CN113351219A - Nano-rod-shaped FeV3O8Preparation method and photocatalytic application thereof - Google Patents
Nano-rod-shaped FeV3O8Preparation method and photocatalytic application thereof Download PDFInfo
- Publication number
- CN113351219A CN113351219A CN202110803133.2A CN202110803133A CN113351219A CN 113351219 A CN113351219 A CN 113351219A CN 202110803133 A CN202110803133 A CN 202110803133A CN 113351219 A CN113351219 A CN 113351219A
- Authority
- CN
- China
- Prior art keywords
- fev
- shaped
- preparation
- solution
- nanorod
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 title abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000006731 degradation reaction Methods 0.000 claims abstract description 20
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 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 claims abstract description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 17
- 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 claims abstract description 16
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002073 nanorod Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000000840 electrochemical analysis Methods 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000011941 photocatalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000001052 transient effect Effects 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
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 101100460754 Drosophila melanogaster NPFR gene Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- UFXGQUPBYNXNEW-UHFFFAOYSA-N photo-fenton reagent Chemical compound C1=CC(C(N(CC(OC)OO)C2=O)=O)=C3C2=CC=C2C(=O)N(CC(OC)OO)C(=O)C1=C32 UFXGQUPBYNXNEW-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- 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
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
The invention provides a method for simply and conveniently preparing 1D nano rodlike FeV3O8And its application in the field of photocatalysis. Compared with the traditional photocatalyst, the forbidden band width is higher, the photoresponse range is mainly concentrated in an ultraviolet region, the application range of the photocatalyst is greatly limited, and the product (1D nano rod-shaped FeV) is prepared by the method3O8) The forbidden band width is 2.28eV, the visible light response is good, and organic pollutants can be catalytically degraded under visible light. 1D nanorod-like FeV3O8The preparation method mainly comprises a hydrothermal method andand combining annealing crystallization processes. The method overcomes the defects of the prior art, prepares the nano rod-shaped structure with uniform appearance and structure, diameter of about 100nm and length of about 1 mu m by a template-free hydrothermal method, has high specific surface area, can achieve the optimal catalytic effect, can completely catalyze and degrade rhodamine B (RhB) and Methylene Blue (MB) within 25min (the degradation rates are respectively 100 percent and 99.8 percent), does not add other surfactants in the preparation process, and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of photocatalyst production, in particular to one-dimensional nano rod-shaped FeV3O8The preparation method and the application thereof.
In recent years, due to energy crisis and environmental pollution, global environmental problems have been real and strategic problems to be solved urgently, and water pollution by pesticides, dyes and the like and air pollution by harmful gases are increasingly intensified. Photocatalytic treatment is one of the most effective, safe and promising methods for eliminating organic and harmful pollutants in water, and has attracted considerable research interest.
Since TiO2 was first reported in 1972 as a photocatalyst, semiconductor photocatalysts have received much attention due to their wide application in environmental decontamination and solar energy conversion. More and more sewage treatment adopts photocatalysis technology. The photocatalyst can decompose organic pollutants in the water into harmless substances with high efficiency in a short time by means of a photocatalyst catalysis technology, and has great advantages in the aspect of environmental protection. Semiconductor materials gain high energy by absorbing photons of appropriate wavelengths, and can transfer electrons from the Valence Band (VB) to the Conduction Band (CB), causing redox reactions and degradation of the dye. In particular, Advanced Oxidation Processes (AOPs) are an ideal and viable method for degrading organic pollutants by converting organic and hazardous pollutants into small molecules (e.g., CO2, H2O) through Fenton, photo-Fenton reactions, and photocatalysis, based on hydroxyl radicals (OH.) generated by the combination of a catalyst and radiation (sometimes with an oxidizing agent). However, some conventional photocatalysts (such as TiO2, ZnO) can only degrade pollutants under ultraviolet light due to large band gap, and the catalytic degradation efficiency is greatly reduced due to high electron-hole recombination, which greatly limits the application of the photocatalysts in the photocatalytic environment. Therefore, researchers have recently been working on the preparation of highly efficient catalysts for the degradation of organic pollutants under visible light. In recent years, iron-based photo-fenton reagent can solve this problem. Iron-based fenton technology is receiving more and more attention due to its characteristics of high efficiency, low cost, easy operation, cleanness and no toxicity. From the development at home and abroad, the research on the catalyst related to the photocatalytic material tends to increase year by year, and many well-known subject groups continuously strive for the research. With the development of photocatalytic materials, people pay more and more attention to the research and development of novel efficient photocatalytic materials, and in order to be widely applied in various fields, people need to solve the problems related to photocatalysis in mining and preparation. Therefore, the development of a novel catalyst with high efficiency, low cost and stable catalytic performance is one of the key steps in the application of the solar photocatalytic technology.
The existing photocatalyst also has the problems of low transfer speed of photo-generated electrons and holes, high recombination rate, low photocatalytic quantum efficiency, low reaction conversion rate and the like. Therefore, it is the key of research of researchers to develop a next generation photocatalyst that can meet the needs of people, replace the existing photocatalyst, and overcome the problems and difficulties brought by its source. To date, various iron-vanadium based photocatalysts with different nanostructures have been reported, including Fe2V4O13 nanobelts, Fe2V4O13 heterogeneous sheets and FeVO4 nanosheets, FeVO4 nanorods, and the like. In the above-described methods of preparing iron-vanadium based photocatalysts, many people use surfactants or annealing to adjust morphology. The preparation process is relatively complex and the cost is relatively high. In recent years, the preparation of the iron-vanadium-based nano material with high specific surface area and unique physicochemical properties by a simple, controllable, green, environment-friendly and template-free method still faces huge challenges.
The invention makes up for their deficiencies to a certain extent. Simultaneously preparing uniform and stable one-dimensional nano rod-shaped FeV3O8Having a large ratioThe surface area (20.06m2/g), and simultaneously the degradation rate of rhodamine B and methylene blue can be completely degraded respectively within 25min by the concerted catalysis of hydrogen peroxide (the degradation rate is respectively 99% and 99.8%), and the degradation rate can still be kept above 98% after four times of circulating catalysis, so that the catalyst has high-efficiency catalytic activity and high catalytic stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides one-dimensional nano rod-shaped FeV3O8The preparation method and the application thereof are characterized in that the one-dimensional nano rod-shaped FeV with uniform and stable appearance structure is obtained by combining a hydrothermal method and annealing treatment3O8And the prepared one-dimensional nanorod-shaped FeV3O8The diameter is 100nm, the length is about 1 mu m, the optimal catalytic effect can be achieved, additional auxiliary agent treatment is not needed, and the production cost is reduced.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
one-dimensional nano rod-shaped FeV3O8A preparation method of the one-dimensional nano rod-shaped FeV3O8 The preparation method comprises the following steps:
(1) preparing raw materials: dissolving 1mol of metallic iron source in 30mL of deionized water to form a solution A, adding 5mol of vanadium source (ammonium metavanadate) into 30mL of deionized water to form a solution B for later use, mixing and stirring the solution A and the solution B uniformly to form a solution C, and then adding 5mmol of oxalic acid into the solution C to obtain a mixed solution for later use;
(2) centrifugal drying: dropwise adding 10mL of glacial acetic acid into the mixed solution to adjust the pH value to 1, transferring the mixed solution into a reaction kettle, reacting at 180 ℃ for 3-24h, reducing the temperature to room temperature, centrifuging, taking precipitate, washing the precipitate with water and alcohol for several times, and performing vacuum drying in an oven to obtain a sample for later use;
(3) annealing process:
preferably, the metallic iron source in step (1) is any one of ferric trichloride, ferric nitrate and ferric acetate.
Preferably, the ratio of the amounts of the metallic iron source and the vanadium source (ammonium metavanadate) in the step (1) is 1: 5.
Preferably, in the step (1), the metallic iron source and the vanadium source are dissolved in deionized water and then stirred for 30min respectively, after mixing, the ultrasonic treatment is carried out for 10-60min under the conditions that the power is 40-60W and the ultrasonic frequency is 20-40Hz, and then the stirring is carried out for 30min at the stirring speed of 500 rad/min.
Preferably, the reagent for adjusting pH in step (2) is glacial acetic acid.
Preferably, the rotation speed of the centrifugation in the step (2) is 8000-10000r/min, and the centrifugation time is 3-5 min.
Preferably, the pressure of vacuum drying in the oven in the step (2) is 0.08-0.10MPa, the temperature is 60 ℃, and the drying time is 12-24 h.
Preferably, in the step (3), the heating rate is 5 ℃/min, the temperature is 500 ℃, and the annealing heat preservation time is 2 h.
The application of the one-dimensional nano rod-shaped FeV3O8 in catalytic degradation of organic pollutants.
The invention provides a preparation method and application of one-dimensional nano rod-shaped FeV3O8, compared with the prior art, the preparation method has the following advantages:
(1) according to the invention, the pH value of the mixed solution of a vanadium source and ferric trichloride is adjusted to 1, then the mixed solution is reacted for 3-24h at 180 ℃, and then the mixed solution is annealed at high temperature of 500 ℃ to obtain the one-dimensional nano rod-shaped FeV3O8 with small particle size, no auxiliary agent is added for adjustment, and the production cost is saved;
(2) the catalyst prepared by the invention can effectively and rapidly degrade organic pollutants, can be recycled, effectively prolongs the service life and improves the use effect of the catalyst, and reduces resource waste;
(3) the invention relates to a one-dimensional nano rod-shaped FeV3O8The photocatalyst has low cost, high catalytic performance and high stability, and further helps to solve the energy crisis and dilemma faced by the human society at present.
Description of the drawings:
FIG. 1: XRD patterns for the products prepared in examples 1-3; the graph shows that the products obtained by different times (3h, 6h and 24h) of the reaction have FeV combined with monoclinic phase3O8The standard card (PDF #75-0811) completely corresponds to each other, and shows that the prepared product has high purity and good crystallinity。
FIG. 2: (a) (b) (c) FESEM pictures of the products of examples 1-3 at different reaction times (3h, 6h and 24h), respectively; FIG. 3: EDS elemental summary spectrum for the product made in example 3;
FIG. 4: the nanorod FeV prepared in example 33O8Ultraviolet absorption spectrogram in the catalytic degradation process;
FIG. 5: one-dimensional nanorod FeV prepared for examples 1-33O8Catalytic degradation (RhB) performance profile;
FIG. 6: the nanorod FeV prepared in example 33O8Ultraviolet absorption spectrogram in the catalytic degradation process;
FIG. 7: one-dimensional nanorod FeV prepared for examples 1-33O8Catalytic degradation (MB) performance graph;
FIG. 8: FeV prepared for example 33O8(180 ℃, 24h) light transient current test chart;
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
one-dimensional nano rod-shaped FeV3O8Preparation method of the one-dimensional nano-rod-shaped FeV3O8The preparation method comprises the following steps:
(1) preparing raw materials: taking a vanadium source (ammonium metavanadate) (0.585g, (5 mmol)): ferric chloride (0.162g, 3mmol) ═ 5: 1, respectively dispersing and dissolving the components in 30ml of water, stirring for 10min, then mixing the two components, performing ultrasonic treatment for 30min under the conditions that the power is 50W and the ultrasonic frequency is 30Hz, and stirring for 30min at the stirring speed of 500rad/min to obtain a mixed solution;
(2) centrifugal drying: regulating the pH value of the mixed solution to 1 by adopting glacial acetic acid, transferring the mixed solution into a reaction kettle, reacting at 180 ℃ for 3h, centrifuging at the rotation speed of 8000-10000r/min for 3min, taking a precipitate, washing the precipitate with water and alcohol for several times, and drying in an oven at the pressure of 0.08-0.10MPa and the temperature of 60 ℃ for 12-24h to obtain a sample for later use;
(3) annealing and crystallizing: putting the dried sample in a tubular furnace, annealing and preserving heat for 2 hours at the temperature of 500 ℃ at the heating rate of 10 ℃/min, and removing crystal water to obtain the one-dimensional nano rod-shaped FeV with uniform and stable size3O8。
Example 2:
similar to the step 1, the difference is that after centrifugal drying, the mixture is transferred into a reaction kettle to react for 6 hours at 180 ℃;
example 3:
similar to the step 1, the difference is that the mixture is transferred into a reaction kettle after centrifugal drying and reacts for 24 hours at 180 ℃;
FIG. 1 is an XRD pattern of the products obtained in examples 1-3; it can be seen that the products obtained at 180 ℃ for different reaction times (3h, 6h, 24h) and monoclinic phase FeV3O8Corresponds exactly to the standard card (PDF # 75-0811). The surface preparation product has high purity and good crystallinity.
FIG. 2 b is the FESEM images of the products of examples 1-3 at different reaction temperatures ((a)3h, (b)6h and (c)24h), respectively; from FIG. 2(a), it can be seen that the amorphous nanoparticles obtained after reaction at 180 ℃ for 3h had an average particle size of 100-200 nm; with the increase of the reaction time (6h), the nanoparticles in the amorphous state undergo Ostwald ripening in a thermodynamic dynamic state, and the surface continuously grows to form a nano flower-like structure with a central core as shown in FIG. 2 (b); in FIG. 2(c), when the reaction is carried out for 24h, the nano flower-like structure of the central core is increased and dispersed under thermodynamic driving, and nano rods (diameter of about 100nm and length of about 1 μm) with nano-scale morphology and uniform structure are formed. Aiming at the morphology forming process of monoclinic phase FeV3O8, an NPFR (nucleotide-Nanoparticles-Nanoflowers-Nanorods) growth model is proposed. In the reaction process (3-24h), crystal grains are dissolved and then are aged by Ostwald to grow into nuclei to form amorphous nano particles, meanwhile, countless small particles are dispersed and aggregated to form a nano flower-shaped structure taking central particles as nuclei due to the driving of specific surface area and reaction thermodynamic energy, and countless nano flower-shaped structures are mutually dispersed and separated from the central nuclei along with the further increase of time, so that the nano rod-shaped structure material with uniform appearance and size is finally formed.
FIG. 3 is the EDS diagram corresponding to example 3, and it can be seen from the EDS diagram that the elements Fe, V and O in the sample are respectively from the synthesized pure monoclinic phase FeV3O8And the atomic ratio of the elements is as follows: fe: v: o-8.54: 25.12: 66.34, atomic ratio of elements Fe, V and O is approximately 1: 3: this is the same atomic ratio as the monoclinic phase of FeV3O8, and is consistent with XRD measurements.
Example 4:
firstly, the method comprises the following steps: photocatalytic degradation performance detection
The prepared sample is tested for the effect of catalyzing and degrading rhodamine B (RhB):
(1) taking three beakers to respectively contain 50ml of 25mg/L rhodamine B (RhB), respectively adding 5mg of the sample prepared in the above example 1-3, and placing for 30 minutes under dark condition;
(2) placing the rhodamine B prepared in the step (1) under xenon lamp light, simulating sunlight, adding 0.5mL of H2O2, taking a rhodamine B (RhB) solution every 5min, and scanning by using an ultraviolet/visible light photometer to obtain data;
(3) the data obtained in step (2) are generated into fig. 4, fig. 5.
FIG. 4 shows that the maximum wavelength of ultraviolet absorption of rhodamine B (RhB) is near 551nm, and the maximum absorption intensity of the absorption wave gradually decreases during the catalysis process, which indicates that the corresponding pollutant concentration is also gradually decreasing;
FIG. 5 shows the one-dimensional nanorod FeV prepared in examples 1-33O8Catalytic degradation (RhB) performance profile; from the figure, the nanorod shape (FeV) can be seen3O824h) the highest catalytic degradation rate (degradation rate of 100%), and the other two are (FeV)3O8，6h)49％，(FeV3O8，3h)43％。
Example 5:
II, secondly: photocatalytic degradation performance detection
The samples prepared above were tested for their effect on catalytic degradation of Methylene Blue (MB):
(1) 50ml of 20mg/L Methylene Blue (MB) was taken from each of the three beakers, 5mg of the sample prepared in example 2 was added thereto, and the mixture was left in the dark for 30 minutes;
(2) placing the methylene blue prepared in the step (1) under xenon lamp light, simulating sunlight, adding 0.5mL of H2O2, taking Methylene Blue (MB) solution every 5min, and scanning by using an ultraviolet/visible light photometer to obtain data;
(3) the data obtained in step (2) are generated into fig. 6, fig. 7.
FIG. 6 shows that the maximum wavelength of ultraviolet absorption of Methylene Blue (MB) is near 664nm, and the absorption intensity of the maximum absorption wave gradually decreases in the catalytic process, which indicates that the corresponding pollutant concentration is also gradually decreasing;
FIG. 7 shows the one-dimensional nanorod FeV prepared in examples 1-33O8Catalytic degradation of methylene blue
(MB) performance map; from the figure, the nanorod shape (FeV) can be seen3 O 824h) has the highest catalytic degradation rate (the degradation rate is 99%), and the other two are respectively nano particles (FeV)3 O 83h) 37% in the form of nanoflower (FeV)3O8，6h)48％。
Example 6:
photoelectrochemical-optical transient current test Photoelectrochemical (PEC) measurements were performed in a standard three-electrode electrochemical test using an electrochemical workstation (CHI760E, CHInstruments) using a carbon rod and Ag/AgC1 electrode (electrolyte 0.5M Na2SO4) as counter and reference electrodes respectively, the working electrode being a glassy carbon electrode (GCE, 3mm diameter).
1) The photocatalytic material prepared in example 3 was dispersed in water at a concentration of 5mg to obtain an electrode modification solution, which was applied to a working electrode at a loading of 0.21mg cm-2 and dried
And coating the electrode protection solution, and drying again.
2) Photoelectrochemical (PEC) measurements were performed using an electrochemical workstation (CHI760E, CHInstruments) using a carbon rod and an Ag/AgC1 electrode (electrolyte 0.5M Na2SO4) as counter and reference electrodes, respectively, the working electrode being a glassy carbon electrode (GCE, 3mm diameter). Taking open circuit voltage (OPCT) as test voltage under the current time (i-t) test; then testing the optical transient current response of the photocatalytic material under the state of switching on and off the xenon lamp for a certain time (100s),
3) the data obtained in step (2) is made into fig. 8.
FIG. 8 shows the one-dimensional nanorod FeV prepared in example 33O8The result shows that the instantaneous photocurrent of the sample can continuously and stably respond under the condition of simulating the instantaneous photocurrent response curve under the visible light condition, which indicates that the prepared nanorod FeV3O8Has strong photocurrent response, and further illustrates monoclinic phase FeV3O8Has excellent visible light response.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. Simple, green and template-free method for preparing one-dimensional nanorod-like FeV3O8The method is characterized in that the one-dimensional nano rod-shaped FeV3O8The preparation method comprises the following steps:
(1) preparing raw materials: dissolving 1mol of metallic iron source in 30mL of deionized water to form a solution A, adding 5mol of vanadium source (ammonium metavanadate) into 30mL of deionized water to form a solution B for later use, mixing and stirring the solution A and the solution B uniformly to form a solution C, and then adding 5mmol of oxalic acid into the solution C to obtain a mixed solution for later use;
(2) adjusting the pH value: adjusting the pH value of the mixed solution to 1, and transferring the mixed solution to a reaction kettle to obtain a precursor solution for reaction for later use;
(3) centrifugal drying: placing the mixed solution in a high-temperature polytetrafluoroethylene reaction kettle, reacting at 180 ℃ for 3-24h, centrifuging, taking a precipitate, washing the precipitate with water and alcohol for several times, and drying in a drying oven in vacuum to obtain a sample for later use;
(4) and (3) annealing and crystallizing process:
and (3) putting the dried sample in a tubular furnace, annealing and preserving heat for 2h at the temperature of 500 ℃ at the heating rate of 10 ℃/min, and removing crystal water to obtain the 1D nano rodlike FeV3O8 with uniform and stable size.
2. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: the metallic iron source in the step (1) is any one of ferric nitrate, ferric trichloride and ferric acetate.
3. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: the amounts of the substances of the metallic iron source and the vanadium source in the step (1)The ratio is 1: 5.
4. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: in the step (1), ferric trichloride and ammonium metavanadate are dissolved in deionized water and then are stirred for 30min respectively, and after mixing, the mixture is subjected to ultrasonic treatment for 10-60min under the conditions that the power is 40-60W and the ultrasonic frequency is 20-40Hz, and then is stirred for 10-30min at the stirring speed of 500 rad/min.
5. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: the reagent for adjusting the pH in the step (2) is glacial acetic acid (C2H4O 2).
6. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: the rotating speed of the centrifugation in the step (2) is 4000-.
7. The one-dimensional nanorod-shaped FeV as defined in claim 13O8The preparation method is characterized by comprising the following steps: and (3) drying in the oven in the step (2) under the vacuum pressure of 0.08-0.10MPa at the temperature of 60 ℃ for 12-24 h.
8. The one-dimensional nanorod-shaped FeV of claim 13O8The application in catalyzing and degrading organic pollutants. The method is characterized in that under the condition of available light, organic pollutants such as rhodamine B (RhB) and Methylene Blue (MB) can be completely degraded within 25min, and the degradation rates are respectively 99% and 99.8%.
9. A photoelectrochemical analysis system comprising an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and an electrolyte, wherein the surface of the working electrode is coated with the one-dimensional nanorod FeV as described in claim 13O8Material preparation and application in photocatalytic degradation of organic pollutants; in thatIn a standard three-electrode electrochemical test, Photoelectrochemical (PEC) measurements were performed using an electrochemical workstation (CHI760E, CHInstruments) using a carbon rod and Ag/AgC1 electrode (0.5M Na2SO4 in electrolyte solution) as counter and reference electrodes, respectively, the working electrode being a glassy carbon electrode (GCE, 3mm diameter).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110803133.2A CN113351219A (en) | 2021-07-15 | 2021-07-15 | Nano-rod-shaped FeV3O8Preparation method and photocatalytic application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110803133.2A CN113351219A (en) | 2021-07-15 | 2021-07-15 | Nano-rod-shaped FeV3O8Preparation method and photocatalytic application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113351219A true CN113351219A (en) | 2021-09-07 |
Family
ID=77539598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110803133.2A Pending CN113351219A (en) | 2021-07-15 | 2021-07-15 | Nano-rod-shaped FeV3O8Preparation method and photocatalytic application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113351219A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644195A (en) * | 2020-07-01 | 2020-09-11 | 济南大学 | Preparation method of catalyst for electrocatalytic degradation of hydrazine environmental pollutants and hydrogen production |
-
2021
- 2021-07-15 CN CN202110803133.2A patent/CN113351219A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644195A (en) * | 2020-07-01 | 2020-09-11 | 济南大学 | Preparation method of catalyst for electrocatalytic degradation of hydrazine environmental pollutants and hydrogen production |
Non-Patent Citations (1)
| Title |
|---|
| 朱皓: "金属钒氧化物纳米材料的简便制备及其光/电性能研究", 《万方学位论文》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102580742B (en) | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof | |
| Bafaqeer et al. | Synthesis of hierarchical ZnV2O6 nanosheets with enhanced activity and stability for visible light driven CO2 reduction to solar fuels | |
| CN101653728B (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| CN111437867B (en) | Composite photocatalyst containing tungsten oxide and preparation method and application thereof | |
| CN107497456B (en) | Preparation method and application of layered bismuth oxychloride visible-light-driven photocatalyst | |
| CN109174082B (en) | Preparation of BiVO4/MnO2Method for preparing composite photocatalytic oxidant | |
| CN108927188B (en) | Bismuth oxycarbonate photocatalyst and preparation method thereof | |
| CN108855131B (en) | Preparation and application of silver-nickel bimetal doped titanium dioxide nano composite material | |
| CN101537354A (en) | Preparation method of visible-light activated cuprous oxide/titanium dioxide nano-composite photocatalyst and applications thereof | |
| CN113663693B (en) | Preparation method of indium zinc sulfide-titanium dioxide composite material and application of indium zinc sulfide-titanium dioxide composite material in production of hydrogen peroxide for wastewater treatment | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| CN106669744B (en) | Ag2Mo2O7@ AgBr composite photocatalyst and preparation method thereof | |
| CN113000056A (en) | MXene doping-based composite material and preparation method thereof | |
| CN110589886A (en) | Preparation method of bismuth oxycarbonate | |
| CN105772039A (en) | Fluorine and boron co-doped TiO2 nano-plate with crystal planes (001) and oxygen vacancy, method for preparing fluorine and boron co-doped TiO2 nano-plate and application thereof | |
| CN105536843A (en) | Preparation method of highly visible light electron transfer g-C3N4/ Au/TiO2 Z type photocatalyst | |
| CN110615470A (en) | One-dimensional metal-doped rutile titanium dioxide nanowire and preparation method thereof | |
| CN113578313B (en) | Manganese-doped sillenite photocatalyst, preparation method thereof and application thereof in synchronous degradation of hexavalent chromium and organic pollutants | |
| CN108273539B (en) | Ta3N5Nanoparticle hybrid TiO2Hollow sphere composite photocatalyst and preparation method and application thereof | |
| CN112495400B (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
| CN113578306A (en) | Preparation method of 2D/1D heterojunction photocatalyst and application thereof in hydrogen production | |
| CN108311163A (en) | A kind of bismuth oxybromide composite photo-catalyst and preparation method thereof for hydrogen manufacturing | |
| CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
| Li et al. | Structure, optical property, and photo-catalytic activity of solid-solution β-AgAl1− xGaxO2 under visible light | |
| CN103041772A (en) | One-dimensional zinc oxide/graphitized carbon core-shell structure hetero-junction and preparation method thereof |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210907 |