CN103964506B - A kind of preparation method of metal chromite series compound nanostructure - Google Patents
A kind of preparation method of metal chromite series compound nanostructure Download PDFInfo
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Abstract
A kind of preparation method of metal chromite series compound nanostructure, it is characterized in that first with potassiumchromate and soluble metallic salt synthesis chromic salt forerunner, in solvent thermal system, utilize aqueous glycol solution to carry out in-situ reducing to chromic salt again, form metal chromite finally by carrying out washing treatment.Technological method involved in the present invention has following obvious advantage: 1. the present invention is based on solvent thermal technology, and technique is simple, easy to operate, low without especial equipment requirements, production cost, and environmentally friendly; 2. this ethylene glycol in-situ reducing technology is wet chemical method, and products therefrom has certain morphological specificity; 3. the preparation of the method to extensive metal chromite series compound has good universality.
Description
Technical field
The invention belongs to inorganic material chemistry field, relate to a kind of general preparative methods of chromite series compound.
Background technology
Metal chromite has perovskite structure (MCrO usually
3, M is trivalent metal, as: rare earth metal etc.) or spinel structure (MCr
2o
4, M is divalent metal, as alkaline-earth metal, transition metal etc.).First, this kind of material has very high fusing point, is good refractory materials, and in addition superior antioxidation property and conduction property make it in Solid Oxide Fuel Cell, have huge applications potentiality; Secondly, the electronic structure of Cr element uniqueness determines this system material and has novel magnetic property, especially for those magnetic transition metal chromites and rare earth chromite, owing to comprising two kinds of magnetic element in material, it is made to show more complicated magnetic characteristic, portion of material also has multiferroic, namely has magnetization character and ferroelectric property concurrently; Finally, metal chromite or effective catalyzer, can be widely used in the fields such as the oxidation of organic compound.
At present, preparing the topmost method of chromite is solid-phase synthesis, and namely utilize chromium sesquioxide and metal oxide to be raw material, at high temperature (>=1000 DEG C) carry out calcining and obtaining.These class methods require heating for multiple times and grinding usually, and need atmosphere protection, and gained sample generally has larger size, and do not have well-regulated form, and chromium sesquioxide itself has very high fusing point in addition, make the purity of final product not ideal enough.Therefore, the method complex process equipment, energy consumption is comparatively large, and production cost is high.In order to reduce temperature of reaction, self-propagating method and mechanochemical reaction are also used to prepare chromite, temperature of reaction can be reduced to less than 1000 DEG C.In the last few years, because chromite receives the concern of vast researcher, many wet chemical preparation methods are also constantly applied in the preparation of metal chromite, as: sol-gel method, coprecipitation method, solution auto-combustion method, sonochemistry method, spray pyrolysis, microwave method, hydrothermal method etc.But, explore a kind of simple, pervasive chemical preparation process, synthesize large-scale metal chromite series compound, especially prepare its nanostructure, there is larger challenge all the time, in fields such as material, physics, chemistry, all there is important Research Significance.
Summary of the invention
In order to improve the universality of chromous acid preparation method, the present invention proposes a kind of ethylene glycol in-situ reducing technology, can be widely used in the preparation of metal chromous acid series compound nanostructure.The method is without the need to complex apparatus, and processing condition are simple, and easy handling controls, and synthesis cost is low.
The present invention is achieved by the following technical solutions.
1) preparation of chromic salt presoma.Soluble metallic salt and potassiumchromate (K is taken by the stoichiometric ratio of prepared chromic salt presoma
2crO
4), both are dissolved in the mixed solvent of ethylene glycol and water respectively, and the volume ratio of ethylene glycol and water is 1:4 ~ 4:1, is then under agitation mixed by two kinds of reaction solns.
2) solvent thermal reaction.The mixing solutions obtained in step 1) is transferred in reaction autoclave, 150 ~ 200 DEG C of constant temperature sealed reactions, after reaction terminates, is cooled to room temperature.
3) carrying out washing treatment.By step 2) in solvent thermal reaction product filter, with the alternately washing of water and ethanol, remove the complete ion of unreacted and residual organism, obtained chromite product after dry.
Soluble metallic salt described in step 1) of the present invention is the rare earth metals such as lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), dysprosium (Dy), holmium (Ho), yttrium (Y), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu), and the one in the divalent transition metal such as iron (Fe), cobalt (Co), zinc (Zn), cadmium (Cd) or copper (Cu).
Rare earth chromite prepared by the present invention has typical orthogonal perovskite structure, and divalent transition metal chromite then has typical cubic spinel structure.
Technological method involved in the present invention has following obvious advantage: 1. the present invention is based on solvent thermal technology, and technique is simple, easy to operate, low without especial equipment requirements, production cost, and environmentally friendly; 2. this ethylene glycol in-situ reducing technology is wet chemical method, and products therefrom has certain morphological specificity; 3. the preparation of the method to extensive metal chromite series compound has good universality.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of embodiment 1 sample after 800 DEG C of annealing.
Fig. 2 is the electron scanning micrograph of embodiment 1 sample after 800 DEG C of annealing.
Fig. 3 is the X-ray diffracting spectrum of embodiment 2 sample after 800 DEG C of annealing.
Fig. 4 is the electron scanning micrograph of embodiment 2 sample after 800 DEG C of annealing.
Fig. 5 is the X-ray diffracting spectrum of embodiment 3 sample after 600 DEG C of annealing.
Fig. 6 is the electron scanning micrograph of embodiment 3 sample after 600 DEG C of annealing.
Fig. 7 is the X-ray diffracting spectrum of embodiment 4 sample after 600 DEG C of annealing.
Fig. 8 is the electron scanning micrograph of embodiment 4 sample after 600 DEG C of annealing.
Embodiment
In order to understand the present invention better, below in conjunction with specific embodiment, the present invention will be further described, but protection content of the present invention is not limited to the following example.
Embodiment 1: chromous acid europium (EuCrO
3) preparation.
1) 2mmol potassiumchromate and 1mmol europium nitrate is taken, both are dissolved in (5mL ethylene glycol+15mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:3), under magnetic stirring, potassium chromate solution is added drop-wise in europium nitrate solution gradually, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain chromous acid europium powdered product.
Embodiment 2: chromous acid neodymium (NdCrO
3) preparation.
1) 2mmol potassiumchromate and 1mmol neodymium nitrate is taken, both are dissolved in (5mL ethylene glycol+15mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:3), under magnetic stirring, potassium chromate solution is added drop-wise to gradually in neodymium nitrate solution, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain chromous acid neodymium powdered product.
Embodiment 3: cobalt chromite (CoCr
2o
4) preparation.
1) 2mmol potassiumchromate and 2mmol cobalt chloride is taken, both are dissolved in (10mL ethylene glycol+10mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:1), under magnetic stirring, potassium chromate solution is added drop-wise in cobalt chloride solution gradually, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 6 ~ 12 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain cobalt chromite powdered product.
Embodiment 4: chromous acid cadmium (CdCr
2o
4) preparation.
1) 2mmol potassiumchromate and 2mmol Cadmium chloride fine powder is taken, both are dissolved in (10mL ethylene glycol+10mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:1), under magnetic stirring, potassium chromate solution is added drop-wise in cadmium chloride solution gradually, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain chromous acid cadmium dust product.
Embodiment 5: chromous acid zinc (ZnCr
2o
4) preparation.
1) 2mmol potassiumchromate and 2mmol zinc acetate is taken, both are dissolved in (10mL ethylene glycol+10mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:1), under magnetic stirring, potassium chromate solution is added drop-wise in acetic acid zinc solution gradually, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain chromous acid zinc powder product.
Embodiment 6: copper chromite (CuCr
2o
4) preparation.
1) 2mmol potassiumchromate and 2mmol cupric chloride is taken, both are dissolved in (10mL ethylene glycol+10mL distilled water in the mixed solvent of 20mL ethylene glycol and water respectively, namely the volume ratio of ethylene glycol and water is 1:1), under magnetic stirring, potassium chromate solution is added drop-wise in Cupric Chloride Solution gradually, forms suspension.
2) gained suspension is transferred in 50mL reaction autoclave, sealing, 150 DEG C of isothermal reactions 12 ~ 24 hours, after reaction terminates, naturally cools to room temperature.
3) hydro-thermal reaction product is carried out suction filtration, alternately wash for several times with water and ethanol, 50 DEG C of dryings 6 hours, obtain copper chromite powdered product.
Claims (1)
1. a preparation method for metal chromite series compound nanostructure, is characterized in that according to the following steps:
1) soluble metallic salt and potassiumchromate is taken by the stoichiometric ratio of prepared chromic salt presoma, both are dissolved in the mixed solvent of ethylene glycol and water respectively, the volume ratio of ethylene glycol and water is 1:4 ~ 4:1, is then under agitation mixed by two kinds of reaction solns;
2) mixing solutions obtained in step 1) is transferred in reaction autoclave, 150 ~ 200 DEG C of constant temperature sealed reactions, after reaction terminates, is cooled to room temperature;
3) by step 2) in reaction product filter, with the alternately washing of water and ethanol, remove the complete ion of unreacted and residual organism, obtained chromite product after dry;
Soluble metallic salt described in step 1) is the one in lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, yttrium, erbium, thulium, ytterbium, lutetium, iron, cobalt, zinc, cadmium or copper metal-salt.
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Effective date of registration: 20201209 Address after: No. 308 Xihu Road, Suqian City, Jiangsu Province (8th floor, Wanyuan commercial building) Patentee after: Jiangsu Tianyuan Project Management Group Co.,Ltd. Address before: 999 No. 330031 Jiangxi province Nanchang Honggutan University Avenue Patentee before: Nanchang University |