CN110898827A - Method for preparing tungsten photocatalyst heterojunction through doping induction - Google Patents
Method for preparing tungsten photocatalyst heterojunction through doping induction Download PDFInfo
- Publication number
- CN110898827A CN110898827A CN201911269578.6A CN201911269578A CN110898827A CN 110898827 A CN110898827 A CN 110898827A CN 201911269578 A CN201911269578 A CN 201911269578A CN 110898827 A CN110898827 A CN 110898827A
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- CN
- China
- Prior art keywords
- tungsten
- heterojunction
- photocatalyst
- tungstate
- doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 68
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 49
- 239000010937 tungsten Substances 0.000 title claims abstract description 49
- 230000006698 induction Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 37
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
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- 150000001342 alkaline earth metals Chemical class 0.000 claims 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 235000013877 carbamide Nutrition 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 claims 1
- QNHNSPNFZFBEQR-UHFFFAOYSA-N n'-(3-trihydroxysilylpropyl)ethane-1,2-diamine Chemical compound NCCNCCC[Si](O)(O)O QNHNSPNFZFBEQR-UHFFFAOYSA-N 0.000 claims 1
- 239000002073 nanorod Substances 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
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- 238000002360 preparation method Methods 0.000 abstract description 9
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- 230000000593 degrading effect Effects 0.000 abstract description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 5
- 229940043267 rhodamine b Drugs 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000005457 optimization Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 26
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000001939 inductive effect Effects 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
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- 238000004458 analytical method Methods 0.000 description 4
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- 238000001035 drying Methods 0.000 description 3
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
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- 239000005642 Oleic acid Substances 0.000 description 2
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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
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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
- 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
- B01J37/082—Decomposition and pyrolysis
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention belongs to the field of materials, and particularly relates to an in-situ heterojunction photocatalyst as well as a preparation method and application thereof. The tungsten heterojunction type photocatalyst provided by the invention is of a core-shell structure, and the inner layer and the outer layer are tungsten semiconductor oxides with different structures. According to the invention, the shell layer structure is controllably adjusted under the induction of the doping ions through the diffusion of the doping ions in the crystal lattice, so that tungsten heterojunction photocatalysts with different 'junction' structures are obtained, the photo-generated electron-hole transmission, the separation efficiency and the optimization of an energy band structure are realized, and the photocatalytic performance of the material is obviously improved. The results of the examples show that when the heterogeneous junction photocatalyst provided by the invention is used for photocatalytic water decomposition, the oxygen generation amount can reach 210 mu mol/h/g, when the heterogeneous junction photocatalyst provided by the invention is used for degrading azo macromolecule rhodamine B, the degradation rate of 100mg/L high-concentration RhB degraded in 60min reaches 93%, and the degradation rate of 10mg/L formaldehyde degraded in 180min reaches 89%.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for preparing a tungsten photocatalyst heterojunction through in-situ doping induction, in particular to a preparation method for preparing different heterojunctions by simply regulating and controlling the crystal phase composition of an inner shell layer and a crystal phase of an outer shell layer and the surface structure of a catalyst through diffusion of doping ions in a tungsten oxide pore channel, so that the photocatalytic performance and the application of the tungsten photocatalyst heterojunction are regulated and controlled.
Background
Over the past few decades, the rapid development of science and technology has brought about a change in human life. However, since human beings depend on fossil fuels which are rapidly exhausted such as petroleum, coal and natural gas, and the use of fossil fuels causes serious pollution to the environment, the development of new energy sources and the effective treatment of environmental problems are not slow. In the exploration of various novel energy sources, the direct conversion of solar energy into chemical energy is found to be one of effective ways for solving the future energy crisis and environmental pollution. To date, semiconductor-based photocatalytic technology has received much attention from researchers in all countries of the world in recent years, making use of inexhaustible clean energy as solar energy. When appropriate semiconductor materials exist, the photocatalysis technology using sunlight as a driving force can perform a plurality of catalytic reactions, such as water decomposition to prepare hydrogen and oxygen, carbon dioxide reduction to prepare hydrocarbon fuels such as methanol and the like, organic pollutant degradation, selective organic synthesis of medical intermediates and the like.
The photocatalytic technology is different from other solar energy utilization technologies in that the photocatalytic technology is a multi-step reaction, wherein the multi-step reaction comprises absorption of photons by a photocatalyst, separation and transmission of photogenerated carriers and surface reaction, the efficiency of each step can greatly influence the final catalytic effect of the photocatalyst, and the corresponding absorption efficiency, separation and transmission efficiency and surface reaction efficiency are also the key for improving the catalytic effect of the catalyst. Therefore, research methods for the respective steps also have been made: (1) in order to improve the absorption efficiency of the catalyst, the catalyst is doped and modified, or a sub-energy level and the like are manufactured by utilizing the plasmon effect of a noble metal material; (2) in order to improve the separation and transmission efficiency of the catalyst, quantum dot effect, shell layer transmission and carrier separation (including heterojunction, p-n junction and the like) driven by built-in electric field are utilized. Among them, regulation of the separation and transmission efficiency of photogenerated carriers is considered to be the most effective means for effectively improving the catalytic performance. Although the efficiency improvement strategy is widely adopted and the performance of the photocatalyst is greatly improved, the improvement effect is not obvious and a plurality of technical bottlenecks exist. For example, the 'junction' structure generally has the defects of reduced carrier energy, too high carrier interface transmission energy barrier, unstable combination of the 'junction' structure and easy separation, and the like.
Disclosure of Invention
The invention aims to provide a method for preparing a tungsten photocatalyst heterojunction through doping induction and application of the tungsten photocatalyst.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention discloses a method for preparing a tungsten photocatalyst heterojunction by doping induction, which comprises the following steps: alkali metal ions (alkaline earth metal ions) are doped into a crystal pore channel structure of the tungsten oxide, and then under the drive of temperature, the doped ions are migrated and induce the surface to generate phase change, so that the tungsten photocatalyst with the core-shell heterostructure is generated.
Preferably, the alkali metal ion includes Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+；
Preferably, the atomic ratio of the alkali metal to the tungsten is 0.01-0.2%;
preferably, the thermal diffusion temperature is 300-800 ℃, and the time of heat treatment is 2-48 h;
preferably, the preparation method for preparing the alkali (earth) metal doped tungsten oxide comprises the following steps:
(1) mixing a certain proportion of tungstate (Na)2WO4·2H2O, potassium tungstate, and the like), alkali (earth) metal sulfate and a complexing agent are quickly dissolved in a certain amount of deionized water under the condition of violent magnetic stirring;
(2) dropwise adding acid with a certain concentration into the solution obtained in the step (1) by using a liquid-transferring gun to adjust the pH value to 1-2;
(3) transferring the solution obtained in the step (2) into a polytetrafluoroethylene reaction kettle, and reacting for 10-24 h at 160-200 ℃ to obtain the alkali (earth) metal doped hexagonal phase tungsten oxide (h-WO)3)。
The invention also provides the application of the tungsten photocatalyst heterojunction photocatalyst prepared by doping induction in the technical scheme in photocatalytic water decomposition or rhodamine B degradation:
according to the doping induction preparation method of the tungsten-based photocatalyst heterojunction photocatalyst, the shell layer structure is controllably adjusted under the induction of the doping ions through the diffusion of the doping ions in crystal lattices, so that the tungsten-based heterojunction photocatalyst with different 'junction' structures is obtained, the photo-generated electron-hole transmission and separation efficiency is realized, the band structure is optimized, and the photocatalytic performance of the material is remarkably improved. The results of the examples show that when the heterogeneous junction photocatalyst provided by the invention is used for photocatalytic water decomposition, the oxygen generation amount can reach 210 mu mol/h/g, and when the heterogeneous junction photocatalyst provided by the invention is used for degrading azo macromolecule rhodamine B, the degradation rate of degrading 100mg/L ultrahigh concentration RhB in 60min reaches 93%.
Drawings
FIG. 1 shows Na-WO obtained in example 1 and comparative example 13And WO3XPS photoelectron spectroscopy;
FIG. 2 shows the calcination of Na-WO at different temperatures in example 13Tungsten prepared by sodium doping induction of a series of precursorsHeterojunction photocatalyst (Na-WO)3-T-2h) and comparative example 1WO3XRD spectrum of (1);
FIG. 3 shows the Na-doped induced tungsten-based heterojunction photocatalyst obtained in example 1, comprising Na-WO3、Na-WO3-470-2h、Na-WO3-500-2h、Na-WO3HR-TEM high power transmission electron micrographs at-800-2 h;
FIG. 4 shows the calcination of Na-WO at different temperatures in example 13Tungsten heterojunction photocatalyst prepared by sodium doping induction of a series of precursors (Na-WO)3-photocatalytic decomposition of water of T-2h) yielding an oxygen activity map;
FIG. 5 shows the calcination of Na-WO at different temperatures in example 13Tungsten heterojunction photocatalyst prepared by sodium doping induction of a series of precursors (Na-WO)3-T-2h) and the photocatalytic decomposition rhodamine B activity diagram of comparative example 1;
FIG. 6 shows K-ion doped tungsten oxide (K-WO) in example 23) Tungsten heterojunction photocatalyst (K-WO) prepared by doping and inducing precursor and potassium3-T-2h) and undoped 2-WO in comparative example 23XRD pattern of (a);
FIG. 7 shows K-ion doped tungsten oxide (K-WO) in example 23) Tungsten heterojunction photocatalyst (K-WO) prepared by doping and inducing precursor and potassium3-T-2h) and undoped 2-WO in comparative example 23The activity diagram of the photocatalytic decomposition of formaldehyde;
FIG. 8 shows the tungsten-based heterojunction photocatalyst K-WO prepared by inducing potassium doping in example 23Circulation stability of photocatalytic degradation of formaldehyde of 800-2 h;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
the preparation method of the tungsten photocatalyst heterojunction photocatalyst by doping and inducing the alkali metal Na ions comprises the following steps:
(1) 0.005mol of sodium tungstate (Na)2WO4·2H2O), 0.025 sodium sulfate (Na)2SO4) And 0.1 citric acid (C)6H8O7) Rapidly dissolving the mixture in 50mL of deionized water under the condition of violent magnetic stirring, and continuing stirring for 10min after the mixture is completely dissolved;
(2) dropwise adding hydrochloric acid (HCl) by using a liquid-moving gun to adjust the pH value to 1.8, and continuing stirring for 10min after the pH reading is stable;
(3) transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out high-temperature reaction for 24 hours at 150 ℃ in a hydrothermal oven, and obtaining a precipitate at the bottom of the reaction kettle after the reaction is finished;
(4) centrifugally washing the obtained precipitate sample, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying the obtained wet sample in a 70 ℃ hydrothermal oven for 12h to obtain Na ion-doped hexagonal phase tungsten oxide (Na-WO)3) A precursor;
(5) uniformly grinding the dried sample, uniformly dispersing the ground sample in a crucible, and roasting the ground sample at different temperatures for 2 hours to obtain a series of sodium-doped induction prepared tungsten heterojunction photocatalysts;
the sample was named Na-WO3-T-T, T representing the firing temperature and T representing the firing time.
Comparative example 1:
the preparation method of the ion-free doped hexagonal tungsten oxide comprises the following steps:
(1) rapidly dissolving 0.005mol of ammonium metatungstate and 0.01mol of oleic acid in 50mL of deionized water under the condition of violent magnetic stirring, and continuing stirring for 10min after the ammonium metatungstate and the oleic acid are completely dissolved;
(2) dropwise adding nitric acid by using a liquid-transferring gun to adjust the pH value to 2.0, and continuously stirring for 10min after the pH reading is stable;
(3) transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out high-temperature reaction for 24 hours at 180 ℃ in a hydrothermal oven, and obtaining a precipitate at the bottom of the reaction kettle after the reaction is finished;
(4) centrifugally washing the obtained precipitate sample, washing with deionized water for three times, washing with anhydrous ethanol for three times, and drying the obtained wet sample in a 70 deg.C hydrothermal oven for 12 hr to obtain ion-free doped tungsten oxide (WO)3) The material is used as a comparative example1。
Na ion-doped tungsten oxide (Na-WO) obtained in example 13) Precursor and WO undoped in comparative example 13X Photoelectron Spectroscopy (XPS) comparison was performed, and the results are shown in fig. 1. The results in FIG. 1(a) show that Na-WO3In the presence of Na ions, Na1s in Na-WO3The binding energy in the material was 1072.0 eV. The O1s result in FIG. 1(b) shows that Na-WO3The binding energy of the intermediate O1s is obviously higher than that of WO3The binding energy of the W-O bond in the medium confirms that Na exists in Na-WO3In the structure, a chemical bond exists between the oxygen and O. The results show that in the doping preparation method, alkali metal ions successfully enter the crystal structure of the tungsten oxide and form chemical bonds with O in the structure.
Tungsten-based heterojunction photocatalyst prepared by sodium doping induction in example 1 Na-WO3Samples of the series T-T and WO obtained in comparative example 13XRD test was performed, and the test results are shown in FIG. 2. As can be seen from FIG. 2, when Na-WO3The calcination temperature of (A) is 300 ℃, 400 ℃ and 430 ℃ (i.e. Na-WO)3-300-2h、Na-WO3400-2h and Na-WO3430-2h samples) with diffraction patterns corresponding to hexagonal phase tungsten oxide (h-WO)3PDF #75-2187), whose diffraction peaks at 2 θ ═ 14.0 °, 22.8 °, 24.4 °, 26.9 °, 28.2 °, 33.6 ° and 36.6 ° correspond to h-WO, respectively3The characteristic diffraction peaks of the (100), (001), (110), (101), (200), (111) and (201) crystal planes of (a) prove at temperature<Under the roasting condition of 430 ℃, the crystal structure of the material is not changed and still maintains a hexagonal crystal phase structure. When the roasting temperature is continuously increased to 450 ℃ (Na-WO)3-450-2h), monoclinic phase tungsten oxide appears at 2 θ ═ 24.4 °, 26.6 °, 33.2 ° and 34.2 ° (m-WO)3Characteristic peaks of the (020), (022), (120) and (202) crystal planes of PDF #83-0950, which demonstrate m-WO under the baking conditions at 450 deg.C3And (4) generating, wherein under the temperature condition, the crystal structure begins to change. As can be seen from the figure, when the roasting temperature is 450-470 ℃ (Na-WO)3450-2h and Na-WO3470-2h), all samples are h-WO3And m-WO3And Na-WO3Samples at-470-2 h were taken at 24.4 °, 26.6 °,diffraction at 33.2 ℃ and 34.2 ℃ compared with Na-WO3The results of the significant increase in diffraction peak intensities at 2 θ of-450 to-2 h at 24.4 °, 26.6 °, 33.2 ° and 34.2 ° indicate that temperature leads to h-WO3To m-WO3And the higher the temperature is, the greater the degree of phase transition occurs, m-WO3The content is increased. When the roasting temperature exceeds 500 ℃ (Na-WO)3After-500-2 h), h-WO3All the characteristic diffraction peaks of (a) disappear, and m-WO3Has increased intensity of characteristic diffraction peak, and has triclinic phase Na at 10.8 deg., 21.8 deg., 25.4 deg. and 29.2 deg2W4O13(T-Na2W4O13Characteristic diffraction peaks of (100), (200), (-301) and (002) crystal planes of PDF # 70-2022). Wherein the Na ion is derived from WO3And doping ions in the pore channel. When the calcination temperature was increased to 600 deg.C (Na-WO)3-600-2h), a new diffraction peak appears at 2 θ ═ 19.3 °, 28.3 °, which can be attributed to the triclinic phase Na5W14O44(T-Na5W14O44The (004) and (200) crystal planes of PDF #89-6724), indicating that the sample formed under this firing condition is m-WO3、T-Na2W4O13And T-Na5W14O44Mixed phase of the three substances. Na-WO when the calcination temperature is further increased to 700 DEG C3700-2h still remained as m-WO3、T-Na2W4O13And T-Na5W14O44A three-phase structure. When the roasting temperature is continuously increased to 800 ℃ (Na-WO)3At-800-2 h), T-Na2W4O13Disappearance of characteristic diffraction peaks of m-WO3And T-Na5W14O44The characteristic diffraction peak of (1) still exists, Na-WO3The material becomes a two-phase structure within 800-2 h. Therefore, Na ion-doped Na-WO according to the analysis result of XRD3Driven by the temperature, the following transformation process occurs: Na-WO3(300～430℃)→m-WO3/h-WO3(450～470℃)→m-WO3(500℃)/T-Na2W4O13→m-WO3/T-Na5W14O44/T-Na2W4O13(600～700℃)→m-WO3/T-Na5W14O44(800 ℃) and therefore the Na ion-induced phase interface composition can be realized through the regulation and control of the temperature, thereby generating various phase interfaces.
Tungsten-based heterojunction photocatalyst prepared by sodium doping induction in example 1 Na-WO3The morphology structure of-500-2 h is tested by scanning electron microscope SEM, and the test result is shown in figure 3. Na ions induce a heterojunction catalyst with a core-shell structure.
For example 1, Na-WO was calcined at different temperatures3Tungsten heterojunction photocatalyst prepared by sodium doping induction of a series of precursors (Na-WO)3The photocatalytic water splitting oxygen generating activity of-T-2 h) was tested. The total reaction of photocatalytic water decomposition is that water is decomposed into oxygen and hydrogen on the surface of a catalyst under irradiation of light, but only a very small amount of photocatalytic material can simultaneously generate hydrogen and oxygen. Most often, the catalytic material has only hydrogen or oxygen producing activity. And finally compounding the hydrogen production catalyst and the oxygen production catalyst by optimizing the gas production rate of the half reaction to obtain the photocatalyst with the full decomposition function. This example 1 provides a method for optimizing the increase in oxygen production activity. The test of photocatalytic water decomposition is carried out in a vacuum circulation reaction system, the system is provided with a vacuum device, a 300W xenon lamp light source, a glass reactor, a cooling water circulation system and a gas chromatograph, wherein the vacuum device is used for ensuring that the content of reaction gas can be accurately measured, the xenon lamp is used for providing the light source, the cooling water is used for ensuring the stability of the reaction temperature, and the gas chromatograph is used for testing the content of generated gas. Firstly 100mg of Na-WO3-T-2h photocatalyst was added to a 250mL reactor, 100mL of 10mM FeCl was added3As a sacrificial agent, samples were taken every 1 hour and the oxygen content produced was tested. FIG. 4 shows Na-WO which is a tungsten heterojunction photocatalyst prepared by sodium doping induction3Samples of the series T-T and WO obtained in comparative example 13Photocatalytic oxygen production activity diagram. The results show that the oxygen-generating activity Na-WO3-500-2h>Na-WO3-470-2h>Na-WO3-450-2h>Na-WO3-600-2h>Na-WO3-800-2h>Na-WO3>Comparative example 1WO3. Namely a tungsten heterojunction photocatalyst (Na-WO) prepared by sodium doping induction3-T-2h) has higher activity of oxygen generated by photocatalytic decomposition of water.
For example 1, Na-WO was calcined at different temperatures3Tungsten heterojunction photocatalyst prepared by sodium doping induction of a series of precursors (Na-WO)3-T-2h) and comparative example 1WO3The activity of photocatalytic decomposition of RhB of (a) was tested. The specific test method and parameters are as follows: 50mg of photocatalyst, including Na-WO in example 1, was weighed out3-T-2h and comparative example 1WO3Put into RhB of 100mg/L and 250mL, and a 250W iodine tungsten lamp is arranged above the container as a light source. The test adopts sampling interval every ten minutes, after 60min of irradiation, the photocatalyst is centrifugally filtered, and clear liquid is taken to measure the absorbance C at the excitation wavelength of 553 nm. The analysis method comprises the following steps: analyzing the concentration of RhB in the filtrate at the wavelength of maximum absorption of RhB, and since the concentration is proportional to the absorbance, the photodegradation rate D of RhB can be found by the following formula:
D＝Co-C/Co×100％
wherein, CoThe absorbance of RhB before light irradiation, and C the absorbance of RhB at the time of light irradiation t.
FIG. 5 shows Na-WO which is a tungsten heterojunction photocatalyst prepared by sodium doping induction3Samples of the series T-T and WO obtained in comparative example 13And (3) photocatalytic degradation of RhB activity diagram. The results show that the RhB degrading activity Na-WO3-500-2h>Na-WO3-450-2h>Na-WO3-470-2h>Na-WO3-600-2h>Na-WO3-800-2h>Na-WO3>Comparative example 1WO3. Tungsten heterojunction photocatalyst prepared by sodium doping induction (Na-WO)3The photocatalytic activity of-T-2 h) was higher than that of comparative example 1.
Example 2:
the preparation method of the tungsten photocatalyst heterojunction photocatalyst by doping and inducing alkali metal K ions comprises the following steps:
(1) adding 3g of potassium tungstate (K)2WO4·2H2O), 1.84g potassium sulfate (K)2SO4) And under the condition of intense magnetic stirring of tartaric acid,quickly dissolving in 50mL of deionized water, and continuously stirring for 10min after the deionized water is completely dissolved;
(2) dropwise adding hydrochloric acid (HCl) by using a liquid-moving gun to adjust the pH value to 2.5;
(3) transferring the solution into a polytetrafluoroethylene reaction kettle, carrying out high-temperature reaction for 30 hours at 180 ℃ in a hydrothermal oven, and obtaining a precipitate at the bottom of the reaction kettle after the reaction is finished;
(4) centrifugally washing the obtained precipitate sample, washing with deionized water for three times, washing with anhydrous ethanol for three times, and drying the obtained wet sample in a 60 ℃ hydrothermal oven for 12h to obtain the K ion-doped tungsten oxide (K-WO)3) A precursor;
(5) uniformly grinding the dried sample, uniformly dispersing the ground sample in a crucible, and roasting the ground sample at different temperatures for 2 hours to obtain a series of sodium-doped induction prepared tungsten heterojunction photocatalysts;
the sample was named K-WO3-T-T, T representing the firing temperature and T representing the firing time.
Comparative example 2:
the preparation method of the ion-free doped tungsten oxide comprises the following steps:
weighing 10g of ammonium tungstate, placing the ammonium tungstate into a muffle furnace, roasting the ammonium tungstate for 1h at the temperature of 400 ℃ to obtain light green ion-free doped tungsten oxide, and comparing the weight with that of the tungsten oxide in the comparative example 2-WO3。
For the K ion-doped tungsten oxide obtained in example 2 (K-WO)3) Tungsten heterojunction photocatalyst (K-WO) prepared by doping and inducing precursor and potassium3T-2h) and comparative example 2 to WO undoped comparative example 23XRD comparison test is carried out, and the test result is shown in figure 1. The test result shows that K-WO3Tungsten oxide in hexagonal phase; K-WO3K-WO obtained when used as a precursor for roasting3500-2h, the structure is still a hexagonal tungsten oxide structure, and the structure is a single structure at the moment, so that no foreign junction is generated; with the increase of the roasting temperature, the hexagonal tungsten oxide is subjected to phase change, and the composition of a crystal phase is also changed: K-WO3600-2h phase transition to hexagonal (h-WO)3) Tungsten oxide of monoclinic structure (m-WO)3) Heterogeneous Structure (h/m-WO)3) And K-WO3Tungsten oxide (m-WO) with 800-2h phase transition to monoclinic structure3) Hexagonal phase potassium tungstate h-K0.33W0.94O3Hexagonal phase potassium tungstate h-K2W4O13A three-phase heterojunction. Non-doped comparative example 2 to WO of comparative example 23The analysis by XRD shows that the tungsten oxide is hexagonal phase tungsten oxide.
Thus, K-ion doped K-WO according to the results of XRD analysis3Driven by the temperature, the following transformation process occurs: h-WO3(K-WO3)→h-WO3(<500℃)→m-WO3/h-WO3(600℃)→m-WO3/h-K0.33W0.94O3/h-K2W4O13Therefore, the composition of the phase interface induced by the K ions can be realized by regulating and controlling the temperature, so that various phase interfaces are generated.
Tungsten oxide doped with K ions in example 2 (K-WO)3) Tungsten heterojunction photocatalyst (K-WO) prepared by doping and inducing precursor and potassium3-T-2h) and undoped 2-WO in comparative example 23The photocatalytic formaldehyde decomposition activity of (2) was tested. The specific test method and parameters are as follows: 50mg of photocatalyst, comprising tungsten oxide doped with K ions as in example 2 (K-WO) was weighed out3) Tungsten heterojunction photocatalyst (K-WO) prepared by doping and inducing precursor and potassium3-T-2h) and undoped 2-WO in comparative example 23Placing into 10 mg/L60 mL formaldehyde, dark adsorbing for 30min, and collecting 4mL suspension, wherein the formaldehyde concentration is defined as initial concentration C0. Then, a 250W iodine tungsten lamp is placed above the container as a light source, the total irradiation time is 180min at sampling intervals of every 30min, 4ml of the sample is taken every time, a disposable water-based filter membrane with the diameter of 0.22 mu m is used for filtering, and the obtained filtrate is immediately placed into a centrifuge tube to be sealed and stored in a shading mode. The content of the degraded residual formaldehyde is measured by adopting an acetylacetone method: sucking 2.5mL of the sample solution, adding into a 25mL centrifuge tube, adding 2.5mL of acetylacetone solution, shaking (acetylacetone solution, adding 50g of ammonium acetate, 6mL of acetic acid and 0.5mL of acetylacetone solution into deionized water, diluting to 100mL, storing in a refrigerator for later use), diluting with deionized water to 25mL, and performing ultraviolet spectrophotometryMethod for measuring absorbance C at absorption wavelength of 412nmt. The analysis method comprises the following steps: the concentration of formaldehyde in the filtrate was analyzed at the wavelength of maximum absorption of the formaldehyde-complex, and since the concentration is proportional to the absorbance, the photodegradation rate D of formaldehyde can be found by the following formula:
Dt＝Co-Ct/Co×100％
wherein, CoIs the absorbance of formaldehyde before illumination, CtThe absorbance of formaldehyde is measured at the time of illumination.
The results of the photocatalytic formaldehyde decomposition activity test are shown in fig. 7. The results show that the formaldehyde degrading activity K-WO3-800-2h>K-WO3-600-2h>K-WO3>Comparative example 2WO3. Tungsten-based heterojunction photocatalyst prepared by potassium doping induction prepared in example 2 (K-WO)3The photocatalytic activity of-T-2 h) was higher than that of comparative example 2.
Tungsten-based heterojunction photocatalyst K-WO prepared by potassium doping induction in example 23The results of formaldehyde removal stability test of-800-2 h show that K-WO3The efficiency of degrading formaldehyde after 5 cycles is reduced by less than 5% in 800-2 h.
In conclusion, the tungsten heterojunction photocatalyst prepared by doping induction provided by the invention has stable photocatalytic activity, and can effectively carry out photocatalytic decomposition on water, degrade organic azo macromolecular dye RhB and decompose formaldehyde. The tungsten photocatalyst provided by the invention combines an alkali (earth) metal doping technology and an in-situ heterogeneous combination technology, improves the absorption efficiency of the photocatalyst to light, greatly improves the transmission efficiency of a current carrier at an interface, greatly makes up for the defect of reduction of the energy of the current carrier of a heterojunction structure based on the lower overpotential of the surface of an alkali (earth) metal compound, improves the absorption, separation, transmission and interface reaction efficiency of the current carrier, and realizes the synthesis and application of the visible photocatalyst with high catalytic activity. Experimental results show that when the heterogeneous junction photocatalyst provided by the invention is used for photocatalytic water decomposition, the oxygen generation amount can reach 210 mu mol/h/g, when the heterogeneous junction photocatalyst is used for degrading azo macromolecule rhodamine B, the degradation rate of 100mg/L high-concentration RhB degraded in 60min reaches 93%, and the degradation rate of 10mg/L formaldehyde degraded in 180min reaches 89%.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (7)
1. The method for preparing the tungsten photocatalyst heterojunction through doping induction comprises the following steps: alkali metal ions (alkaline earth metal ions) are doped into a pore channel structure of tungsten oxide, and then under the drive of temperature, the doped ions are migrated and induce a surface phase to be changed, so that the tungsten photocatalyst heterostructure with a core-shell structure is generated.
2. The method for preparing the tungsten-based photocatalyst heterojunction as claimed in claim 1, which is characterized by comprising the following steps:
step 1, dissolving tungstate and a complexing agent in deionized water; then adding alkali metal (alkaline earth metal) sulfate as a doping ion source;
step 2, adjusting the solution obtained in the step 1 to a pH value of 1-2 by using acid to obtain a yellow tungstic acid precursor;
step 3, putting the precursor obtained in the step 2 into a hydrothermal oven to react for 10-48 h at 160-200 ℃ to obtain the one-dimensional tungsten oxide nanorod doped with alkali metal (alkaline earth metal);
step 4, roasting the tungsten oxide with different doping ions prepared in the step 3, and driving the doping ions to the WO in the step 33And (4) surface diffusion, and preparing the heterojunction with different core-shell structures in one step.
3. The method for preparing a tungsten-based photocatalyst heterojunction as claimed in claim 2, wherein said tungstate comprises lithium tungstate, sodium tungstate, potassium tungstate, rubidium tungstate, cesium tungstate, magnesium tungstate, calcium tungstate; the complexing agent comprises citric acid, tartaric acid, oxalic acid and urea; alkali metal (alkaline earth metal) sulfates including lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, magnesium sulfate; the acid includes hydrochloric acid and nitric acid.
4. The method for preparing the tungsten-based photocatalyst heterojunction through doping induction as claimed in claim 2, wherein the mass ratio of the complexing agent to the tungstate is (0.5-4): 1.
5. The method for preparing a tungsten-based photocatalyst heterojunction as claimed in claim 2, wherein the concentration of acid is 2-6 mol/L.
6. The method for preparing the tungsten photocatalyst heterojunction through doping induction according to claim 2, wherein the tungsten oxide with different doping ions obtained in the step 4 is roasted at the temperature of 300-900 ℃ for 1-10 h; the phase change goes through the precursor → hexagonal phase tungsten oxide → hexagonal (h-WO)3) Tungsten oxide of monoclinic structure (m-WO)3) Hetero-phase structure → alkali (earth) metal tungstate/monoclinic tungsten oxide hetero-junction structure.
7. Use of the tungsten-based photocatalyst heterojunction as claimed in any one of claims 1 to 6 in photocatalytic water decomposition, organic dye degradation and formaldehyde decomposition.
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| CN115007136A (en) * | 2022-06-29 | 2022-09-06 | 河南大学 | Tungsten oxide photocatalyst with hollow structure and preparation method and application thereof |
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