CN113042032A - Tungsten oxide photocatalyst with high-efficiency heterogeneous phase and preparation method and application thereof - Google Patents
Tungsten oxide photocatalyst with high-efficiency heterogeneous phase and preparation method and application thereof Download PDFInfo
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- CN113042032A CN113042032A CN202110353962.5A CN202110353962A CN113042032A CN 113042032 A CN113042032 A CN 113042032A CN 202110353962 A CN202110353962 A CN 202110353962A CN 113042032 A CN113042032 A CN 113042032A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 71
- 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 22
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000001699 photocatalysis Effects 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 53
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- -1 alkali metal tungstate Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 11
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 206010019909 Hernia Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
-
- 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
- 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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- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- 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
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- 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
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Abstract
The invention relates to the technical field of photocatalysts, in particular to a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, and a preparation method and application thereof. The photocatalyst provided by the invention comprises WO3·0.33H2O and in said WO3·0.33H2m-WO with O in-situ phase change3Said WO3·0.33H2O and m-WO3The interface of (a) forms a heterogeneous phase. In the present invention, WO3·0.33H2O and m-WO3Capable of forming high-efficiency hetero-phase and greatly promoting photo-generated electrons and holesSeparation, thereby improving the photocatalytic activity of the photocatalyst of the present invention; at the same time, due to WO3·0.33H2O and m-WO3Is also WO3System of WO3·0.33H2O and m-WO3The condition of energy level matching is easier to meet, and the electronic structure with two similar components can make the photoproduction electrons easier to realize the migration in the heterogeneous phase, thereby improving the activity of photocatalytic water decomposition.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, and a preparation method and application thereof.
Background
Among the many methods for producing hydrogen energy by decomposing water, photocatalytic water decomposition is widely regarded as a simple and easy-to-operate method for producing hydrogen. In recent years, although some photocatalysts have been disclosed, for example, chinese patent CN109261215A discloses a catalyst for photocatalytic water splitting to prepare hydrogen, the hydrogen production capacity of the disclosed graphene-supported metal platinum catalyst is 0.8 μmol/h at most, and chinese patent CN111229260A discloses a cadmium sulfide nanoparticle and molybdenum disulfide nanobelt heterostructure catalyst for hydrogen production by water splitting under visible light and a preparation method thereof, the hydrogen production capacity of the disclosed heterojunction catalyst IDE is 203.7 μmol/(h · g) at most, but the photocatalyst capable of photocatalytic water splitting with high efficiency is rare, mainly because: the separation of the electron and hole pairs of the catalyst is difficult. In the prior art, the electron and hole pairs of the catalyst have better separation effect by methods such as increasing the crystallization degree of the catalyst, carrying a cocatalyst, carrying out doping modification and the like, but the improvement of the factors has limited improvement on the photocatalytic activity.
The tungsten oxide-based semiconductor photocatalyst has the advantages of visible light absorption, easiness in preparation and the like as the photocatalyst, but the tungsten oxide-based semiconductor photocatalyst also limits the development of the tungsten oxide-based semiconductor photocatalyst in the field of photocatalysis due to the problem of higher recombination probability of photon-generated carriers.
Disclosure of Invention
The invention aims to provide a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, comprising WO3·0.33H2O and in said WO3·0.33H2m-WO with O in-situ phase change3，
Said WO3·0.33H2O and m-WO3The interface of (a) forms a heterogeneous phase.
Preferably, said WO3·0.33H2O and m-WO3The mass ratio of (4-9): (1-6).
The invention provides a preparation method of a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, which comprises the following steps:
mixing alkali metal tungstate with water to obtain an alkali metal tungstate aqueous solution, and carrying out a first hydrothermal reaction to obtain WO3·0.33H2O；
Subjecting said WO to3·0.33H2Mixing O with water to obtain WO3·0.33H2And carrying out a second hydrothermal reaction on the O aqueous solution to obtain the photocatalyst.
Preferably, the alkali metal tungstate is sodium tungstate or potassium tungstate.
Preferably, the mass concentration of the alkali metal tungstate aqueous solution is 0.01-0.03 g/mL.
Preferably, the pH values of the first hydrothermal reaction and the second hydrothermal reaction are independently 0.5-1.5.
Preferably, the temperature of the first hydrothermal reaction and the temperature of the second hydrothermal reaction are independently 180-200 ℃.
Preferably, the time of the first hydrothermal reaction is 3-6 hours, and the time of the second hydrothermal reaction is 1-48 hours.
The invention provides the application of the tungsten oxide photocatalyst with the high-efficiency heterogeneous phase obtained by the preparation method in the technical scheme or the application of the tungsten oxide photocatalyst with the high-efficiency heterogeneous phase obtained by the preparation method in photocatalytic water decomposition.
Preferably, the mass concentration of the photocatalyst in a photocatalytic water splitting system is 0.001-0.005 g/mL.
The invention provides a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, comprising WO3·0.33H2O and in said WO3·0.33H2m-WO with O in-situ phase change3Said WO3·0.33H2O and m-WO3The interface of (a) forms a heterogeneous phase. In the present invention, the WO3·0.33H2O is an orthogonal phase, the conduction band position is-0.53 eV, the valence band position is 2.67eV, and the m-WO3Is monoclinic phase, the position of the conduction band is-0.03 eV, the position of the valence band is 2.77eV, WO3·0.33H2O and m-WO3The conduction band and the valence band of (1) are in proper positions and can form a high-efficiency hetero-junction, WO3·0.33H2O and m-WO3The construction of the 'junction' in the formed heterogeneous phase greatly promotes the separation of photo-generated electrons and holes, thereby improving the photocatalytic activity of the photocatalyst; at the same time, due to WO3·0.33H2O and m-WO3Is also WO3System of WO3·0.33H2O and m-WO3The condition of energy level matching is easier to meet, the electron structure with two similar components can make the photoproduction electrons easier to realize the migration in the heterogeneous phase, and the WO is obviously improved3·0.33H2Photogenerated electrons in O and m-WO3The separation efficiency of the mesogenic holes is improved, thereby improving the activity of photocatalytic water decomposition. According to the results of the embodiment, the hydrogen production rate and the oxygen production rate of the photocatalyst provided by the invention are 0.3-0.7 mu mol/h and 6.8-7.7 mu mol/h respectively when the photocatalyst is used for decomposing water through photocatalysis.
The invention also provides a preparation method of the photocatalyst, which is prepared in WO through hydrothermal reaction3·0.33H2O in situ phase transition to m-WO3The preparation method is simple and easy to implement.
Drawings
FIG. 1 is an XRD pattern of the photocatalyst described in example 3;
FIG. 2 is a component ratio diagram of the photocatalysts described in examples 1-3 and comparative examples 1-2;
FIG. 3 is a hydrogen production activity test chart of the photocatalysts of examples 1-3 and comparative examples 1-2;
FIG. 4 is a graph showing the oxygen generating activity of the photocatalysts according to examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
The invention provides a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, comprising WO3·0.33H2O and in said WO3·0.33H2m-WO with O in-situ phase change3Said WO3·0.33H2O and m-WO3The interface of (a) forms a heterogeneous phase.
The photocatalyst provided by the invention comprises WO3·0.33H2O, said WO3·0.33H2The O conduction band position is-0.53 eV, and the valence band position is 2.67 eV; the photocatalyst provided by the invention comprises m-WO3Said m-WO3The conduction band position of (A) is-0.03 eV, and the valence band position is 2.77 eV; in the present invention, the WO3·0.33H2O and m-WO3The heterogeneous junction of the photocatalyst greatly promotes the separation of photo-generated electrons and holes of the photocatalyst, thereby improving the photocatalytic activity of the photocatalyst.
WO in the invention for the photocatalyst3·0.33H2O and m-WO3The mass ratio of (A) to (B) is not particularly limited, and in the present invention, the WO is3·0.33H2O and m-WO3The mass ratio of (1) to (9): (1-6), more preferably (4.5-7): (2-5), most preferably (5-6): (3-4).
The invention provides a preparation method of a tungsten oxide photocatalyst with high-efficiency heterogeneous phase, which comprises the following steps:
mixing alkali metal tungstate with water to obtain an alkali metal tungstate aqueous solution, and carrying out a first hydrothermal reaction to obtain WO3·0.33H2O；
Subjecting said WO to3·0.33H2Mixing O with water to obtain WO3·0.33H2And carrying out a second hydrothermal reaction on the O aqueous solution to obtain the photocatalyst.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
The invention mixes alkali metal tungstate with water to obtain alkali metal tungstate aqueous solution, and carries out first hydrothermal reaction to obtain WO3·0.33H2O; in the present invention, the alkali metal tungstate is preferably sodium tungstate or potassium tungstate, more preferably sodium tungstate, and most preferably sodium tungstate dihydrate; the mass concentration of the alkali metal tungstate aqueous solution is preferably 0.01-0.03 g/mL, and more preferably 0.015-0.025 g/mL.
In the invention, the pH value of the first hydrothermal reaction is preferably 0.5-1.5, and more preferably 0.8-1.2, the pH value of the first hydrothermal reaction is preferably obtained by adjusting a pH adjusting agent, the pH adjusting agent preferably comprises a strong acid, the strong acid preferably comprises nitric acid or hydrochloric acid, and the mass concentration of the strong acid is 10-30%.
In the invention, the temperature of the first hydrothermal reaction is preferably 180-200 ℃, and more preferably 180 ℃; the time of the first hydrothermal reaction is preferably 3-6 h, and more preferably 4-5 h.
In the present invention, the first hydrothermal reaction is preferably performed in a forced air drying oven, and the present invention is not particularly limited to the specific embodiment of the first hydrothermal reaction, and may be performed by a method known to those skilled in the art.
In the present invention, the alkali metal tungstate is first reacted to H by a first hydrothermal reaction2WO4，H2WO4Continued reaction with water to form water and oxygenates WO3·0.33H2O。
In the invention, water and oxide WO are obtained by controlling the pH value, hydrothermal time and hydrothermal reaction temperature in the first hydrothermal reaction process3·0.33H2O。
The invention preferably carries out post-treatment on the solid product of the first hydrothermal reaction to obtain the WO3·0.33H2In the present invention, the post-treatment preferably comprises sequentially: washing and drying, in the present inventionThe washed solvent is preferably a mixed solution of ethanol and strong acid, and the mass ratio of the ethanol to the strong acid is preferably 200 mL: and 100 μ L of strong acid, wherein the protection range of the strong acid is preferably the same as that of the strong acid used for pH adjustment, which is not described herein, and in the present invention, the number of washing is preferably 3 to 5, and more preferably 4. The washed solid product is preferably dried, in the invention, the drying is preferably freeze drying, the temperature of the freeze drying is preferably-50 to-60 ℃, and the time of the freeze drying is preferably 10 to 30 hours, and more preferably 12 to 20 hours.
To obtain WO3·0.33H2After O, WO is added to the invention3·0.33H2Mixing O with water to obtain WO3·0.33H2Carrying out a second hydrothermal reaction on the O aqueous solution to obtain the photocatalyst; in the present invention, the WO3·0.33H2The mass concentration of the O aqueous solution is preferably 0.012-0.05 g/mL, more preferably 0.02-0.03 g/mL; in the present invention, the water is preferably deionized water.
In the present invention, the pH value of the second hydrothermal reaction is preferably within the same range as the pH value of the first hydrothermal reaction, and is not described herein again.
In the invention, the temperature of the second hydrothermal reaction is preferably 180-200 ℃, and more preferably 200 ℃; the time of the second hydrothermal reaction is preferably 1-18 h, and more preferably 12-24 h.
In the present invention, the WO3·0.33H2In-situ phase change of O during the second hydrothermal reaction to generate m-WO3The invention obtains the m-WO by controlling the pH value and the hydrothermal reaction temperature in the second hydrothermal reaction process3And (4) phase(s). In the present invention, m-WO is contained in the photocatalyst3The content of the phase is positively correlated with the time of the second hydrothermal reaction, and the m-WO in the photocatalyst is increased along with the increase of the time of the second hydrothermal reaction3The content of the phase becomes large.
In the present invention, the second hydrothermal reaction is preferably performed in a forced air drying oven, and the embodiment of the second hydrothermal reaction is not particularly limited, and may be performed by a process known to those skilled in the art.
In the invention, the post-treatment is preferably carried out on the solid product of the second hydrothermal reaction to obtain the photocatalyst, and the protection range of the post-treatment is preferably the same as that of the post-treatment of the first hydrothermal reaction, and is not described herein again.
m-WO in heterogeneous phase formed by photocatalyst prepared by the preparation method provided by the invention3Is prepared from WO3·0.33H2O in situ phase change to cause WO3·0.33H2O and m-WO3The condition of energy level matching is more easily met, and the WO is remarkably improved3·0.33H2Photogenerated electrons in O and m-WO3The separation efficiency of the mesogenic holes is improved, thereby improving the activity of photocatalytic water decomposition.
The invention provides the application of the tungsten oxide photocatalyst with the high-efficiency heterogeneous phase obtained by the preparation method in the technical scheme or the application of the tungsten oxide photocatalyst with the high-efficiency heterogeneous phase obtained by the preparation method in photocatalytic water decomposition.
In the invention, the mass concentration of the photocatalyst in a photocatalytic water decomposition system is preferably 0.001-0.005 g/mL, and more preferably 0.002-0.004 g/mL; in the invention, the light source of the photocatalytic water splitting system is preferably a hernia lamp, and the power of the hernia lamp is preferably 300W; in the invention, the photocatalytic water splitting system preferably comprises a photocatalytic water splitting hydrogen production system or a photocatalytic water splitting oxygen production system.
In the invention, the system for preparing hydrogen by photocatalytic water decomposition preferably comprises a photocatalyst, a cocatalyst, a sacrificial agent and water, wherein the water is preferably deionized water; in the invention, the cocatalyst is preferably simple substance platinum or chloroplatinic acid, and in the invention, the mass ratio of the cocatalyst to water is preferably (0.3-0.6) g: 100mL, in the invention, the sacrificial agent is preferably methanol, and the volume ratio of the sacrificial agent to water is preferably (1-2): 10.
in the invention, the oxygen production system by photocatalytic water decomposition preferably comprises a photocatalyst, a sacrificial agent and water, wherein the water is preferably deionized water; in the invention, the sacrificial agent is preferably silver nitrate, and the mass concentration of the sacrificial agent is preferably 0.001-0.002 g/mL.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the condition of stirring, 0.9896g of sodium tungstate dihydrate and 50mL of deionized water are mixed until the sodium tungstate dihydrate and the deionized water are completely dissolved, and HNO with the mass concentration of 20% is dropwise added3The mixed system is adjusted to pH value of 0.5, hydrothermal reaction is carried out for 4 hours at 180 ℃, and EtOH-HNO is used3(volume 200 mL: 100. mu.L, wherein the nitric acid volume concentration is 0.05%) was washed 4 times and freeze-dried at-55 ℃ for 16 hours to obtain WO3·0.33H2O。
0.62g of WO3·0.33H2Mixing O and 50mL of deionized water until all the O is dissolved, and then dropwise adding HNO3The mixed system was heated under hydrothermal reaction at 200 ℃ for 4 hours at pH 1, and EtOH-HNO was added3Washing the mixed solution for 4 times, and freeze-drying the mixed solution for 16 hours at the temperature of minus 55 ℃ to obtain the photocatalyst which is recorded as NWO-1, WO in NWO-13·0.33H2O and m-WO3The mass ratio of (A) to (B) is 87: 13.
example 2
Under the condition of stirring, 0.9896g of sodium tungstate dihydrate and 50mL of deionized water are mixed until the sodium tungstate dihydrate and the deionized water are completely dissolved, and HNO with the mass concentration of 20% is dropwise added3The mixed system is adjusted to pH 1.5, hydrothermal reaction is carried out for 4 hours at 180 ℃, and EtOH-HNO is used3(volume 200 mL: 100. mu.L, wherein the nitric acid volume concentration is 0.05%) was washed 4 times and freeze-dried at-55 ℃ for 16 hours to obtain WO3·0.33H2O。
0.62g of WO3·0.33H2O was mixed with 50mL of deionized waterMixing until all the HNO is dissolved, and then dropwise adding HNO3The mixed system is made to have a pH value of 1, hydrothermal reaction is carried out for 8 hours at 200 ℃, and EtOH-HNO is used3Washing the mixed solution for 4 times, and freeze-drying the mixed solution for 16 hours at the temperature of minus 55 ℃ to obtain the photocatalyst which is recorded as NWO-2, wherein WO in the NWO-23·0.33H2O and m-WO3The mass ratio of (A) to (B) is 81: 19.
example 3
Under the condition of stirring, 0.9896g of sodium tungstate dihydrate and 50mL of deionized water are mixed until the sodium tungstate dihydrate and the deionized water are completely dissolved, and HNO with the mass concentration of 20% is dropwise added3The mixed system is made to have a pH value of 1, hydrothermal reaction is carried out for 4 hours at 180 ℃, and EtOH-HNO is used3(volume 200 mL: 100. mu.L, wherein the nitric acid volume concentration is 0.05%) was washed 4 times and freeze-dried at-55 ℃ for 16 hours to obtain WO3·0.33H2O。
0.62g of WO3·0.33H2Mixing O and 50mL of deionized water until all the O is dissolved, and then dropwise adding HNO3The mixed system is made to have a pH value of 1, hydrothermal reaction is carried out for 12 hours at 200 ℃, and EtOH-HNO is used3Washing the mixed solution for 4 times, and freeze-drying the mixed solution for 16 hours at the temperature of minus 55 ℃ to obtain the photocatalyst which is recorded as NWO-3, wherein WO in the NWO-33·0.33H2O and m-WO3The mass ratio of (A) to (B) is 41: 59.
comparative example 1
Under the condition of stirring, 0.9896g of sodium tungstate dihydrate and 50mL of deionized water are mixed until the sodium tungstate dihydrate and the deionized water are completely dissolved, and HNO with the mass concentration of 20% is dropwise added3The mixed system is adjusted to pH value of 0.5, hydrothermal reaction is carried out for 4 hours at 180 ℃, and EtOH-HNO is used3The mixed solution (with the volume of 200 mL: 100 mu L, wherein the volume concentration of the nitric acid is 0.05%) is washed for 4 times and is frozen and dried for 16h at the temperature of minus 55 ℃ to obtain the photocatalyst, which is recorded as NWO-4 in NWO-43·0.33H2O and m-WO3The mass ratio is 100: 0.
comparative example 2
Under the condition of stirring, 0.9896g of sodium tungstate dihydrate and 50mL of deionized water are mixed until the sodium tungstate dihydrate and the deionized water are completely dissolved, and HNO with the mass concentration of 20% is dropwise added3The mixed system is adjusted to pH value of 0.5, hydrothermal reaction is carried out for 4 hours at 180 ℃, and EtOH-HNO is used3(volume 200 mL: 100. mu.L, wherein the nitric acid volume concentration is 0.05%) was washed 4 times and freeze-dried at-55 ℃ for 16 hours to obtain WO3·0.33H2O。
0.62g of WO3·0.33H2Mixing O and 50mL of deionized water until all the O is dissolved, and then dropwise adding HNO3The mixed system is made to have a pH value of 1, hydrothermal reaction is carried out for 48 hours at 200 ℃, and EtOH-HNO is used3Washing the mixed solution for 4 times, and freeze-drying the mixed solution for 16 hours at the temperature of-55 ℃ to obtain the photocatalyst which is recorded as NWO-5, WO in NWO-53·0.33H2O and m-WO3Is 0: 100.
test example 1
The photocatalyst described in example 3 was subjected to XRD testing, and the results are shown in fig. 1. The peaks appearing at diffraction angles of 14 °, 18 °, 27 °, 36 ° and 49 ° are WO3·0.33H2Characteristic peak of O, and WO3·0.33H2The O standard card (PDF #72-0199) is consistent; peaks appearing at diffraction angles of 23 °, 34 °, 39 ° and 48 ° are m-WO3Characteristic peak, with m-WO3Standard card (PDF #71-2141) was in agreement, indicating that example 3 successfully prepared WO3·0.33H2O and m-WO3The heterogeneous junction photocatalyst of (1). Said WO3·0.33H2The O conduction band position is-0.53 eV, and the valence band position is 2.67 eV; the photocatalyst provided by the invention comprises m-WO3Said m-WO3The conduction band position of (A) is-0.03 eV, and the valence band position of (B) is 2.77 eV.
Application example 1
The photocatalysts prepared in the examples 1-3 and the comparative examples 1-2 are subjected to a catalytic activity test:
and (3) testing hydrogen production activity: 0.1g of photocatalyst and 90mL of deionized water were placed in a reactor, and mixed with stirring to constitute a suspension system, and 50. mu.L of chloroplatinic acid (concentration 10mg/mL in terms of Pt) and 10mL of methanol were added in this order. And (3) connecting the reactor into a photocatalytic test system, vacuumizing for 20min to remove dissolved oxygen contained in water, starting a xenon lamp for irradiation, and carrying out photocatalytic water decomposition reaction under the irradiation of a 300W xenon lamp light source. And carrying out the light deposition reaction 2 hours before turning on the lamp, removing the light source after the light deposition is finished, vacuumizing for 5min to remove gas generated by the light deposition reaction in the photocatalysis test circulation system, moving the light source back to carry out the photocatalysis water decomposition reaction, starting timing from the moment, sampling for 1 time every 1 hour, and sampling for 4h after the timing is started. The hydrogen production activity is displayed by a gas chromatograph connected with a photocatalytic test system.
Oxygen production activity test: 0.1g of photocatalyst and 100ml of deionized water were placed in a reactor, mixed with stirring to form a suspension, and 0.1699g of silver nitrate was added. And (3) connecting the reactor into a photocatalytic test system, vacuumizing for 20min to remove dissolved oxygen contained in water, starting a xenon lamp for irradiation, and carrying out photocatalytic water decomposition reaction under the irradiation of a 300W xenon lamp light source. And starting timing after the lamp is turned on, sampling for 1 time every 1h, and sampling until the 4h after timing is started. The oxygen generating activity is demonstrated by a gas chromatograph connected to a photocatalytic test system.
The test results are shown in FIG. 3, and the data from FIG. 3 are presented in Table 1. As shown in FIG. 3 and Table 1, the photocatalyst provided by the present invention is formed of WO3·0.33H2O and m-WO3The interface heterogeneous phase of the photocatalyst greatly promotes the separation of photo-generated electrons and holes of the catalyst, so that the photocatalytic activity of the photocatalyst is improved, when water is decomposed by photocatalysis, the hydrogen production rate is 0.3-0.7 mu mol/h, the oxygen production rate is 6.8-7.7 mu mol/h, and the catalyst prepared in the comparative example 1 is only WO3·0.33H2O, the hydrogen production rate is 0.02 mu mol/h, the oxygen production rate is 3.7 mu mol/h, and the catalyst prepared in the comparative example 2 is only m-WO3The hydrogen production rate is 0 mu mol/h, the oxygen production rate is 6.2 mu mol/h, and the hydrogen production rate and the oxygen production rate are all lower than the catalyst products obtained in the embodiments 1 to 3.
TABLE 1 hydrogen and oxygen generating Activity of different photocatalysts
| Serial number | H2The rate of formation is μmol/h | O2The rate of formation is μmol/h |
| NWO-1 | 0.7 | 6.8 |
| NWO-2 | 0.5 | 7.7 |
| NWO-3 | 0.3 | 7.5 |
| NWO-4 | 0.02 | 3.7 |
| NWO-5 | 0 | 6.2 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A tungsten oxide photocatalyst having a high-efficiency heterogeneous phase, characterized by comprising WO3·0.33H2O and in said WO3·0.33H2m-WO with O in-situ phase change3，
Said WO3·0.33H2O and m-WO3The interface of (a) forms a heterogeneous phase.
2. The tungsten oxide photocatalyst having a high-potency heterogeneous phase difference according to claim 1, wherein the WO is3·0.33H2O and m-WO3The mass ratio of (4-9): (1-6).
3. The method for preparing a tungsten oxide photocatalyst having a high-efficiency heterogeneous phase according to claim 1 or 2, comprising the steps of:
mixing alkali metal tungstate with water to obtain an alkali metal tungstate aqueous solution, and carrying out a first hydrothermal reaction to obtain WO3·0.33H2O；
Subjecting said WO to3·0.33H2Mixing O with water to obtain WO3·0.33H2And carrying out a second hydrothermal reaction on the O aqueous solution to obtain the photocatalyst.
4. The method according to claim 3, wherein the alkali metal tungstate is sodium tungstate or potassium tungstate.
5. The method according to claim 3 or 4, wherein the mass concentration of the aqueous solution of the alkali metal tungstate is 0.01 to 0.03 g/mL.
6. The method according to claim 3, wherein the first hydrothermal reaction and the second hydrothermal reaction independently have a pH of 0.5 to 1.5.
7. The method according to claim 3, wherein the temperatures of the first hydrothermal reaction and the second hydrothermal reaction are independently 180 to 200 ℃.
8. The preparation method according to claim 3, wherein the time for the first hydrothermal reaction is 3 to 6 hours, and the time for the second hydrothermal reaction is 1 to 48 hours.
9. Use of the tungsten oxide photocatalyst with a high-efficiency heterogeneous phase according to claim 1 or 2 or the tungsten oxide photocatalyst with a high-efficiency heterogeneous phase obtained by the preparation method according to claims 3-8 in photocatalytic water decomposition.
10. The use of claim 9, wherein the mass concentration of the photocatalyst in the photocatalytic water splitting system is 0.001-0.005 g/mL.
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