CN114392734B - Tungsten oxide composite material and preparation method and application thereof - Google Patents
Tungsten oxide composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114392734B CN114392734B CN202111642266.2A CN202111642266A CN114392734B CN 114392734 B CN114392734 B CN 114392734B CN 202111642266 A CN202111642266 A CN 202111642266A CN 114392734 B CN114392734 B CN 114392734B
- Authority
- CN
- China
- Prior art keywords
- composite material
- tungsten oxide
- oxide composite
- solution
- reaction
- 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.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims abstract description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 238000001514 detection method Methods 0.000 claims abstract description 18
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004729 solvothermal method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 14
- 239000011162 core material Substances 0.000 claims abstract description 11
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 33
- 230000009977 dual effect Effects 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000009123 feedback regulation Effects 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/23—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
-
- 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
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of nano materials, in particular to a tungsten oxide composite material and a preparation method and application thereof, wherein the preparation method of the tungsten oxide composite material comprises the following steps: mixing NaCl solution and sodium tungstate solution, regulating pH, and performing hydrothermal reaction to obtain nanometer WO 3 A core material; then bismuth nitrate solution is mixed with the nano WO 3 The core materials are mixed and subjected to solvothermal reaction. The preparation method of the tungsten oxide composite material provided by the invention is environment-friendly, stable, reliable, simple, convenient and feasible, and high in controllability, and the obtained composite material is uniform in size, fine in morphology and convenient to apply. The tungsten oxide composite material prepared by the invention has the dual functions of photocatalytic degradation and SERS detection, and has excellent dual-function application performance and remarkable effect.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a tungsten oxide composite material and a preparation method and application thereof.
Background
Along with environmental pollution and ecological destruction, the treatment of pollutants such as water, air, soil and the like has become a serious problem to be solved, and particularly, after industrialization is advanced, a large amount of factory and farm wastewater is discharged without treatment, and a large amount of organic pollutants harmful to human beings and other organisms are contained in the wastewater. As a modern green energy-saving technology, the photocatalysis technology has great potential in the aspect of wastewater treatment and gradually becomes a research hot spot in the field of environmental protection. Among the numerous photocatalysts, tungsten trioxide (WO 3 ) As an n-type semiconductor material, isThe cheap and stable transition metal oxide has unique physical and chemical properties and is widely applied to the fields of environment, energy sources, life sciences, information technology and the like.
WO 3 The narrow bandgap structure ensures that the light source has an extended spectral response, can effectively utilize the visible light part in natural light, greatly improves the utilization rate of sunlight, but has adverse effects on the other hand, such as fast photo-generated electron-hole pair recombination, low photocatalytic activity and the like; and WO 3 Lower conduction band positions may also hinder the progress of the reductive reaction. The general approach to solve this problem is to compound the target semiconductor with other semiconductors or metals having corresponding band-enabling structures, to construct hetero/homojunctions, and to compensate for each other's structural defects by synergistic action. In recent years, with development of nano technology, nano-scale composite tungsten oxide materials gradually enter the field of view of people, and compared with large-size tungsten oxide materials, nano-scale tungsten oxide has the advantages of controllable surface energy, remarkably increased specific surface area, quantum confinement effect and the like, and is attracting attention of more researchers.
The physical and chemical properties of the material are mainly controlled by the preparation method and the specific preparation process, and the particle size, the crystal structure, the usability, the practical application condition and the like of the synthesized material are directly influenced. In the present method for preparing tungsten oxide, the raw materials and the reaction process can be roughly divided into: a gas phase method (sputtering method, thermal evaporation method, arc discharge deposition method, etc.), a liquid phase method (sol-gel method, electrochemical method, chemical deposition method, hydrothermal/solvothermal method, etc.), and a solid phase method (mechanical pulverization method, solid phase reaction method, etc.). Although there are many preparation methods, from the viewpoint of preparing a functional composite material, it is still a research difficulty in the current academic community to find a method capable of stably preparing a composite material and making the prepared material have excellent performance in non-single functional applications.
Disclosure of Invention
In order to solve the technical problems, the invention provides a tungsten oxide composite material, and a preparation method and application thereof.
In a first aspect, the present inventionThe preparation method of the tungsten oxide composite material comprises the following steps: mixing NaCl solution and sodium tungstate solution, regulating pH, and performing hydrothermal reaction to obtain nanometer WO 3 A core material; then bismuth nitrate solution is mixed with the nano WO 3 The core materials are mixed and subjected to solvothermal reaction.
The invention discovers that the hydrothermal/solvothermal method provided by the invention can prepare the tungsten oxide composite material with excellent performance in two steps, solves a great difficulty in the field at present, stably prepares the composite material with multiple application functions, simultaneously, the raw materials required by the reaction are all raw materials which are convenient and easy to obtain in the market, the sources are wide, the types are various, the selectable range is wide, the preparation method has the advantages of environmental protection, stability, reliability, simplicity, convenience, practicability, high controllability and the like, the obtained composite material has uniform size, fine particles and convenient application, and the prepared tungsten oxide composite material has the dual functions of photocatalytic degradation and SERS detection, and has excellent dual-function application performance and remarkable effect of achieving spontaneous feedback regulation.
The preparation method of the tungsten oxide composite material provided by the invention comprises the following steps:
1) Dropwise adding the NaCl solution into the sodium tungstate solution, stirring, and adding hydrochloric acid to adjust the pH value to obtain a mixed solution;
2) Carrying out hydrothermal reaction on the mixed solution obtained in the step 1), cooling, washing, centrifuging and drying to obtain the nano WO 3 A core material;
3) Combining bismuth nitrate solution with the nano WO obtained in step 2) 3 Mixing the kernel materials, performing solvothermal reaction, cooling, washing, centrifuging and drying.
Further preferably, in the step 1), the concentration of the NaCl solution is 4.5 to 5.5mol/L; and/or the concentration of the sodium tungstate solution is 0.12-0.16 mmol/L; and/or the concentration of the hydrochloric acid is 2.4-2.6 mol/L, and the pH value is 1.8-2.5.
The NaCl solution, the sodium tungstate solution and the hydrochloric acid are prepared by pure water, the concentration is not limited, but when the concentration of the NaCl solution is 4.5-5.5 mol/L, the concentration of the sodium tungstate solutionWhen the concentration of the hydrochloric acid is 0.12-0.16 mmol/L and 2.4-2.6 mol/L and the pH value of the solution is regulated to be 1.8-2.5, the generation of side reaction can be effectively avoided, and the hydrothermal reaction is improved to obtain the nano WO 3 The structure and the performance of the core material are beneficial to subsequent reaction, so that the morphology and the application effect of the tungsten oxide composite material are better ensured. The inventors found that the preferred concentration ranges are as follows: 5mol/L NaCl solution, 0.14mmol/L sodium tungstate solution and 2.5mol/L hydrochloric acid, and the pH value of the solution is adjusted to be optimal=2.
Preferably, in the step 2), the hydrothermal reaction is carried out for 6-24 hours at 160-280 ℃; and/or in the step 3), the solvothermal reaction is carried out for 6-24 hours at 160-280 ℃. Further preferably, the optimal reaction conditions for both the hydrothermal reaction and the solvothermal reaction are 180 ℃ for 9 hours.
The invention can improve the output and purity of the product by adding the preferable reaction conditions, so that the obtained product has complete structure, uniform appearance and excellent photoelectric property, and is beneficial to subsequent application. Meanwhile, by adding the preferable reaction conditions, the phenomena of incomplete reaction (the required product cannot be obtained) or excessive reaction (structural damage such as structural collapse, fracture and adhesion caused by excessive reaction) and the like of the product in the reaction process can be further avoided, and the application effect of the prepared composite material is ensured to be more excellent.
Preferably, in the step 3), the concentration of the bismuth nitrate solution is 0.01 to 0.5mol/L.
Further preferably, the concentration of the bismuth nitrate solution is 0.05mol/L.
The preferred bismuth nitrate concentration of the present invention is aimed at providing a product with good application properties. Proper bismuth nitrate concentration is critical to obtaining a Bi-containing composite product, and the concentration is too small, so that the morphology and the structure of the composite product are incomplete; excessive concentration can cause by-product generation, increase the processing difficulty of subsequent steps, and influence the application effect of the final product.
Preferably, in step 3), the solvent used in the solvothermal reaction may be an organic solvent such as methanol, ethanol, ethylene glycol, butanol, etc., so long as bismuth nitrate is ensured to be soluble therein and participate in the reaction.
Further preferably, the solvent for the solvothermal reaction is ethylene glycol.
The preferred ethylene glycol of the invention aims at having considerable solubility of bismuth nitrate in ethylene glycol, and the viscosity and density of ethylene glycol are suitable, so that the uniform and stable progress of the reaction process is ensured, the property of the final product is stable, and the application is facilitated.
According to the preparation method of the tungsten oxide composite material provided by the invention, the step 3) further comprises the following steps: and adding a dispersing agent into the bismuth nitrate solution.
Further preferably, the dispersant comprises one or more of CTAB, EDTA, SDS.
The present invention optionally adds a dispersant to the bismuth nitrate solution, or does not, but preferably adds a dispersant, including one or more of CTAB, EDTA, SDS, but most preferably EDTA, in view of the end use effect of the product. Preferably, the concentration of EDTA in the bismuth nitrate solution is set to 1.7 to 10.3mmol/L. Further preferably, the concentration of EDTA is 6.8mmol/L.
Preferably, the nano WO 3 The molar ratio of W in the core material to Bi in the bismuth nitrate solution is 0.72-71.8:30-1500; further preferably 50.3:150.
the invention adopts specific raw materials and condition parameters to prepare the nano WO through a hydrothermal method 3 And preparing the core material by a solvothermal method, and then, actually applying the obtained composite material to photocatalytic degradation of organic pollutants and SERS detection of the organic pollutants. The method is environment-friendly, stable, reliable, simple, convenient and easy to operate, high in controllability, uniform in size, fine in appearance, simple and convenient to apply, and capable of being applied to photocatalytic degradation of organic pollutants and SERS detection of the organic pollutants, plays the dual functions, and achieves remarkable effect of spontaneous feedback regulation. The method is applied to photocatalytic degradation of organic pollutants and SERS detection of the organic pollutants, plays a dual-functional role, and achieves the effect of spontaneous feedback regulation. The preparation method provided by the invention is environment-friendly, stable, reliable, simple and easyThe obtained composite material has uniform size, fine appearance, simple and convenient application and obvious effect, and can provide theoretical basis and technical support for the preparation and application of tungsten oxide and other functional semiconductor materials.
Further preferably, in steps 2) and 3), the washing comprises washing with deionized water and/or ethanol.
According to the preferred embodiment of the invention, the washing conditions are not limited to deionized water and ethanol, and residual organic/inorganic matters possibly existing in the product can be removed, but the washing effect is optimal by adopting deionized water and ethanol; in the invention, the rotation speed of the centrifugal machine is not limited, and the solution and the product can be effectively separated, and experiments show that the separation effect is optimal at 3000 r/min; in the invention, the drying method is not limited, and the modes of blowing-drying by a blower, drying by a drying box and the like can be adopted, so that the product structure is not damaged in the drying process. The optimal drying condition is found to be 60 ℃ for 12 hours through experiments. Further preferably, both the hydrothermal reaction and the solvothermal reaction are carried out in an autoclave, the temperature of which is optimally set at 180 ℃. It is still to be understood that the specific preparation and application conditions involved in the present invention are defined to yield the best and preferred products, but it is not excluded that certain products may be produced after reasonable extrapolation of the defined conditions and should be considered as falling within the scope of the present invention.
In a second aspect, the present invention provides a tungsten oxide composite material prepared by the above method.
The composite material prepared by the method is practically applied to photocatalytic degradation of organic pollutants and SERS detection of the organic pollutants, and plays a double function role. The practical application effect shows that the composite material prepared by the method has excellent dual-function application performance and obvious effect. The invention also provides theoretical basis and technical support for the preparation and application of tungsten oxide and other semiconductor materials with similar functions.
In a third aspect, the present invention provides an application of the tungsten oxide composite material prepared by the above method, including one or more of the following applications:
a) The tungsten oxide composite material is applied to photocatalytic degradation of organic pollutants;
b) The tungsten oxide composite material is applied to SERS detection of organic pollutants.
The invention discovers that the tungsten oxide composite material prepared by the invention is practically applied to photocatalytic degradation of organic pollutants and SERS detection of the organic pollutants, can well play the double functions of the tungsten oxide composite material, and achieves the effect of spontaneous feedback regulation.
Preferably, the specific application method comprises the following steps: 4) Uniformly dispersing the tungsten oxide composite material in an organic pollutant solution with a certain concentration, and placing the tungsten oxide composite material under a light source to perform photocatalytic degradation on the organic pollutant, wherein the final degradation effect of the material is excellent; 5) And uniformly dispersing the tungsten oxide composite material in a pollutant solution with a certain concentration to form a mixed solution, dripping a certain amount of mixed solution on a substrate, and immediately performing SERS detection after drying to obtain the material with excellent enhancement effect on a pollutant Raman signal peak.
Preferably, the organic contaminants include methylene blue, methylene orange, rhodamine B, BPA, and the like, preferably, the refractory methylene blue.
In the specific application example of the invention, the quality and the pollutant concentration of the used composite material are not limited, and the composite material can properly meet the photocatalysis requirement; the light source can be sunlight or simulated sunlight, and the used simulated sunlight equipment is not limited, and can be a xenon lamp, a mercury-xenon arc lamp, a high-pressure mercury lamp, an ultraviolet/visible lamp and the like, so that the illumination required by the catalytic process can be met. If the pollutant solution is required to be prepared in the application process, the solvent type of the pollutant solution can sufficiently dissolve the pollutant, but ethanol is preferred in consideration of the subsequent drying requirement; the substrate type used for detecting the organic pollutants by SERS is not limited, and can be a quartz plate, a mica plate, a ceramic plate and the like, and the subsequent SERS detection is not affected.
The invention has the advantages that: the hydrothermal/solvothermal two-step preparation method provided by the invention can controllably prepare the tungsten oxide composite material with excellent performance, and solves the problem in the prior art that the composite material with multiple application functions is stably prepared; the raw materials required by the reaction are all convenient and easily available in the market, and have wide sources, various types and wide optional range; the method provided by the invention is environment-friendly, stable, reliable, simple, convenient and feasible, and high in controllability, the obtained composite material is uniform in size, fine in particles and excellent in performance, the prepared composite material not only has photocatalytic performance, but also has excellent SERS enhancement effect, and the dual-function application of the composite material is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM photograph of the product obtained in example 1 of the present invention (a is WO, B and c are B/BO/WO).
Figure 2 is an XRD pattern of the product obtained in example 1 of the present invention.
FIG. 3 is an SEM photograph of the product obtained in comparative example 1 of the present invention.
Figure 4 is an XRD pattern of the product obtained in comparative example 1 of the present invention.
FIG. 5 is a graph showing the effect of photocatalytic degradation of the composite product in example 2 of the present invention.
FIG. 6 is a graph showing the effect of photocatalytic degradation of the composite product in comparative example 2 according to the present invention.
FIG. 7 shows the detection of the Raman signal of the complex product to contaminants in example 3 of the present invention.
Fig. 8 shows the signal peak (a) of the pure MB solution and the SERS performance Enhancement Factor (EF) quantification calculation result (b) of the composite material in example 3 of the present invention.
FIG. 9 shows the detection of the Raman signal of the complex of comparative example 3 against contaminants.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, which are used for illustrating the present invention but are not intended to limit the scope of the present invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or instruments used are not noted to manufacturers, are conventional products purchased by normal channel suppliers, and are all of the grade of commercial analytical purity.
Example 1
Weigh 0.0125mmol Na 2 WO 4 ·2H 2 O is dissolved in 90ml of pure water, and is fully stirred and dissolved to form solution A; weighing 0.1mol of NaCl, dissolving in 20ml of pure water, and fully stirring to dissolve to form a solution B; solution a was continuously stirred magnetically, solution B was added dropwise, the ph=2 was adjusted with 2.5M HCl (aq), and then the mixture was placed in an autoclave, subjected to hydrothermal reaction at 180 ℃ for 9h, cooled to room temperature, washed with deionized water and ethanol, centrifuged (rotation speed 3000 r/min) for several times, and dried at 60 ℃ for 12h, to prepare a hydrothermal sample WO, as shown in fig. 1 a.
Weigh 0.003mol Bi (NO) 3 ) 3 ·5H 2 O is dissolved in 60ml of glycol, stirred for 30min at room temperature, 0.12g of EDTA is added into the mixture, the mixture is fully stirred for 60min at room temperature, 0.7g of WO prepared by the hydrothermal method is added into the mixture, the mixture is uniformly stirred, the mixture is put into an autoclave, reacted for 9h at 180 ℃, cooled to room temperature, washed with deionized water and ethanol respectively, centrifuged (with the rotating speed of 3000 r/min) for multiple times, and dried at 60 ℃ for 12h to obtain a composite sample B/BO/WO, as shown in figure 1B.
As can be seen from FIG. 1, the method of the present invention can be used to prepare a nano-scale 3D composite product with uniform size and good morphology, wherein WO 3 The length of the nano rod is 1-2 mu m, and the diameter is 25-60nm (figure 1 a); bi (Bi) 2 O 3 The thickness of the nano-sheet is about 10nm, and Bi 2 O 3 And WO 3 Forming a 3D flower-like structure (Bi 2 O 3 Vertical adhesion of nanoplatelets to WO 3 Surface growth of nanorods) to form a structure that does not overlap and fully utilizes space (fig. 1 b); bi is small spheres, about a few hundred nanometers in diameter (fig. 1 c).
FIG. 2 is XRD patterns of two products obtained in example 1, where the WO sample corresponds to h-WO 3 Phase, B/BO/WO sample corresponds to Bi/Bi 2 O 3 /WO 3 The product prepared by the invention has good crystallinity and does not contain other impurities.
Comparative example 1
Directly weighing 0.003mol Bi (NO) 3 ) 3 ·5H 2 Dissolving O in 60ml of ethylene glycol, stirring at room temperature for 30min, adding 0.12g of EDTA, stirring at room temperature for 60min, placing into an autoclave, reacting at 180deg.C for 9h, cooling to room temperature, washing with deionized water and ethanol respectively, centrifuging (rotation speed 3000 r/min) for multiple times, and drying at 60deg.C for 12h to obtain compound sample B/BO, which is shown in figure 4 and comprises Bi and Bi 2 O 3 Composition is prepared. Also as can be seen from FIG. 3, the products prepared by the method other than the present invention are micron-sized Bi pellets, and Bi 2 O 3 The micro-scale nearly spherical structure formed by the nano-sheets has extremely irregular shape, the spherical structure has small and uneven size, and no obvious interface connection or 3D structure is formed, which is unfavorable for the practical application effect of the material, and is shown in comparative example 2 and comparative example 3.
Example 2
The procedure for the preparation of the complex product is the same as in example 1, which is mainly used for explaining the application effect of photocatalytic degradation of the organic dye MB, which is one of the dual functions of the prepared complex product.
Dispersing 10mg of the composite product in 100ml of 10mg/L MB solution, and stirring for 30min under the dark condition to achieve adsorption balance; then placing the sample on a xenon lamp device (420 nm filter plate, 20A current), simulating the degradation process of MB under visible light under the condition of continuous stirring, sampling in a fixed period, detecting the MB content in the solution after centrifugal separation, and calculating the degradation efficiency corresponding to the product in a certain time. The final degradation effect is shown in fig. 5, and it can be seen that the composite product has a good degradation effect on MB, reaching 95% at 210 min.
Comparative example 2
The procedure for the preparation of the product is the same as in comparative example 1, which is mainly intended to illustrate the photocatalytic function, i.e. the effect of the photocatalytic degradation of the organic dye MB, of the product prepared by a method other than the one according to the invention.
Dispersing 10mg of the product in 100ml of 10mg/L MB solution, and stirring for 30min under the dark condition to reach adsorption balance; then placing the sample on a xenon lamp device (420 nm filter plate, 20A current), simulating the degradation process of MB under visible light under the condition of continuous stirring, sampling in a fixed period, detecting the MB content in the solution after centrifugal separation, and calculating the degradation efficiency corresponding to the product in a certain time. The final degradation effect is shown in fig. 6, and it can be seen that the degradation rate of the prepared product is only 52% at 210min, and the degradation effect is general. As compared with the results of example 2, the application effect of the material prepared by the invention is obviously better.
Example 3
The preparation process of the composite product is the same as in example 1, which is mainly used for explaining the application effect of the prepared composite product in the difunctional two-SERS detection of the organic dye MB.
Respectively taking a proper amount of compound products, and uniformly dispersing in the concentration range of 10 -3 M-10 -8 M to form a mixed solution, dripping 20 mu L of the mixed solution into 2 x 2cm 2 And (3) carrying out SERS detection immediately after drying on the substrate, and obtaining the enhancement condition of the material on the Raman signal peak of the pollutant under 532nm excitation wave. The final signal peaks are shown in FIG. 7, and it can be seen that as the concentration of the solution decreases, the characteristic peak intensity also gradually decreases, up to 10 -8 M, 1622 and 1395cm -1 The characteristic peaks at the positions are still distinguishable, which indicates that the material has excellent SERS application performance. Simultaneous comparison of 10 -2 The signal peak of the pure MB solution (fig. 8 a), the SERS performance enhancement coefficient (EF) of the composite material was quantitatively calculated (fig. 8 b), and a clear linear relationship between dye concentration and peak intensity was found, which indicates that the material has stable SERS application performance.
Comparative example 3
The procedure for the preparation of the product is the same as in comparative example 1, which is mainly used for illustrating the SERS function of the product prepared by the method other than the present invention, i.e. the application effect of SERS detection of the organic dye MB. Respectively taking a proper amount of products, and uniformly dispersing the products in the concentrationIn the range of 10 -3 M and 10 -5 M to form a mixed solution, dripping 20 mu L of the mixed solution into 2 x 2cm 2 And (3) carrying out SERS detection immediately after drying on the substrate, and obtaining the enhancement condition of the material on the Raman signal peak of the pollutant under 532nm excitation wave. The final signal peaks are shown in FIG. 9, and it can be seen that the solution concentration is 10 -3 At M, the characteristic peak of part of MB is still distinguishable, but when the solution concentration is reduced to 10 -5 At M, the MB characteristic peak was not discernable, in sharp contrast to the effect of the application in example 3, indicating that the SERS detection function of this material was significantly worse than the effect of the material prepared using the present invention.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for preparing a tungsten oxide composite material, comprising the steps of: mixing NaCl solution and sodium tungstate solution, regulating pH, and performing hydrothermal reaction to obtain nanometer WO 3 A core material; then bismuth nitrate solution is mixed with the nano WO 3 Mixing kernel materials, and performing solvothermal reaction; wherein the concentration of the bismuth nitrate solution is 0.01-0.5 mol/L, the solvent for solvothermal reaction is methanol, ethanol, glycol and butanol, and the nano WO 3 The molar ratio of W in the core material to Bi in the bismuth nitrate solution is 0.72-71.8:30-1500, and the solvothermal reaction is carried out for 6-24 h at 160-280 ℃.
2. The method for preparing a tungsten oxide composite material according to claim 1, comprising the steps of:
1) Dropwise adding the NaCl solution into the sodium tungstate solution, stirring, and adding hydrochloric acid to adjust the pH value to obtain a mixed solution;
2) Subjecting the mixed solution obtained in the step 1) to waterThermal reaction, cooling, washing, centrifuging and drying to obtain the nano WO 3 A core material;
3) Combining bismuth nitrate solution with the nano WO obtained in step 2) 3 Mixing the kernel materials, performing solvothermal reaction, cooling, washing, centrifuging and drying.
3. The method for producing a tungsten oxide composite material according to claim 2, wherein in step 1), the concentration of the NaCl solution is 4.5 to 5.5mol/L; and/or the concentration of the sodium tungstate solution is 0.12-0.16 mmol/L; and/or the concentration of the hydrochloric acid is 2.4-2.6 mol/L, and the pH value is 1.8-2.5.
4. A method of preparing a tungsten oxide composite according to claim 2 or 3, wherein in step 2), the hydrothermal reaction is carried out at 160-280 ℃ for 6-24 hours.
5. The method of preparing a tungsten oxide composite material according to claim 2, wherein step 3) further comprises: and adding a dispersing agent into the bismuth nitrate solution.
6. The method of preparing a tungsten oxide composite according to claim 5, wherein the dispersant comprises one or more of CTAB, EDTA, SDS.
7. A tungsten oxide composite material, characterized in that the tungsten oxide composite material is prepared according to the method of any one of claims 1-6.
8. Use of the tungsten oxide composite material prepared by the method according to any one of claims 1 to 6, comprising one or more of the following applications:
a) The tungsten oxide composite material is applied to photocatalytic degradation of organic pollutants;
b) The tungsten oxide composite material is applied to SERS detection of organic pollutants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111642266.2A CN114392734B (en) | 2021-12-29 | 2021-12-29 | Tungsten oxide composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111642266.2A CN114392734B (en) | 2021-12-29 | 2021-12-29 | Tungsten oxide composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114392734A CN114392734A (en) | 2022-04-26 |
| CN114392734B true CN114392734B (en) | 2024-01-30 |
Family
ID=81228080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111642266.2A Active CN114392734B (en) | 2021-12-29 | 2021-12-29 | Tungsten oxide composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114392734B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477290B (en) * | 2022-02-23 | 2024-03-01 | 中国科学院合肥物质科学研究院 | Sodium tungsten bronze nanosheet array SERS substrate and preparation method and application thereof |
| CN114772646B (en) * | 2022-04-29 | 2023-11-10 | 福州大学 | Preparation method of tungsten oxide nano material and application of tungsten oxide nano material in photocatalytic desulfurization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030179A (en) * | 2013-01-08 | 2013-04-10 | 江苏大学 | Tungsten trioxide nano-sheet prepared by hydrothermal method and application of tungsten trioxide nano-sheet |
| CN103657692A (en) * | 2013-11-22 | 2014-03-26 | 华东师范大学 | Compound bismuthyl bromide photocatalyst |
| CN105688953A (en) * | 2015-12-31 | 2016-06-22 | 江苏大学 | Method for preparing BiOI/WO3 composite heterojunction photocatalyst |
| CN105797760A (en) * | 2016-04-18 | 2016-07-27 | 河南师范大学 | Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof |
| CN105854912A (en) * | 2016-04-18 | 2016-08-17 | 河南师范大学 | BiPO4-WO3 composite photocatalyst and preparation method thereof |
| CN110841626A (en) * | 2019-10-24 | 2020-02-28 | 江苏大学 | Tungsten oxide/bismuth oxide net-sheet composite material and preparation method and application thereof |
-
2021
- 2021-12-29 CN CN202111642266.2A patent/CN114392734B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030179A (en) * | 2013-01-08 | 2013-04-10 | 江苏大学 | Tungsten trioxide nano-sheet prepared by hydrothermal method and application of tungsten trioxide nano-sheet |
| CN103657692A (en) * | 2013-11-22 | 2014-03-26 | 华东师范大学 | Compound bismuthyl bromide photocatalyst |
| CN105688953A (en) * | 2015-12-31 | 2016-06-22 | 江苏大学 | Method for preparing BiOI/WO3 composite heterojunction photocatalyst |
| CN105797760A (en) * | 2016-04-18 | 2016-07-27 | 河南师范大学 | Bi2O2CO3-WO3 composite photocatalyst and preparation method thereof |
| CN105854912A (en) * | 2016-04-18 | 2016-08-17 | 河南师范大学 | BiPO4-WO3 composite photocatalyst and preparation method thereof |
| CN110841626A (en) * | 2019-10-24 | 2020-02-28 | 江苏大学 | Tungsten oxide/bismuth oxide net-sheet composite material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Bi2O3和WO3纳米粒子协同增强NR/WO3/Bi2O3复合材料r射线屏蔽性能;李银涛等;《高分子材料科学与工程》;第57-62页 * |
| One-pot hydrothermal synthesis of Bi2O3-WO3 p-n heterojunction film for photoelectrocatalytic degradation of norfloxacin;Tao Jiang et al.;《Separation and Purification Technology》;第1-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114392734A (en) | 2022-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Imam et al. | The photocatalytic potential of BiOBr for wastewater treatment: A mini-review | |
| Song et al. | Photocatalytic activities of Cd-doped ZnWO4 nanorods prepared by a hydrothermal process | |
| CN114392734B (en) | Tungsten oxide composite material and preparation method and application thereof | |
| Yu et al. | Constructing SrTiO3-T/CdZnS heterostructure with tunable oxygen vacancies for solar-light-driven photocatalytic hydrogen evolution | |
| Zhao et al. | Rose-like CuS microflowers and their enhanced visible-light photocatalytic performance | |
| Liu et al. | Solvothermal synthesis, photoluminescence and photocatalytic properties of pencil-like ZnO microrods | |
| Liu et al. | Superb photocatalytic activity of 2D/2D Cl doped g-C3N4 nanodisc/Bi2WO6 nanosheet heterojunction: Exploration of photoinduced carrier migration in S-scheme heterojunction | |
| Zhang et al. | UV-Vis-NIR-light-driven Ag2O/Ag2S/CuBi2O4 double Z-scheme configuration for enhanced photocatalytic applications | |
| CN108675339B (en) | Preparation method of rodlike self-assembled spherical zinc-cadmium-sulfur solid solution material | |
| CN105879884A (en) | One-dimensional ZnS (zinc sulfide)/CdS-C nanocomposite material and preparation method thereof | |
| CN112246272A (en) | Has a defect g-C3N4Preparation method of nanosheet photocatalyst | |
| Wang et al. | Facile synthesis of Cu3Se2/Cu2Se/Cu2O hollow microspheres by sacrificial template method at room temperature and excellent photodegradation activity | |
| Zhang et al. | Hollow anisotropic semiconductor nanoprisms with highly crystalline frameworks for high-efficiency photoelectrochemical water splitting | |
| CN114522709B (en) | Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof | |
| CN107935047B (en) | A kind of control synthetic method of different-shape and the nano-manganese dioxide of size | |
| Xiao et al. | Synthesis and application of one-dimensional La (OH) 3 nanostructures: an overview | |
| CN113289646A (en) | Core-shell structured nanoflower/nanoparticle bismuth oxybromide/titanium dioxide visible-light-driven photocatalyst and preparation method and application thereof | |
| Wang et al. | Hydrothermal synthesis of SnO2 nanoflower arrays and their optical properties | |
| CN109647510B (en) | Polyion liquid modified cerium-doped nano-zinc oxide photocatalyst and preparation method and application thereof | |
| CN108722442B (en) | Molybdenum disulfide/manganese tungstate nanorod composite material and preparation method and application thereof | |
| CN108996478B (en) | MN (Mobile node)xSuper crystal and preparation method and application thereof | |
| CN107662906B (en) | A kind of preparation method of two selenizings W film and the application of photocatalytic reduction of carbon oxide | |
| CN108031481B (en) | Ultrathin bismuth oxyhalide nanosheet photocatalyst stripped by silver intercalation and preparation method thereof | |
| CN101343043A (en) | Amphoteric metal compound nano-material and method of preparing the same | |
| CN114849762B (en) | g-C for degrading lipophilic azonaphthalene compound 3 N 4 /BiOI/Ag 2 CrO 4 Preparation method and application of ternary heterojunction photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |