stirring for 10min to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a polytetrafluoroethylene lining hydrothermal kettle for hydrothermal reaction at 200 ℃ for 24 hours, and naturally cooling to room temperature after the reaction is finished;
s3, respectively washing the product obtained in the step S2 with 5mol/L NaOH solution, ethanol and deionized water for three times, wherein the washing speed is 5000r/min, and the product is centrifuged for 5min each time to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven at 80 ℃ for 10h, grinding for 30min, transferring to a corundum crucible, placing in a muffle furnace together for annealing reaction at 450 ℃ for 3h, heatingThe speed is 5 ℃/min, and the TiO is obtained after the reaction is finished and the reaction is naturally cooled to the room temperature2Homogeneous heterogeneous phase nanometer material.
TiO prepared in examples 1 to 3 of the present invention2Structural component morphology analysis of heterogeneous phase nano-material, as shown in figure 1, graphs a-c and d-f are TiO prepared with 3, 4 and 5mL hydrochloric acid addition amount respectively2SEM and low power TEM patterns of the heterogeneous phase, it can be seen that all images exhibit a pronounced coexisting structure of small particles and rods. Further, it can be seen that as the addition amount of hydrochloric acid increases, the small particles are obviously reduced, the rod-shaped structure is changed from thick to thin, and the exposed crystal face is changed.
For TiO prepared in example 1 of the invention2Phase structure analysis of heterogeneous phase nano material (3mL hydrochloric acid addition amount) as shown in FIG. 2, wherein a is high power TEM image, and the synthesized TiO can be determined by lattice spacing comparison2The small particles of the heterogeneous phase are anatase and the rods are rutile. FIG. b is a graph of the prepared photo-deposited TiO with 1% Pt by mass2The preparation method of the TEM image of the homojunction comprises the following steps: 160mL of water, 40mL of methanol and 200mg of the solid catalyst prepared in the example 1 are added into a photocatalytic reactor, argon is used for purging for 20min before reaction, air in the reactor is discharged, chloroplatinic acid solution with the concentration of 5.24mmol/L is added, then a 300W xenon lamp is used for simulating sunlight to irradiate the loaded cocatalyst Pt for 30min, then centrifugal separation is carried out for 5min at the rotating speed of 5000r/min, the upper solution is filtered, and finally vacuum drying is carried out for 10h at the temperature of 80 ℃ to obtain solid powder. It can be seen from the figure that the Pt particles are clearly uniformly distributed, with a particle size less than 5nm and mostly distributed on the rod-like surface of the rutile phase and at the particle-rod interface. The EDX Mapping images in the graphs c-f show that the uniform distribution of the particles and the discrete distribution of the Pt particles are obviously seen.
TiO prepared according to examples 1 to 3 of the invention2The XRD analysis of the crystal structure of the heterogeneous phase is shown in fig. 3. It can be seen that the TiO prepared by adding 3, 4, 5mL of hydrochloric acid according to the invention2The heterogeneous homojunction shows two obvious crystal structures of anatase and rutile and the peak intensityThe anatase peak gradually decreased and the rutile phase gradually increased with increasing hydrochloric acid addition, consistent with the analysis of FIGS. 1 and 2 above.
TiO prepared according to examples 1 to 3 of the present invention2The heterogeneous-homogeneous phase is used as a solid catalyst and applied to photocatalytic water decomposition for hydrogen production, and the specific method for photocatalytic water decomposition for hydrogen production comprises the following steps: 160mL of water, 40mL of methanol and 200mg of solid catalyst were added to a photocatalytic reactor, argon gas was used for purging for 20min before the reaction, air in the reactor was discharged, a chloroplatinic acid solution with a concentration of 5.24mmol/L was added, and the mass of added Pt was controlled by controlling the amount of the added Pt, so as to obtain TiO obtained in example 12Taking the homogeneous-heterogeneous solid catalyst as an example, the mass of Pt accounts for 0.1%, 0.3%, 0.5%, 1%, 2%, 3% and 10% of the mass of the solid catalyst respectively, and during the reaction, a 300W xenon lamp is used for simulating sunlight, the sunlight is firstly irradiated for 30min to load the cocatalyst Pt, and then the cocatalyst Pt is continuously irradiated for 5 h.
The corresponding photocatalytic water splitting performance is shown in FIG. 4, where a is the TiO prepared by gradient addition of hydrochloric acid concentrations (3, 4, 5mL) in examples 1-3 of the present invention2The photocatalytic hydrogen production efficiency chart of the heterogeneous phase combination with the optical load mass fraction of 1% Pt shows that the photocatalytic hydrogen production efficiency is highest when the addition amount of hydrochloric acid is 3mL, the anatase proportion is the highest at the moment, the anatase proportion is reduced along with the further increase of the hydrochloric acid concentration, and the photocatalytic activity also shows a descending trend. This indicates that the TiO of the present invention2The proportion relationship of anatase and rutile in the homojunction is closely related to the photocatalytic activity. FIGS. b-c are graphs showing TiO prepared in example 1 using 3mL of hydrochloric acid2The photocatalytic hydrogen production performance of the homojunction is along with the relationship curve of the promoter Pt loaded with different mass ratios by the light deposition. It can be seen that the photocatalytic hydrogen production activity shows a trend of increasing and then decreasing along with the loading amount of the catalyst promoter, because the catalyst promoter can reduce overpotential and promote charge transfer and surface reaction, but can increase light scattering and hinder light absorption of the main catalyst. This competing relationship results in an optimum ratio of interface coordination with the main catalyst. Panel d is the most active selectedThe quantum efficiency curve of the catalyst is excellent, and the TiO provided by the invention can be seen2The highest quantum efficiency of the heterogeneous phase can reach 82.6%, which is the highest value reported at present.
TiO prepared by the invention2The band matching and charge transport mechanism of the homo-hetero-junction is shown in fig. 5. Calculating to obtain band gap and band edge positions through a K-M equation and a Mott-Schottky curve, calculating to obtain the positions of a work function and a Fermi energy level through a first property principle (DFT), determining the charge transmission and the corresponding band bending direction of an electric field of charges, and finally providing a charge transmission mechanism of the Z-type homojunction: electrons at the anatase conduction band position are compounded with rutile valence band holes under the action of electric field force, and the corresponding rutile conduction band electrons and the anatase valence band holes respectively perform reduction and oxidation reactions with water and methanol to finally generate hydrogen and oxidation products. The existence of the combination accelerates charge transmission and promotes the improvement of the efficiency of hydrogen production by photocatalytic water decomposition.
In conclusion, the invention provides a preparation method for simultaneously constructing a homogeneous heterogeneous phase and a growth active surface by a one-step method, changes the dynamic behavior of nucleation and growth of crystals by changing the saturation degree of a growth unit, couples two processes of phase change dynamics and specific crystal face directional growth, realizes the simultaneous construction of the homogeneous heterogeneous phase and the active surface, and achieves the purpose of one-arrow double-carving. DFT calculation and test results prove that the TiO prepared by the invention2The heterogeneous phase can promote the interface separation and the high-efficiency transmission of charges and has high-efficiency surface catalytic activity, and the TiO is2The homogeneous heterogeneous structure is formed by symbiosis of 'zero-dimension-one-dimension' anatase particles to a rutile rod-shaped surface. Excellent photocatalytic activity is obtained under the condition of supporting a cocatalyst, and the efficiency of hydrogen production by photocatalytic decomposition of water is 2.2mmol h under the condition of supporting 1 wt% of platinum (Pt) as the cocatalyst-1And the apparent quantum efficiency at 365nm reaches 82.6 percent, thereby showing good application prospect.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundary of the appended claims, or the equivalents of such scope and boundary.
Claims (10)
1. TiO (titanium dioxide)2The preparation method of the heterogeneous phase-change nano material is characterized by comprising the following steps:
s1, placing titanium tetraisopropoxide and a concentrated hydrochloric acid solution in a sealed container, introducing protective gas, and stirring to uniformly mix the materials;
s2, transferring the mixture obtained in the step S1 to a hydrothermal kettle for hydrothermal reaction at the temperature of 160-240 ℃ for 12-48h, and cooling after the reaction is finished;
s3, washing the product obtained in the step S2 with NaOH solution, ethanol and deionized water respectively to obtain white solid precipitate;
s4, drying the white precipitate in a vacuum oven, grinding, transferring to a corundum crucible, placing in a muffle furnace together for annealing reaction, and naturally cooling to room temperature after the reaction is finished to obtain TiO2Homogeneous heterogeneous phase nano material.
2. A TiO according to claim 12The preparation method of the homogeneous heterogeneous nano material is characterized in that the volume ratio of the titanium tetraisopropoxide to the concentrated hydrochloric acid solution in the step S1 is 10-30:3-6, and the protective gas is one or a mixture of argon and nitrogen.
3. The TiO of claim 12The preparation method of the homogeneous heterogeneous nano material is characterized in that NaOH solution, ethanol and deionized water are respectively used for centrifugal cleaning for three times in the step S3, and the concentration of the NaOH solution is 5 mol/L; the centrifugal speed is 5000r/min, and the time of each centrifugation is 5 min.
4. According toThe TiO of claim 12The preparation method of the heterogeneous phase-change nano material is characterized in that in the step S4, the drying temperature is 80 ℃, and the drying time is 10 hours; the annealing reaction temperature is 450 ℃, the time is 3h, and the heating rate is 5 ℃/min.
5. TiO (titanium dioxide)2A heterogeneous phase-change nanomaterial obtained by the method according to any one of claims 1 to 4, wherein the TiO is2The homogeneous heterogeneous phase nanometer material contains a zero-dimensional-one-dimensional symbiotic structure coexisting with zero-dimensional particles and one-dimensional edge rods, wherein the zero-dimensional particles are in an anatase phase, and the one-dimensional edge rods are in a rutile phase.
6. The TiO of claim 52The homogeneous heterogeneous phase nanometer material features that granular anatase of 10-20nm size, prismatic rutile of 50-200nm thickness and 200-1000nm length.
7. The TiO of claim 52The application of the homogeneous and heterogeneous junction nano material in photocatalytic water splitting hydrogen production.
8. A method for preparing hydrogen by photocatalytic water decomposition is characterized by comprising the following steps: adding water, methanol and a solid catalyst to the photocatalytic reactor, wherein the solid catalyst is the TiO according to claim 52And (3) the heterogeneous nano material is subjected to homogeneous phase combination, air in the reactor is exhausted before reaction, a Pt source is added, and a xenon lamp is used for simulating sunlight irradiation during reaction.
9. The method for preparing hydrogen by photocatalytic water splitting according to claim 8, wherein argon is used for purging for 15-20min before reaction, and air in the reactor is discharged; during the reaction, a 300W xenon lamp is used for simulating sunlight to irradiate the supported cocatalyst Pt for 10-60min and then continuously irradiate for 5 h.
10. The method for preparing hydrogen by photocatalytic decomposition of water according to claim 8, wherein the Pt source adopts a chloroplatinic acid solution, the concentration of the chloroplatinic acid solution is 0.1-10mg/mL, the mass of Pt is 0.1-10% of the total mass of the solid catalyst, the volume ratio of methanol to water is 0.1-0.3:1, and the ratio of the mass of the solid catalyst to the total volume of methanol and water is 10-200mg/80-220 mL.
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