CN115007136A - Tungsten oxide photocatalyst with hollow structure and preparation method and application thereof - Google Patents
Tungsten oxide photocatalyst with hollow structure and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
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- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 12
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 5
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- 239000007789 gas Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
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- AVFBYUADVDVJQL-UHFFFAOYSA-N phosphoric acid;trioxotungsten;hydrate Chemical compound O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O AVFBYUADVDVJQL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/39—
-
- B01J35/51—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of photocatalysts, and particularly relates to a tungsten oxide photocatalyst with a hollow structure, and a preparation method and application thereof. The preparation method of the tungsten oxide photocatalyst comprises the following steps: 1) mixing WCl 6 Dissolving in a solvent to obtain a mixed solution, and then cooling the mixed solution at the temperature of 5-10 ℃; 2) carrying out solvothermal reaction on the cooled mixed solution in the step 1) at 175-190 ℃, and then washing and vacuum drying to obtain a precursor W 18 O 49 (ii) a 3) In an air atmosphere, and without adding a template, the precursor W 18 O 49 Directly calcining for 2-2.5 h at the temperature of 750-800 ℃, and then cooling to obtain the catalyst. By combining the solvothermal method with the calcining process, the invention can synchronously realize the regulation and control of the oxygen vacancy concentration and the construction of the particle morphology under the condition of no template agent, greatly improve the photocatalytic water oxidation performance of the material and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a tungsten oxide photocatalyst as well as a preparation method and application thereof.
Background
The semiconductor photocatalytic water splitting hydrogen production is an important way for realizing solar energy conversion and is one of effective methods for solving the problems of environmental pollution and energy. The water decomposition reaction can be divided into two half reactions of hydrogen production and oxygen production. The photoproduction cavity in the oxygen production reaction oxidizes water to produce oxygen and protons, and the protons further react with the photoproduction electrons to produce hydrogen. The oxygen-generating reaction is the rate-limiting step in water splitting. Therefore, a key issue in improving solar conversion efficiency is to design a highly efficient semiconductor oxygen-producing photocatalyst and to improve water oxidation efficiency by lowering the catalytic reaction energy barrier or enhancing the utilization of photo-generated carriers. Based on this, the development of a modified high-efficiency oxygen-producing catalyst with low overpotential and good stability is the key to improve the photocatalytic water splitting efficiency.
WO 3 Has the advantages of proper band gap, good stability and environmental friendliness, and becomes one of the most attractive candidate materials for photocatalytic water decomposition. Nevertheless, it is submitted to WO 3 Limitation of intrinsic electronic structure, WO 3 The photocatalytic water splitting efficiency of (a) is still limited by the severe recombination of photogenerated electrons and holes and the slow surface reaction kinetics. Thus, a novel method was developed to enhance WO 3 The photocatalytic activity of (a) is still an important research direction. In recent years, researchers have further improved the photocatalytic water oxidation activity of tungsten oxide catalysts by various modification methods. Common improvement methods include metal and nonmetal doping, morphology control, defect construction, heterojunction construction and the like. Oxygen vacancies as WO 3 One of the common drawbacks of (1) has been shown to contribute to WO 3 Visible light absorption and charge carrier separation, but excess oxygen defects become recombination centers of electron-hole pairs, which is not favorable for improving the activity of the catalyst. In addition, the shape control of the crystal is a promising strategy for enhancing the photocatalytic water oxidation, and WO is reported 3 Including nanowires and nanometersSpheres, hollow structures, nanoparticles, nanosheets, nanorods, and the like.
In the prior art WO 3 When oxygen vacancies are built up, they are mostly derived from intact WO 3 Starting from crystals, the oxygen vacancies being created by chemical or physical methods, e.g. patent application CN109663584A, i.e. using WO 3 And the corresponding metal simple substance particles are mixed and sintered to prepare the oxygen vacancy metal oxide catalyst. Although the preparation process is simple, the requirements on the particle size of raw materials (metal oxide and metal simple substance particles) are strict (both need to be less than 200nm), which limits the application of some metal oxides with larger particles to the method.
In addition, in the prior art, when the crystal morphology is regulated, a hard template or a soft template method is mostly adopted to obtain a hollow structure. For example, patent application CN104874389A discloses a hollow mesoporous WO 3-x A preparation method of a visible light catalyst adopts a mesoporous silica molecular sieve KIT-6 as a hard template, silicotungstic acid or phosphotungstic acid hydrate as a tungsten trioxide precursor, firstly roasting to obtain a template loaded with tungsten trioxide, and then adopting high-purity H 2 And (3) as a reducing agent, roasting to obtain a template with a hollow structure and loaded with tungsten trioxide, and finally removing the template by adopting HF (hydrogen fluoride) to obtain the mesoporous WO3-x visible light catalyst with the hollow structure. During the preparation process, part of the reagent (such as 10% HF) used is highly toxic, and high-purity H 2 The operation condition safety coefficient is lower due to calcination in the atmosphere, the preparation process is complex, the cost is higher, and the collapse of the hollow structure after the template is removed is inevitable, so that the stability of the material is poor, and the photocatalytic water oxidation performance of the catalytic material cannot be effectively improved.
In view of the above circumstances, how to explore a simple and convenient preparation method, which can comprehensively regulate the oxygen vacancy concentration of tungsten oxide and endow the material crystal with a stable hollow structure, thereby further improving the light capture and charge carrier separation efficiency of the material and improving the photocatalytic water oxidation performance, is a technical problem to be solved urgently.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a method for preparing a tungsten oxide photocatalyst having a hollow structure, which is simple in operation, efficient, environmentally friendly, and low in cost, and can impart excellent light trapping and charge carrier separation efficiency to a catalytic material, thereby further improving the photocatalytic water oxidation performance of the photocatalyst material.
It is another object of the present invention to provide a tungsten oxide photocatalyst having a hollow structure, which has an appropriate oxygen vacancy concentration and a special hollow sphere structure, and which can exhibit excellent photocatalytic water oxidation performance.
The invention also aims to provide application of the tungsten oxide photocatalyst with a hollow structure.
In order to achieve the purpose, the preparation method of the tungsten oxide photocatalyst with a hollow structure adopts the technical scheme that:
a preparation method of a tungsten oxide photocatalyst with a hollow structure comprises the following steps:
1) mixing WCl 6 Dissolving in a solvent to obtain a mixed solution, and then cooling the mixed solution at the temperature of 5-10 ℃;
2) carrying out solvothermal reaction on the cooled mixed solution in the step 1) at 175-190 ℃, and then washing and vacuum drying to obtain a precursor W 18 O 49 ；
3) In an air atmosphere, and without adding a template, the precursor W 18 O 49 Calcining for 2-2.5 hours at the temperature of 750-800 ℃, and then cooling to obtain the catalyst;
wherein the solvent is absolute ethyl alcohol, and the WCl 6 The adding proportion of the alcohol to the absolute ethyl alcohol is 1g to (70-80) mL.
When the tungsten oxide photocatalyst with a hollow structure is prepared, the WCl is used 6 Preparing W with non-stoichiometric ratio by solvent thermal reaction 18 O 49 (WO 3-x ) And as a precursor, further controlling the calcination temperature in air to be 750-800 ℃, thereby preparing the tungsten oxide photocatalyst with proper oxygen vacancy concentration and a hollow structure.
The invention is in the test probeThe discovery is initiated in the research: by adopting a solvothermal method combined with a calcination process and strictly controlling action conditions, the concentration of oxygen vacancies can be synchronously regulated and controlled and particles can be aggregated under the condition of no template agent 3 And (5) constructing the appearance. The special structure and the appropriate oxygen vacancy concentration of the hollow sphere improve the light capture and charge carrier separation efficiency, so that the catalyst material of the invention has better photocatalytic water oxidation performance than other forms. In addition, the preparation process has the characteristics of simple operation, high efficiency, environmental protection and low cost, and is suitable for large-scale process production.
Based on promoting WCl 6 In consideration of the effect of dissolving the raw material, it is preferable that, in step 1), the dissolution is performed under ultrasound.
Tungsten chloride dissolved in ethanol can generate a rapid alcoholysis reaction, release a large amount of heat and influence the preparation appearance and sintering effect of a subsequent precursor. Therefore, in order to ensure the morphology of the obtained precursor for the subsequent solvothermal reaction, in the step 1), the cooling time is preferably 20 to 32 hours, and more preferably 24 hours.
The method adopts a solvothermal method to synthesize the precursor, and has the characteristics of environmental friendliness and simplicity in operation. The solvothermal method is a method for synthesizing a material by heating and pressurizing a reaction system (or self-generated steam pressure) with a solvent as the reaction system in a specially-made closed reactor such as a high-pressure reaction kettle to create a relatively high-temperature and high-pressure reaction environment and react or recrystallize the material. In the present invention, W is used 6+ Formation of precursor W by ion alcoholysis 18 O 49 In order to prepare W meeting the requirements of subsequent calcination 18 O 49 And (3) effectively controlling the morphology of the material and oxygen vacancy by using the precursor, preferably, in the step 2), the solvothermal reaction time is 22-30 h, and more preferably 24 h.
Further, in the step 3), the temperature is increased to 750-800 ℃ at a temperature increase rate of 8-12 ℃/min, preferably 10 ℃/min.
The invention also provides a tungsten oxide photocatalyst with a hollow structure, which is prepared by adopting the preparation method.
Photocatalytic performance verification experiments prove that the tungsten oxide photocatalyst with a hollow structure has more excellent photocatalytic water oxidation performance than other forms such as nanospheres and nano particle materials, the photocatalytic activity is 7 times and 4 times of that of solid nanospheres and block particles respectively, and the tungsten oxide photocatalyst has a good application prospect in the field of photocatalytic water decomposition hydrogen production.
The invention also provides application of the tungsten oxide photocatalyst with the hollow structure, in particular application to photocatalytic water decomposition hydrogen production.
The tungsten oxide photocatalyst with the hollow structure is used as a catalytic material for photocatalytic water decomposition hydrogen production, can effectively improve photocatalytic water decomposition efficiency, and is suitable for popularization and application.
Drawings
FIG. 1 shows precursors W according to examples 1 to 2 and comparative examples 1 to 3 of the present invention 18 O 49 And XRD patterns of the catalyst samples obtained at different temperatures;
FIG. 2 shows W in examples 1 to 2 of the present invention and comparative examples 1 to 3 18 O 49 SEM images of catalyst samples obtained at different temperatures and TEM image of WO-800-2;
FIG. 3 shows W in examples 1 to 2 of the present invention and comparative examples 1 to 3 18 O 49 And ultraviolet-visible diffuse reflection spectrograms of the catalyst samples obtained at different temperatures;
FIG. 4 is a graph showing fluorescence spectra of catalyst samples obtained at different temperatures according to examples 1 to 2 and comparative examples 1 to 3 of the present invention;
FIG. 5 is a graph showing oxygen generating activity of catalyst samples obtained at different temperatures according to examples 1 to 2 and comparative examples 1 to 3 of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, but is not to be construed as limited thereto. The starting materials and the operating techniques referred to in the following examples are, unless otherwise specified, conventional in the art. Wherein, WCl 6 Materials were from Shanghai Michelin Biochemical technology, Inc., CAS number: 13283-01-7, purity: 99 percent.
Example 1
The preparation method of the tungsten oxide photocatalyst with the hollow structure comprises the following steps:
1) 1g WCl was added to a 250mL Erlenmeyer flask 6 And 75mL of absolute ethyl alcohol, performing ultrasonic treatment until the absolute ethyl alcohol is completely dissolved to obtain a mixed solution, and cooling the mixed solution at the temperature of 8 ℃ for 24 hours;
2) transferring the mixed solution cooled in the step 1) into a high-pressure reaction kettle with a Polytetrafluoroethylene (PTFE) lining, heating at 180 ℃ for 24 hours, then sequentially washing with distilled water and absolute ethyl alcohol to be neutral, and drying in vacuum to obtain a precursor W 18 O 49 ；
3) Taking the precursor W obtained in the step 2) in an air atmosphere without adding a template 18 O 49 Heating to 800 ℃ at the speed of 10 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the catalyst.
The tungsten oxide photocatalyst having a hollow structure according to the present example was prepared by the preparation method according to the present example (described as WO-800-2).
Example 2
The preparation method of the tungsten oxide photocatalyst with a hollow structure in the embodiment comprises the following steps:
1) to a 250mL Erlenmeyer flask was added 1g WCl 6 And 75mL of absolute ethyl alcohol, performing ultrasonic treatment until the absolute ethyl alcohol is completely dissolved to obtain a mixed solution, and cooling the mixed solution at the temperature of 8 ℃ for 24 hours;
2) transferring the mixed solution cooled in the step 1) into a high-pressure reaction kettle with a Polytetrafluoroethylene (PTFE) lining, heating the mixed solution at 180 ℃ for 24 hours, and then sequentially washing the mixed solution by using distilled water and absolute ethyl alcohol until the mixed solution is neutral to obtain a precursor W 18 O 49 ；
3) Taking the precursor W obtained in the step 2) in an air atmosphere without adding a template 18 O 49 Heating to 750 ℃ at the speed of 10 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the catalyst.
The tungsten oxide photocatalyst having a hollow structure according to the present example was prepared by the preparation method according to the present example (described as WO-750-2).
Example 3
The preparation method of the tungsten oxide photocatalyst with a hollow structure in the embodiment comprises the following steps:
1) 1g WCl was added to a 250mL Erlenmeyer flask 6 And 80mL of absolute ethyl alcohol, performing ultrasonic treatment until the absolute ethyl alcohol is completely dissolved to obtain a mixed solution, and cooling the mixed solution at the temperature of 10 ℃ for 32 hours;
2) transferring the cooled mixed solution obtained in the step 1) to a high-pressure reaction kettle with a Polytetrafluoroethylene (PTFE) lining, heating at 190 ℃ for 22h, then sequentially washing the mixed solution to be neutral by using distilled water and absolute ethyl alcohol, and drying in vacuum to obtain a precursor W 18 O 49 ；
3) Taking the precursor W obtained in the step 2) in an air atmosphere without adding a template 18 O 49 Heating to 800 ℃ at the speed of 10 ℃/min, calcining for 2h, and naturally cooling to room temperature to obtain the catalyst.
The tungsten oxide photocatalyst having a hollow structure in this example was prepared by the preparation method in this example.
Example 4
The preparation method of the tungsten oxide photocatalyst with a hollow structure in the embodiment comprises the following steps:
1) to a 250mL Erlenmeyer flask was added 1g WCl 6 And 75mL of absolute ethyl alcohol, performing ultrasonic treatment until the absolute ethyl alcohol is completely dissolved to obtain a mixed solution, and cooling the mixed solution at the temperature of 5 ℃ for 20 hours;
2) transferring the cooled mixed solution obtained in the step 1) to a high-pressure reaction kettle with a Polytetrafluoroethylene (PTFE) lining, heating the mixed solution at 175 ℃ for 30h, then sequentially washing the mixed solution to be neutral by using distilled water and absolute ethyl alcohol, and drying the washed solution in vacuum to obtain a precursor W 18 O 49 ；
3) Taking the precursor W obtained in the step 2) in an air atmosphere without adding a template 18 O 49 Heating to 800 deg.C at a rate of 10 deg.C/min, calcining for 2.5h, and naturally cooling to room temperature.
The tungsten oxide photocatalyst having a hollow structure in this example was prepared by the preparation method in this example.
Comparative example 1
The tungsten oxide photocatalyst of this comparative example was prepared in substantially the same manner as in example 1, except that: the calcination temperature adopted in the step 3) is 400 ℃, and the obtained photocatalyst is recorded as WO-400-2.
Comparative example 2
The preparation method of the tungsten oxide photocatalyst of the comparative example is basically the same as that of example 1, except that: the calcination temperature adopted in the step 3) is 500 ℃, and the obtained photocatalyst is recorded as WO-500-2.
Comparative example 3
The preparation method of the tungsten oxide photocatalyst of the comparative example is basically the same as that of example 1, except that: the calcination temperature adopted in the step 3) is 900 ℃, and the obtained photocatalyst is recorded as WO-900-2.
Comparative example 4
The preparation method of the tungsten oxide photocatalyst of the comparative example is basically the same as the example, except that: the cooling step in the step 1) is omitted, and the dissolved mixed solution is directly subjected to the operation of the step 2).
Comparative example 5
The preparation method of the tungsten oxide photocatalyst of the comparative example is carried out by referring to the prior art of CN109663584A, and comprises the following specific steps: 2g of commercially available WO was taken 3 The powder and 0.05g of metal tungsten powder were thoroughly ground and mixed. And (3) carrying out heat treatment on the mixture for 2h at 800 ℃ in a tube furnace in Ar protective atmosphere, and naturally cooling to room temperature to obtain the tungsten oxide photocatalyst containing oxygen vacancies.
Comparative example 6
The preparation method of the tungsten oxide photocatalyst of the comparative example refers to a template method of CN104874389A in the prior art, and specifically adopts a mesoporous silica molecular sieve KIT-6 as a hard template, silicotungstic acid or phosphotungstic acid hydrate as a tungsten trioxide precursor, firstly roasting to obtain a tungsten trioxide-loaded template, and then using high-purity H 2 Roasting to obtain a template with a hollow structure and loaded with tungsten trioxide as a reducing agent, and finally removing the template by adopting HF (hydrogen fluoride) to obtain mesoporous WO with a hollow structure 3-x A visible light photocatalyst.
Experimental example 1 structural characterization of catalyst materials
The crystal phase structure of the sample is measured on a German Bruker Apex II X-ray diffractometer, Cu-Kalpha radiation is used for measuring, the scanning range is 20 degrees to 70 degrees, and the pace speed is 0.04 degrees. Scanning Electron Microscope (SEM) images were obtained on a Gemini SEM 500 electron microscope. The nitrogen desorption isotherm of the sample was measured using Quadrasorb SI-4 at 77K and the specific surface area of the sample was analyzed by Brunauer-Emmett-teller (bet) equation. By using BaSO 4 (analytical purity) as a reference, an ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS) analysis was performed on an Shimadzu U-3010 spectrometer equipped with an integrating sphere. Photoluminescence spectra (PL) were obtained on a HORIBA Fluoromax + fluorescence spectrometer. The results are shown in FIGS. 1 to 4.
From the XRD results of FIG. 1, it can be seen that WCl 6 The XRD pattern of the sample obtained by solvothermal treatment in ethanol showed mainly two diffraction peaks corresponding to the monoclinic W 18 O 49 The (010) and (020) crystal planes of the structure (JCPDS No. 36-101). WO began to appear on the sample after calcination for 2h at 400 deg.C (comparative example 1) 3 The characteristic peak of (1), in this case the sample is WO 3 And W 18 O 49 (ii) a heterogeneous junction structure (figure 1 a). W 18 O 49 XRD diffraction peaks of samples obtained by treating the samples at 500 deg.C (comparative example 2), 750 deg.C (example 2), 800 deg.C (example 1) and 900 deg.C (comparative example 3) all belong to WO 3 Monoclinic phase (JCPDS No.72-0677), in which WO 3 Has a standard lattice parameter of
α is 90 °, β is 90.91 ° and γ is 90 °. Typical monoclinic phase WO is shown at 23.1 DEG, 23.6 DEG and 24.4 DEG 3 The (001), (010) and (100) planes, the intensity of the diffraction peaks shows that the sample is along WO 3 The (001), (010) and (100) planes of (c) preferentially grow (fig. 1 b). Furthermore, the intensity of the main diffraction peak increased with increasing temperature, indicating that the synthesized WO 3 Has better crystallinity at higher temperature.
Further, as can be seen from the TEM image of FIG. 2, W is 18 O 49 Is sea urchin with diameter of about 1 μmShape (FIG. 2a), the sample after calcination at 500 ℃ (WO-500-2) is in the shape of a solid sphere (FIG. 2 b); when the calcination temperature reached 750 ℃, hollow spheres WO-750-2 (fig. 2c) formed by irregular particle packing began to form; when the temperature reaches 800 ℃, a plurality of nanoparticles with better crystallinity form a hollow sphere WO-800-2 structure (figure 2e), and a sample is hollow as can be seen from some broken spheres. The internal hollow structure of WO-800-2 can also be confirmed by TEM images (FIG. 2 f). When the temperature reached 900 ℃, the hollow spheres collapsed into nanoparticles (fig. 2 d). In the experimental process, the invention discovers that W 6+ The alcoholysis of ions can form W in the shape of sea urchin 18 O 49 And the nanowires collapse and pile up into nanospheres after high-temperature calcination. In the calcining process, the nano-wires can gradually form nano-particles along with the increase of the temperature. Because the nanoparticles are more energetic, they will gradually self-agglomerate into a hollow sphere structure, reaching the lowest energetic state. However, when the calcination temperature is further increased, the hollow structure is destroyed.
From the DRS diagram of FIG. 3, W 18 O 49 The material has stronger light absorption capacity in an ultraviolet-visible light region, and the visible light absorption of a sample is gradually weakened along with the reduction of the concentration of oxygen vacancies in the sample (figure 3 a). Fig. 3b shows the absorption pattern of the samples obtained at temperatures above 500 c, from which it can be seen that several samples maintain almost the same absorption intensity in the visible region. The absorption tail in the visible region disappeared, which indicates that the oxygen vacancy content in these samples was already low, resulting in a near stoichiometric WO sample 3 . Therefore, the activity of the sample obtained at a temperature higher than 500 ℃ is mainly attributed to the morphology and crystallinity of the sample. It can also be seen from fig. 3b that the sample having the hollow sphere structure has a strong light absorption capability in the ultraviolet region, and when the hollow sphere structure is broken, the ultraviolet light absorption is reduced, and thus, the light absorption of the hollow sphere sample is enhanced due to multiple reflections in the cavity inside the sphere.
As can be seen from the fluorescence intensity results of FIG. 4, the PL signal peak intensity of the hollow structure sample (WO-800-2) was significantly reduced as compared with that of the other morphological samples. Indicating that hollow structures can improve the separation of photogenerated electrons and holes. The increase in fluorescence intensity of the sample obtained after calcination at 900 ℃ is probably due to the increase in carrier recombination rate caused by the collapse of the hollow structure. This further illustrates that the improved separation efficiency of the charge carriers is due to the special hollow structure of WO-800-2.
Experimental example 2 photocatalytic activity test
Photocatalytic decomposition water oxygen activity test was performed on a reaction system of CEL-SPH2N on-line system (zhongzhi gold source limited, beijing). The reactor consists of a top quartz glass cover and a lower quartz reactor. The incident light source of the reaction system is 300W Xe lamp (CEL-HXF300, Beijing), and the light intensity is fixed at 230mW/cm 2 . In the specific operation, 50mg of the catalyst samples of examples 1 to 2 and comparative examples 1 to 6 were dispersed in 100mL of 0.05mol/L AgNO 3 In (1). The system was evacuated beforehand for 30min to remove dissolved gases from the solution. The reaction solution is illuminated for 5 hours under the condition of continuous stirring, 1mL of gas is automatically extracted every hour in the reaction process, and the gas is analyzed and detected by an online GC-7920 gas chromatograph (CEAULIGHT, China), so that the photocatalytic activity is determined. The results are shown in Table 1 and FIG. 5.
TABLE 1 results of oxygen generating activity of catalyst samples related to examples 1 to 2 and comparative examples 1 to 6
| Numbering | Photocatalytic oxygen generating Activity (μmol. g) -1 ·h -1 ) |
| Example 1 | 1082.58 |
| Example 2 | 590.5 |
| Comparative example 1 | 0 |
| Comparative example 2 | 157.03 |
| Comparative example 3 | 252.76 |
| Comparative example 4 | 217.71 |
| Comparative example 5 | 85.98 |
| Comparative example 6 | 301.69 |
As can be seen from FIG. 5, W 18 O 49 And the catalyst samples calcined at the temperature below 500 ℃ have no photocatalytic oxygen production activity, while the samples calcined at the temperature above 500 ℃ have photocatalytic oxygen production activity, and the activity is WO-800-2>WO-750-2>WO-900-2>WO-500-2. When the temperature is lower than 500 ℃, the sample forms an outer part of WO 3 The interior is still W 18 O 49 Out of phase junctions of, the photogenerated holes have WO 3 Migration to interior W 18 O 49 And cannot be contacted with water, so that it has no photocatalytic activity. As the calcination temperature is increased, the oxygen defects in the sample are reduced, and the sample is gradually converted into WO 3 . The hollow sphere sample WO-800-2 has higher photocatalytic activity than the solid sphere sample WO-500-2 and the bulk particle sample WO-900-2, which are 7 times and 4 times higher than the solid sphere and the bulk particle, respectively. The specific surface areas of the samples WO-500-2, WO-750-2, WO-800-2 and WO-900-2 were measured by BET to obtain specific surface areas of 24.17, 2.48, 1.86 and 0.38m, respectively 2 ·g -1 It can be seen that although the hollow sphere has a smaller specific surface area, it produces much higher oxygen activity than the samples of several other morphologies, which is enhanced in the ultraviolet region of lightAbsorption and improved carrier separation efficiency.
Further combining the results of comparative examples 4-6 in table 1, it can be seen that compared with the methods for regulating oxygen vacancies and constructing a hollow result in the prior art, the method provided by the invention can also significantly improve the photocatalytic oxygen production activity, and also proves the outstanding improvement effect of the invention on the performance of the catalyst material.
As a result of comprehensive analysis of the above results, the present invention was made by calcining W in air 18 O 49 The method increases the stoichiometric ratio of the oxygen vacancies, and prepares WO with different concentrations and different shapes at different calcination temperatures 3 . By characterizing the invention, it has surprisingly been found that, with increasing calcination temperature, WO 3 Gradually increases in crystallinity and forms a specific morphology containing different crystal planes. At a temperature of less than 500 ℃, the system coexists with WO 3 And W 18 O 49 These two phases and form a heterogeneous phase. WO obtained by calcination at 500 ℃ or higher 3 The oxygen vacancy content is low, and when the temperature reaches 800 ℃, a hollow spherical sample is formed. This is a template-free method of synthesizing WO consisting of nanoparticles 3 And (4) hollow spheres. The hollow ball is formed by sea urchin-shaped W 18 O 49 The process of aggregation of nanowires into solid spheres, re-sintering into hollow spheres of particle aggregation, followed by collapse into nanoparticles. The morphology of the sample can be controlled by simply adjusting the temperature, and the hollow nano-structure shows excellent photocatalytic water oxidation activity compared with solid spheres and bulk particles. Meanwhile, the specific surface area of the hollow sphere is not the highest, but the photocatalytic water oxidation activity of the hollow sphere is far higher than that of samples with other morphologies through experiments. The improvement of the photocatalytic performance is mainly due to the fact that the carrier separation is promoted by the nanometer structure of the hollow sphere, and in addition, the light reflection in the cavity of the hollow sphere is also beneficial to improving the light absorption capacity of the catalyst.
In summary, the invention adopts the solvothermal method combined with the calcination process, and strictly controls the action conditions, so that the regulation and control of the oxygen vacancy concentration and the particle aggregation can be synchronously realized under the condition without a template agent 3 And (5) constructing the appearance. And the special structure of the hollow ballAnd the appropriate oxygen vacancy concentration, the light capture and charge carrier separation efficiency is improved, so that the catalyst material of the invention has better photocatalytic water oxidation performance than other forms, and can be effectively used for industrial application of photocatalytic water decomposition hydrogen production.
Claims (7)
1. A preparation method of a tungsten oxide photocatalyst with a hollow structure is characterized by comprising the following steps:
1) mixing WCl 6 Dissolving in a solvent to obtain a mixed solution, and then cooling the mixed solution at the temperature of 5-10 ℃;
2) carrying out solvothermal reaction on the cooled mixed solution in the step 1) at 175-190 ℃, and then washing and vacuum drying to obtain a precursor W 18 O 49 ；
3) In an air atmosphere, and without adding a template, the precursor W 18 O 49 Calcining for 2-2.5 hours at the temperature of 750-800 ℃, and then cooling to obtain the catalyst;
wherein the solvent is absolute ethyl alcohol; WCl 6 The adding proportion of the alcohol to the absolute ethyl alcohol is 1g to (70-80) mL.
2. The method for preparing a tungsten oxide photocatalyst having a hollow structure according to claim 1, wherein in the step 1), the dissolution is performed under ultrasound.
3. The method for preparing the tungsten oxide photocatalyst having a hollow structure according to claim 1, wherein in the step 1), the cooling time is 20 to 32 hours.
4. The method for preparing the tungsten oxide photocatalyst with a hollow structure according to claim 1, wherein in the step 2), the solvothermal reaction time is 22-30 h.
5. The method for preparing the tungsten oxide photocatalyst having a hollow structure according to claim 1, wherein in the step 3), the temperature is raised to 750 to 800 ℃ at a temperature raising rate of 8 to 12 ℃/min.
6. A tungsten oxide photocatalyst with a hollow structure, which is prepared by the preparation method of any one of claims 1 to 5.
7. Use of the tungsten oxide photocatalyst having a hollow structure according to claim 6, wherein: the application in photocatalytic water splitting hydrogen production.
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