Synthetic method of ferric oxide nanorod
阅读说明：本技术 一种三氧化二铁纳米棒的合成方法 (Synthetic method of ferric oxide nanorod ) 是由 陶菲菲 兰明轩 毛君 于 2019-10-25 设计创作，主要内容包括：本申请提供一种三氧化二铁纳米棒的合成方法,属于用于材料和表面科学的纳米结构制造或处理技术领域。取六水合三氯化铁分散在无水乙醇中,搅拌状态下,依次加入离子液体1-丁基-3-甲基咪唑氯盐[BMIM]Cl和NaOH固体,转移至内衬为聚四氟乙烯的不锈钢高压釜中,溶剂热反应结束后,真空干燥,置于马弗炉中热处理,自然冷却至室温,即可得α-Fe<Sub>2</Sub>O<Sub>3</Sub>纳米棒。将本申请作为光催化剂应用于染料降解,具有尺寸均一、分散性好、结晶度好等优点,在光催化领域具有潜在的应用价值。(the application provides a ferric oxide nanorod synthesis method, which belongs to the technical field of nanostructure manufacturing or processing for material and surface science, ferric trichloride hexahydrate is dispersed in absolute ethyl alcohol, ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl and NaOH solid are sequentially added under the stirring state, the mixture is transferred to a stainless steel autoclave lined with polytetrafluoroethylene, after the solvent thermal reaction is finished, vacuum drying is carried out, the mixture is placed in a muffle furnace for heat treatment, and the mixture is naturally cooled to room temperature, so that the alpha-Fe 2 O 3 nanorod is obtained.)
1. A synthetic method of an iron trioxide nanorod is characterized by comprising the following steps:
(1) Dispersing ferric trichloride hexahydrate in absolute ethyl alcohol;
(2) Under the stirring state, sequentially adding ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl and NaOH solid into the solution in the step (1), and continuing stirring;
(3) Transferring the solution in the step (2) into a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, sealing the kettle, placing the kettle in an oven, and carrying out solvothermal reaction at the temperature of (160-;
(4) After the reaction is finished, naturally cooling the autoclave to room temperature, centrifugally separating precipitates, sequentially washing the precipitates by deionized water and absolute ethyl alcohol, collecting products, and drying the products in vacuum;
(5) And putting the dried powder in a muffle furnace, heating to 380-420 ℃ at the heating rate of (3-7) DEG C/min -1 for heat treatment for 2-4 h, and naturally cooling to room temperature to obtain the alpha-Fe 2 O 3 nanorod.
2. The method for synthesizing the ferric oxide nanorod according to claim 1, wherein the method comprises the following steps: in the step (1), ferric chloride hexahydrate is dispersed in absolute ethyl alcohol by an ultrasonic method.
3. the method for synthesizing the ferric oxide nanorod according to claim 1, wherein the method comprises the following steps: (4-6) mmol of ferric chloride hexahydrate corresponding to (4-6) mmol of ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl, (15-25) mmol of solid NaOH.
4. The method for synthesizing the ferric oxide nanorod according to claim 2, wherein the method comprises the following steps: in the step (3), the volume filling rate in the autoclave was 80%.
5. the method for synthesizing ferric oxide nanorods according to claim 2, characterized in that in step (5), the heating rate is 5 ℃ min -1, the heat treatment temperature is 400 ℃, and the heat treatment time is 3 h.
6. A synthetic method of an iron trioxide nanorod is characterized by comprising the following steps:
(1) Weighing (4-6) mmol ferric chloride hexahydrate and dispersing in absolute ethyl alcohol;
(2) Under the condition of stirring, sequentially adding (4-6) mmol of ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl and (15-25) mmol of NaOH solid into the solution in the step (1), and continuously stirring;
(3) Transferring the solution in the step (2) into a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, sealing the kettle, and performing solvothermal reaction at the temperature of (160-;
(4) After the reaction is finished, naturally cooling the high-pressure autoclave to room temperature, centrifugally separating precipitates, sequentially washing the precipitates for at least 5 times by deionized water and absolute ethyl alcohol, and collecting a product to be dried for 12 hours in vacuum at 80 ℃;
(5) And putting the dried powder in a muffle furnace, heating to 400 ℃ at the temperature rising speed of 5 ℃ min -1, carrying out heat treatment for 3h, and naturally cooling to room temperature to obtain the Fe 2 O 3 nanorod.
7. The method of synthesizing ferric oxide nanorods according to claim 6, characterized in that: in the step (1), ferric chloride hexahydrate is dispersed in absolute ethyl alcohol by an ultrasonic method.
Technical Field
the application relates to a method for synthesizing ferric oxide nano-rods, belonging to the nano-structure manufacture or treatment for material and surface science.
Background
With the rapid development of global economy and the continuous improvement of living standard of people, the environmental pollution and energy consumption crisis caused by the global economy are more and more obvious. Chemical, textile, printing and dyeing, pharmaceutical and paper industries all produce a large amount of wastewater, and the industrial wastewater contains a large amount of organic pollutants and needs to be subjected to sewage treatment before being discharged. The traditional sewage treatment methods, such as adsorption, coagulating sedimentation, biological treatment, membrane technology, high-temperature incineration and the like, have the disadvantages of complex process, long reaction time, high operation cost, incomplete removal of pollutants and easy generation of secondary pollution. Therefore, a new method which is low in energy consumption and effectively overcomes the problem of water pollution is urgently needed to be found.
the method is characterized in that a semiconductor nano photocatalyst is widely accepted as a photocatalyst capable of efficiently removing colored pollutants, Fe 2 O 3 is an iron oxide which is most stable and abundant in natural environment, Fe 2 O 3 nano material has the advantages of unique shape structure, stable property, abundant sources, low price, no toxicity, high activity and the like, and has potential application value in the fields of photocatalysis, photoelectrocatalysis, gas-sensitive sensors and the like.
In order to obtain a visible light catalyst with high activity and high stability, a solvothermal method, a solution method, a sol-gel method, a heat treatment method and the like are adopted to synthesize an alpha-Fe 2 O 3 micro-nano material such as microspheres, nanoflowers, nanotubes and nanorods, for example, an ionic liquid assisted solvothermal and heat treatment method is adopted to prepare porous self-assembled alpha-Fe 2 O 3 hollow microspheres such as H.YIn, and the like, wherein the ionic liquid [ C 4 Mim ] BF 7 is used as a soft template and plays an important role in controlling the morphology of the hollow structure of the product, and the rate constant of photocatalytic degradation of rhodamine B is 2-3 times that of alpha-Fe 2 O 3 particles (H.YIn, et al Frost ions in Chemistry,2019,7,58.) C.Ye and the like, and the rate of photocatalytic degradation of Fe 2 O 3 particles is 2-3 times that of H.YIN, H.R. 11 in Chemistry,2019,7,58.) C.Ye and the like are prepared by a soft template P123 synthesis method, and have the catalytic degradation rate of a crystal surface area of a crystal of a bisphenol A72, which is improved by irradiation, and a visible light irradiation temperature of a visible light irradiation of a visible light source of a crystal aging crystal, a visible light source, a.
Disclosure of Invention
in view of the above, the present application provides a method for synthesizing an iron sesquioxide (α -Fe 2 O 3) nanorod, which comprises preparing a complex of iron ions and ionic liquid [ BMIM ] Cl under the control of NaOH solids and under the high temperature and pressure conditions generated by an autoclave, and decomposing the complex by heat treatment to obtain a nanorod-like α -Fe 2 O 3, wherein the nanorod-like α -Fe 2 O 3 is uniform in shape, size and yield, and has a large amount of microporous structures on the surface, so that the specific surface area of the product can be increased, the active sites of the reaction are increased, and the α -Fe 2 O 3 has good visible light catalytic performance.
The synthesis method of the alpha-Fe 2 O 3 nanorod provided by the application comprises the following specific steps:
(1) Dispersing ferric trichloride hexahydrate in absolute ethyl alcohol;
(2) under the stirring state, sequentially adding ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl and NaOH solid into the solution in the step (1), and continuing stirring;
(3) Transferring the solution in the step (2) into a stainless steel high-pressure kettle with a polytetrafluoroethylene lining, sealing the kettle, placing the kettle in an oven, and carrying out solvothermal reaction at the temperature of (160-;
(4) after the reaction is finished, naturally cooling the autoclave to room temperature, centrifugally separating precipitates, sequentially washing the precipitates by deionized water and absolute ethyl alcohol, collecting products, and drying the products in vacuum;
(5) And putting the dried powder in a muffle furnace, heating to 380-420 ℃ at the heating rate of (3-7) DEG C/min -1 for heat treatment for 2-4 h, and naturally cooling to room temperature to obtain the alpha-Fe 2 O 3 nanorod.
The alpha-Fe 2 O 3 rod synthesized by the method is powder, the crystalline phase is a hexagonal structure, the rhombohedral system is a nano rod-shaped structure, the diameter of the particle is about 40nm-200nm, the length is about 0.1 mu m-2.0 mu m, and the shape and the structure of the obtained target product are represented by an X-ray diffractometer (XRD, Empyrean, Parnake, the Netherlands) and a transmission electron microscope (TEM, JEM-1011, Japanese electron and 80kV of acceleration voltage).
Preferably, the above scheme can also be set as follows:
(1) Accurately weighing (4-6) mmol ferric chloride hexahydrate and dispersing in 20mL absolute ethyl alcohol;
(2) Under the condition of violent stirring, sequentially adding (4-6) mmol of ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl and (15-25) mmol of NaOH solid into the solution in the step (1), and continuously stirring;
(3) transferring the solution in the step (2) into a stainless steel high-pressure autoclave with a polytetrafluoroethylene lining, sealing the autoclave with the volume filling rate of 80 percent, and placing the high-pressure autoclave in an oven (160-;
(4) After the reaction is finished, naturally cooling the high-pressure autoclave to room temperature, centrifugally separating precipitates, sequentially washing the precipitates for at least 5 times by deionized water and absolute ethyl alcohol, and collecting a product to be dried for 12 hours in vacuum at 80 ℃;
(5) And putting the dried powder in a muffle furnace, heating to 400 ℃ at the temperature rising speed of 5 ℃ min -1, carrying out heat treatment for 3h, and naturally cooling to room temperature to obtain the alpha-Fe 2 O 3 nanorod.
in the step (1), ferric chloride hexahydrate is dispersed in absolute ethyl alcohol by an ultrasonic method.
(4-6) mmol of ferric chloride hexahydrate corresponding to (4-6) mmol of ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl, (15-25) mmol of solid NaOH.
In the step (3), the volume filling rate in the autoclave was 80%.
The heat treatment parameters in the step (5) are that the heating rate is 5 ℃ min -1, the heat treatment temperature is 400 ℃, and the heat treatment time is 3 h.
The working principle and the beneficial effects of the application can be summarized as follows:
(1) The method comprises the steps of forming a complex by utilizing the interaction between iron ions and ionic liquid 1-butyl-3-methylimidazolium chloride [ BMIM ] Cl, and combining solvothermal reaction with thermal treatment to prepare the alpha-Fe 2 O 3 nanorod.
(2) the size of the alpha-Fe 2 O 3 nanorod can be regulated and controlled by the concentration of an iron precursor, the solvothermal reaction temperature, the solvothermal reaction time and the like, the iron precursor can be decomposed by a heat treatment method to obtain the high-purity alpha-Fe 2 O 3 nanorod, the crystal form, the porous structure and the morphological integrity of the alpha-Fe 2 O 3 can be influenced by the heating rate, the heat treatment time and the temperature of the heat treatment, and the morphology and the surface porous structure of a product can be damaged by too fast heating rate, too high heat treatment temperature and too long heat treatment time.
(3) The alpha-Fe 2 O 3 nanorod prepared by the method is simple and easy to control by controlling the adding amount of iron precursors, ionic liquid [ BMIM ] Cl and NaOH solids and the temperature and time of solvothermal reaction, and the diameter and the length of the alpha-Fe 2 O 3 nanorod are regulated and controlled, and the special morphology and the surface porous structure of the alpha-Fe 2 O 3 nanorod have higher application value as a visible light catalyst.
The present application is further described with reference to the following drawings and detailed description.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the synthesized α -Fe 2 O 3 nanorod in example 5;
FIG. 2 is a Transmission Electron Microscope (TEM) photograph of α -Fe 2 O 3 nanorods synthesized in example 5;
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of synthesized α -Fe 2 O 3 nanorods of example 6;
FIG. 4 is a Transmission Electron Microscope (TEM) photograph of α -Fe 2 O 3 nanorods synthesized in example 7.
Detailed Description