CN110586133A - Niobium acid-based sulfide composite material and preparation method thereof - Google Patents
Niobium acid-based sulfide composite material and preparation method thereof Download PDFInfo
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- CN110586133A CN110586133A CN201910860580.4A CN201910860580A CN110586133A CN 110586133 A CN110586133 A CN 110586133A CN 201910860580 A CN201910860580 A CN 201910860580A CN 110586133 A CN110586133 A CN 110586133A
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- niobate
- composite material
- black precipitate
- sulfide
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- 239000010955 niobium Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000002253 acid Substances 0.000 title claims abstract description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 title claims abstract description 9
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000002244 precipitate Substances 0.000 claims abstract description 53
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- 238000005303 weighing Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 239000004005 microsphere Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical group [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 25
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 10
- 235000018660 ammonium molybdate Nutrition 0.000 description 10
- 239000011609 ammonium molybdate Substances 0.000 description 10
- 229940010552 ammonium molybdate Drugs 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 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 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 241001503974 Adriana Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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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- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a niobium acid group sulfide composite material and a preparation method thereof, wherein the niobium acid group sulfide composite material has a structural formula of AxBySz‑H4Nb2O7Wherein A, B is one or two of different metal elements of Co, Mo, Ni, Cu, Zn and Fe, wherein x is more than 0 and less than 10, y is more than 0 and less than 10, z is more than 0 and less than 10, and the concrete formula isThe numerical value is determined according to the specific valence of the compound. Weighing tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding one or two soluble metal salts and thiourea, dissolving the metal salts and the thiourea in water, and carrying out hydrothermal reaction to obtain a black precipitate; filtering and washing the black precipitate, placing the black precipitate in a vacuum drying oven, and drying to obtain AxBySz‑H4Nb2O7A composite material. The preparation method has the advantages of low preparation conditions and simple operation, and the sulfide uniformly grows on the surface of the niobic acid, so that more reactive sites are provided for the reaction, and the reactivity of the metal sulfide in the catalytic reaction is fully improved.
Description
Technical Field
The invention belongs to the technical field of synthesis of novel catalytic materials, and particularly relates to preparation of a novel microspherical metal sulfide-niobic acid composite material.
Background
Sulfide materials have been extensively studied because they exhibit certain catalytic capabilities in the areas of photolysis of water to produce hydrogen, photocatalytic degradation of dyes, photocatalytic reduction of carbon dioxide, electrocatalysis, and biomass conversion. Sulfide is cheap and is considered as a cheap material which can replace noble metal and be applied to industrial production. The material represented by molybdenum disulfide is a typical transition metal bis-alkyl halide, and adjacent nano sheets are connected together and stacked through weak van der waals interaction to form a sandwich structure, and each unit nano sheet is composed of three atom (S-Mo-S) layers which are covalently bonded.
Transition metal sulfide catalytic materials have also been widely used in hydrodesulfurization, hydrodeoxygenation, hydrodenitrogenation, and other biomass catalytic conversion reactions. The catalytic activity of the molybdenum disulfide material is derived from unsaturated atoms at the edges of the molybdenum disulfide material, and increasing the number of active sites exposed at the edges can increase the catalytic activity of the molybdenum disulfide material. The research shows that the material, whether supported or unsupported, has excellent catalytic activity. And the structure of the material has a great influence on the activity of the material, and the current research focuses on changing the structure and the shape of the material so as to improve the activity of the material.
Niobium-based solid acids are gradually used as materials due to their stronger surface acidity and water resistanceVectors were investigated. Adriana et al synthesized Pb composites with niobium pentoxide as the carrier, as compared to SiO2A supported catalyst material having a reaction rate of SiO in the hydrodeoxygenation of phenol290 times of the carrier. The high activity of the material may be due to Nb5+/Nb4+Strong interaction between the oxophilic sites represented by the cations and the molecular oxygen of phenol. However, in recent studies, the metallic phase in the composite material is mostly concentrated on the noble metal, and the non-noble metal composite material based on the niobium-based solid acid is currently less studied.
Disclosure of Invention
In order to explore the composite material of the sulfide with a novel structure and a novel shape and further expand the application range of the niobate-based material, the invention provides a hydrothermal-in-situ composite preparation method for preparing the sulfide-niobate composite material. The preparation method has mild conditions and simple operation, and the prepared niobate-based material has certain application potential in the aspects of photocatalysis and lignin catalytic conversion. And the active metal phase in the composite material is non-noble metal, so that the price is relatively low, and a foundation is laid for the large-scale application of the material.
In order to achieve the purpose, the invention adopts the technical scheme that:
a composite material of sulfide on niobate radical with the structural formula of AxBySz-H4Nb2O7A, B is one or two of different metal elements of Co, Mo, Ni, Cu, Zn and Fe, wherein x is more than 0 and less than 10, y is more than or equal to 0 and less than 10, z is more than 0 and less than 10, and the specific numerical value is generally determined according to the valence state of a compound;
the niobic acid is a microsphere with the size of 1-5 mu m, and the metal sulfide is uniformly dispersed on the surface layer of the niobic acid microsphere.
The preparation method of the metal sulfide composite material on the niobate base comprises the following steps:
1) weighing tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding one or two soluble metal salts and thiourea, adding a hydrochloric acid solution to adjust the pH value to 0.7-1.0, putting the mixture into a kettle, and reacting to obtain a black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven for drying to obtain AxBySz-H4Nb2O7A composite material.
The hydrothermal reaction temperature in the step 1) is 100-; the metal soluble salt can be molybdate, nitrate, acetate, chloride or sulfate;
the mass ratio of the metal salt to the tin niobate in the step 1) is 5: 1-20: 1, and the mass ratio of the thiourea to the metal salt is 0.4: 1-2: 1; adding 0.1-0.2 mol/L hydrochloric acid solution, wherein the ratio of the volume of the hydrochloric acid to the addition amount of the tin niobate is 50-300 mL/g
The drying temperature in the step 2) is 60-120 ℃, and the drying time is 6-12 h;
the invention firstly prepares microspherical tin niobate precursor according to literature, and then carries out the steps of hydrothermal-in-situ synthesis and the like to generate the corresponding metal sulfide-niobate composite material. The preparation method adopts thiourea as a sulfur source, and avoids the application of H in the conventional sulfide synthesis method2And S, the synthesis process is cleaner and safer and is easy to control in the high-temperature vulcanization process.
The metal sulfide-niobic acid composite material prepared by the method can be used for photocatalytic hydrolysis hydrogen production and photocatalytic degradation of dyes, such as rhodamine B.
The specific operation of photocatalytic degradation of rhodamine B is as follows: 0.05g of the composite material and 50mL of rhodamine B solution with the concentration of 20mg/L are added into a reactor, and the mixture is irradiated for 2 hours by a xenon lamp with a 420nm filter. After the irradiation is finished, the absorbance of the solution at 554nm is measured by using an ultraviolet spectrophotometer to determine the degradation rate.
The invention has the following remarkable advantages:
1. the preparation method has low preparation conditions and simple operation, and the sulfide can uniformly grow on the surface of the niobic acid, so that more reactive sites are provided for catalytic reaction, and the reactivity of the metal sulfide in the catalytic reaction can be fully improved.
2. Adopted in the inventionHydrothermal method for forming metal sulfide without using H2S is subjected to high-temperature vulcanization, the operation is simple, the safety is high, the synthesis difficulty is greatly reduced, and the niobium-based composite material prepared in the invention is not added with any noble metal, so that the material preparation cost is low and the application potential is large.
3. The sulfide-niobate composite material prepared by the invention has good crystallinity and high purity, and the formation of high-purity niobate crystal phase can be obviously observed by XRD.
4. The invention innovatively combines the sulfide and the niobic acid, and widens the application range of the niobium-based solid acid material. The material has a degradation rate of 93.1% in the reaction of degrading rhodamine B through photocatalysis, which is 13 times of that of the common molybdenum disulfide material.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the materials of the various examples of the invention described below.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
MoS2-H4Nb2O7Preparation of
1) Weighing 0.1g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 1.84g of ammonium molybdate and 2.4g of thiourea, adding 30mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12 hours at 160 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-H4Nb2O7A composite material.
Example 2
CoS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 2.9g of cobalt nitrate hexahydrate and 2.4g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 2 hours at 200 ℃ to obtain black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6 hours to obtain CoS2-H4Nb2O7A composite material.
Example 3
FeS2-H4Nb2O7Preparation of
1) Weighing 0.15g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 2.8g of ferrous sulfate and 1.2g of thiourea, adding 45mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12h at 200 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain FeS2-H4Nb2O7A composite material.
Example 4
ZnS-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 3.0 g of zinc nitrate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12 hours at 160 ℃ to obtain black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6 hours to obtain ZnS-H4Nb2O7A composite material.
Example 5
NiS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 2.9g of nickel nitrate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12 hours at 200 ℃ to obtain black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 80 ℃ for drying for 10 hours to obtainTo NiS2-H4Nb2O7A composite material.
Example 6
CuS-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 1.87g of copper chloride and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 15h at 150 ℃ to obtain black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6 hours to obtain CuS-H4Nb2O7A composite material.
Example 7
MoS2-CoS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate, 2.0g of cobalt nitrate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, filling the mixture into a kettle, and reacting at 200 ℃ for 12 hours to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 90 ℃ for drying for 12h to obtain MoS2-CoS2-H4Nb2O7A composite material.
Example 8
MoS2-ZnS-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate, 1.25g of zinc nitrate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, filling the mixture into a kettle, and reacting at 180 ℃ for 24 hours to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-ZnS-H4Nb2O7A composite material.
Example 9
MoS2-NiS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate, 2.0g of nickel nitrate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, filling the mixture into a kettle, and reacting at 160 ℃ for 24 hours to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 10h to obtain MoS2-NiS2-H4Nb2O7A composite material.
Example 10
MoS2-FeS-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate, 1.95g of ferrous sulfate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, filling the mixture into a kettle, and reacting at 200 ℃ for 12 hours to obtain black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6 hours to obtain MoS2-FeS-H4Nb2O7A composite material.
Example 11
MoS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 1.84g of ammonium molybdate and 2.4g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12 hours at 160 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-H4Nb2O7A composite material.
Example 12
MoS2-H4Nb2O7Preparation of
1) Weighing 0.15g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate and 1.2g of thiourea, adding 45mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12h at 160 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-H4Nb2O7A composite material.
Example 13
MoS2-H4Nb2O7Preparation of
1) Weighing 0.2g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.92g of ammonium molybdate and 1.2g of thiourea, adding 60mL of 0.12mol/L hydrochloric acid solution to adjust the pH value to 0.9, putting the mixture into a kettle, and reacting for 12 hours at 160 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-H4Nb2O7A composite material.
Example 14
MoS2-H4Nb2O7Preparation of
1) Weighing 0.1g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 0.5g of ammonium molybdate and 1g of thiourea, adding 5mL of 0.2mol/L hydrochloric acid solution to adjust the pH value to 0.7, putting the mixture into a kettle, and reacting for 2 hours at 100 ℃ to obtain black precipitate;
2) carrying out suction filtration and washing on the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven at 60 ℃ for drying for 6h to obtain MoS2-H4Nb2O7A composite material.
Example 15
MoS2-H4Nb2O7Preparation of
1) Weighing 0.1g of tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding 2g of ammonium molybdate and 4g of thiourea, adding 30mL of 0.1mol/L hydrochloric acid solution, adjusting the pH value to 1.0, putting the mixture into a kettle, and reacting for 48 hours at 200 ℃ to obtain black precipitate;
2) black color obtained after 1) reactionThe precipitate is filtered and washed, and is placed in a vacuum drying oven at 120 ℃ for drying for 12h to obtain MoS2-H4Nb2O7A composite material.
Figure 1 is an XRD pattern of molybdenum disulfide and molybdenum disulfide-niobic acid material. Because there is no H in standard card library4Nb2O7Standard cards, therefore, we determined the purity and crystallinity of the prepared samples by comparing the tantalum acid standard card (PDF # 26-0756).
As can be seen from the figure, the diffraction peaks of the obtained sample correspond to the standard cards one by one, and no other miscellaneous peaks exist, which indicates that the molybdenum disulfide-niobic acid composite material is successfully prepared by the hydrothermal-in-situ synthesis method, and the sample has good crystallinity.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (8)
1. A composite material of sulfide on niobate base is characterized in that the structural formula is AxBySz-H4Nb2O7Wherein A, B is one or two of different metal elements of Co, Mo, Ni, Cu, Zn and Fe. Wherein x is more than 0 and less than 10, y is more than or equal to 0 and less than 10, and z is more than 0 and less than 10, and the specific numerical value is generally determined according to the valence state of the compound.
2. The niobate-based sulfide-on-niobate composite material according to claim 1, wherein the metal sulfide is uniformly dispersed in a surface layer of the niobate microsphere.
3. A method of preparing a niobium acid based sulfide composite material as claimed in claim 1, characterized by comprising the steps of:
1) weighing tin niobate, adding the tin niobate into a polytetrafluoroethylene lining, adding one or two soluble metal salts and thiourea, adding a hydrochloric acid solution to adjust the pH value to 0.7-1.0, putting the mixture into a kettle, and reacting to obtain a black precipitate;
2) filtering and washing the black precipitate obtained after the reaction of 1) and placing the black precipitate in a vacuum drying oven for drying to obtain AxBySz-H4Nb2O7A catalyst.
4. The method as set forth in claim 3, characterized in that the hydrothermal reaction temperature in step 1) is 100-200 ℃ and the reaction time is 2-48 h.
5. The method of claim 3, wherein the metal soluble salt is a molybdate, nitrate, acetate, chloride or sulfate.
6. The method according to claim 3, wherein the mass ratio of the metal salt to the tin niobate is 5:1 to 20:1, and the mass ratio of the thiourea to the metal salt is in the range of 0.2:1 to 2: 1.
7. The method as set forth in claim 3, wherein 0.1 to 0.2mol/L hydrochloric acid solution is added, and the ratio of the volume of hydrochloric acid to the amount of tin niobate added is 50 to 300 mL/g.
8. The method as set forth in claim 3, wherein the drying temperature in the step 2) is 60 ℃ to 120 ℃ for 6h to 12 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337457A (en) * | 2020-11-11 | 2021-02-09 | 郑州轻工业大学 | Mo-doped HNb3O8Preparation method and application of nanosheet |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733161A (en) * | 2009-12-15 | 2010-06-16 | 华南师范大学 | Photochemical preparation method of chitosan loaded metal sulfide photocatalyst |
| CN101816957A (en) * | 2010-03-12 | 2010-09-01 | 华南师范大学 | Photochemical preparation method of phyllosilicate loaded metal sulphide photocatalyst |
| CN103143370A (en) * | 2013-03-08 | 2013-06-12 | 南昌大学 | Preparation method of sulfide/graphene composite nano material |
| CN103920506A (en) * | 2014-05-08 | 2014-07-16 | 湘潭大学 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
| CN104152171A (en) * | 2014-07-24 | 2014-11-19 | 大连理工大学 | Method for preparing alkane liquid fuel by catalysis of lignin derivative aryl ether |
| CN105056988A (en) * | 2015-08-09 | 2015-11-18 | 大连理工大学 | Binary niobate-based hydrodeoxygenation catalyst, preparation therefor and application thereof |
| CN106238075A (en) * | 2016-07-23 | 2016-12-21 | 天津大学 | Molybdenum sulfide catalyst and preparation thereof and the application in fragrance phenol and ether compound hydrogenation degraded |
| CN107008484A (en) * | 2017-04-17 | 2017-08-04 | 武汉理工大学 | A kind of binary metal sulfide/carbonitride composite photocatalyst material and preparation method thereof |
| CN107224986A (en) * | 2017-07-21 | 2017-10-03 | 江苏大学 | A kind of molybdenum disulfide/niobic acid tin composite nano materials and purposes |
| CN108295870A (en) * | 2018-01-30 | 2018-07-20 | 上海大学 | The preparation method of sulfide-graphene composite material photoelectric |
-
2019
- 2019-09-11 CN CN201910860580.4A patent/CN110586133A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733161A (en) * | 2009-12-15 | 2010-06-16 | 华南师范大学 | Photochemical preparation method of chitosan loaded metal sulfide photocatalyst |
| CN101816957A (en) * | 2010-03-12 | 2010-09-01 | 华南师范大学 | Photochemical preparation method of phyllosilicate loaded metal sulphide photocatalyst |
| CN103143370A (en) * | 2013-03-08 | 2013-06-12 | 南昌大学 | Preparation method of sulfide/graphene composite nano material |
| CN103920506A (en) * | 2014-05-08 | 2014-07-16 | 湘潭大学 | Double-metal-sulfide catalyst with high hydrodeoxygenation activity and preparation method thereof |
| CN104152171A (en) * | 2014-07-24 | 2014-11-19 | 大连理工大学 | Method for preparing alkane liquid fuel by catalysis of lignin derivative aryl ether |
| CN105056988A (en) * | 2015-08-09 | 2015-11-18 | 大连理工大学 | Binary niobate-based hydrodeoxygenation catalyst, preparation therefor and application thereof |
| CN106238075A (en) * | 2016-07-23 | 2016-12-21 | 天津大学 | Molybdenum sulfide catalyst and preparation thereof and the application in fragrance phenol and ether compound hydrogenation degraded |
| CN107008484A (en) * | 2017-04-17 | 2017-08-04 | 武汉理工大学 | A kind of binary metal sulfide/carbonitride composite photocatalyst material and preparation method thereof |
| CN107224986A (en) * | 2017-07-21 | 2017-10-03 | 江苏大学 | A kind of molybdenum disulfide/niobic acid tin composite nano materials and purposes |
| CN108295870A (en) * | 2018-01-30 | 2018-07-20 | 上海大学 | The preparation method of sulfide-graphene composite material photoelectric |
Non-Patent Citations (2)
| Title |
|---|
| CHAO ZHOU ET.AL: ""A Sustainable Strategy for the Synthesis of Pyrochlore H4Nb2O7 Hollow Microspheres as Photocatalysts for Overall Water Splitting"", 《CHEMPLUSCHEM》 * |
| 姜春杰等: "多酸基硫化钼复合材料的制备、表征及性能", 《徐州工程学院学报(自然科学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337457A (en) * | 2020-11-11 | 2021-02-09 | 郑州轻工业大学 | Mo-doped HNb3O8Preparation method and application of nanosheet |
| CN112337457B (en) * | 2020-11-11 | 2023-02-03 | 郑州轻工业大学 | Mo-doped HNb 3 O 8 Preparation method and application of nanosheet |
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