CN100383052C - Method for preparing nano sodium bismuthate by chemical oxidation method - Google Patents
Method for preparing nano sodium bismuthate by chemical oxidation method Download PDFInfo
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- CN100383052C CN100383052C CNB2004100914714A CN200410091471A CN100383052C CN 100383052 C CN100383052 C CN 100383052C CN B2004100914714 A CNB2004100914714 A CN B2004100914714A CN 200410091471 A CN200410091471 A CN 200410091471A CN 100383052 C CN100383052 C CN 100383052C
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Abstract
The invention relates to a method for preparing nano sodium bismuthate, which is characterized in that soluble bismuth salt solution or bismuth salt powder is slowly added into mixed solution of hypochlorite and alkali liquor under the condition of controlling a certain temperature and the concentration of the hypochlorite and the alkali liquor to prepare nano sodium bismuthate crystal. The nano sodium bismuthate prepared by the invention has the characteristics of complete crystal form, high purity, small particle size, simple synthesis process and the like, is suitable for an additive of an alkaline zinc-manganese primary battery or a rechargeable alkaline zinc-manganese secondary battery anode, and can also be used in other occasions requiring sodium bismuthate, such as organic oxidation synthesis, novel inorganic material research and development and the like.
Description
The invention belongs to the technical field
The present invention belongs to the field of inorganic chemistry, in the concrete, it belongs to the synthesis technology of nano inorganic salt.
Second, the technical background of the invention
The invention relates to a method for synthesizing nano bismuthate (mainly sodium bismuthate). In particular to a synthesis method for preparing high-purity nano sodium bismuthate by chemically oxidizing bismuth nitrate with a mixed solution of sodium hypochlorite and sodium hydroxide.
Bismuth is usually present as an element or as trivalent bismuth [ Bi (III)]Exists in the form of (B), but can obtain pentavalent bismuth [ Bi (V) under the action of strong oxidant]A compound, which is usually present in the form of a bismuthate. Sodium bismuthate (NaBiO) 3 ·2H 2 O) is a novel inorganic functional material, has special strong oxidizing property, electromagnetic property and electrochemical activity, and is successfully applied to the fields of organic synthesis, superconductors, electrochemistry and the like. The traditional method for preparing sodium bismuthate with common particle size usually adopts strong oxidant Cl 2 Oxidizing bismuth hydroxide in strongly alkaline solution or by Na at high temperature 2 O 2 And Bi 2 O 3 The sodium bismuthate obtained by the method mainly exists: large grain size, low purity and the like. Kumadan et al, abroad, reported that ion exchange methods improve the synthesis process of bismuthate, but have the disadvantage that these synthesis methods require heating times of up to several days.
Electrode material for developing high specific capacityThe material has become a hot spot of the research of inorganic functional materials at present. Although the rechargeable alkaline manganese battery is a potential novel secondary battery due to abundant resources and low price, the key point of the current manganese dioxide secondary is to improve the reversibility of deep discharge of a manganese dioxide electrode, so that a great deal of research is carried out on a modified additive of manganese dioxide by a plurality of chemists from various angles, and the additive reported at present is Bi 2 O 3 PbO and TiO 2 Etc., the use of these additives can increase MnO to some extent 2 Discharge capacity and cycle performance of the electrode. Xixi et al report nano Bi 2 O 3 And TiO 2 2 The results of the synthesis and the doping modification of the manganese dioxide anode of the alkaline zinc-manganese battery show that the manganese dioxide anode is doped with nano Bi 2 O 3 The performance after the particles is better than that of the common Bi doped 2 O 3 The particles have a significant improvement in electrochemical performance. The previous research results show that the electrochemical performance of the manganese dioxide anode doped with sodium bismuthate is obviously superior to that of Bi with equivalent doped particle size 2 O 3 The electrochemical activity of the manganese dioxide positive electrode is increased along with the reduction of the particle size of the sodium bismuthate, which is probably due to the high specific surface area of the small-particle-size particlesHaving a high surface energy. Therefore, it is necessary to research how to rapidly synthesize sodium bismuthate with small particle size, especially sodium bismuthate with nano particle size range, but no relevant report about the synthesis method of nano sodium bismuthate is found at home and abroad.
Third, summary of the invention
The invention aims to provide a chemical synthesis method of nano sodium bismuthate aiming at the problems of the existing bismuthate synthesis technology, namely, the nano sodium bismuthate is prepared by a liquid-phase oxidation method. The nano sodium bismuthate prepared by the synthesis method has the advantages of complete crystal form, high purity, small particle size, simple and easy operation process and the like, is particularly suitable for additives of anodes of alkaline zinc-manganese primary batteries or rechargeable alkaline zinc-manganese secondary batteries, and can also be used in other occasions requiring the sodium bismuthate, such as organic oxidation synthesis, novel inorganic material research and development and the like. The invention firstly provides and invents a novel synthesis method for preparing high-purity nano sodium bismuthate by directly oxidizing soluble bismuth salt by adopting a high-concentration hypochlorite and sodium hydroxide mixed solution. According to the novel chemical synthesis method, the nanometer-sized superfine sodium bismuthate can be directly and rapidly synthesized. Research results show that the high-purity hydrated sodium bismuthate crystal can be directly obtained by controlling the condition of oxidation synthesis. Meanwhile, the traditional process matched with the synthesis process is improved to a certain extent, so that the synthesis process is more suitable for a new synthesis method. Compared with other preparation methods, the new method is faster and more effective, generally only needs about 60 minutes, not only obviously shortens the time required by sedimentation, filtration and washing, but also prepares ferrate with higher purity, generally the purity of a once-crystallized product after washing can reach more than 92 percent or above, and can directly meet the requirement of analyzing a pure-grade reagent.
The synthesis process of the present invention is thus achieved. Bismuth ion solution with certain concentration, such as 5-45 wt% bismuth nitrate or bismuth chloride solution (or other bismuth salts, such as bismuth sulfate and bismuth acetate) is slowly added into the mixed solution of hypochlorite and alkali solution under the condition of controlling certain temperature and concentration of hypochlorite and alkali solution, at the moment, white active bismuth hydroxide microcrystals are firstly separated out and then quickly converted into light yellow nano sodium bismuthate crystals. The hypochlorite is sodium hypochlorite, potassium hypochlorite, calcium hypochlorite or a mixture thereof in any ratio, and among them, sodium hypochlorite is preferable. The alkali liquor is sodium hydroxide solution, potassium hydroxide solution or their mixture in any proportion. The reaction temperature of the above reaction is usually 5 to 45 ℃ and the alkali solution concentration is 5 to 53% by weight. Wherein the reaction temperature is preferably 15-30 ℃, and the concentration of the alkali liquor is 20-45 percent by weight of sodium hydroxide. The nano sodium bismuthate is subjected to centrifugal dehydration or standing sedimentation, is subjected to suction filtration or filter pressing and is dried, is washed by 0.1-3 mol/L NaOH, and is washed by purified water until the pH value of a washing liquid is 8-13. Drying for 1-10 h under the condition of controlling the temperature to be 15-105 ℃, preferably drying for 3-16 h under the vacuum condition and the temperature to be 50-75 ℃ to obtain the nano sodium bismuthate crystal with the water content of less than 5 percent. Or directly reacting solid bismuth salt (such as bismuth chloride, bismuth nitrate, bismuth sulfate or bismuth acetate) with the mixed solution to obtain hydrated sodium bismuth crystal, washing, and drying to obtain nanometer crystal with the same crystal form.
The specific synthetic process is as follows: adding Cl 2 The NaOH solution is added into the solution with the weight percentage of 22 to 40 percent until the alkali liquor absorbs the chlorine gas to reach the sodium hypochlorite solution with the available chlorine content of 10 to 25 percent, the chlorine gas is stopped being added, and the method generally prefers the available chlorine content to be 15 to 23 percent. Then adding a proper amount of NaOH solid into the solution to ensure that the content of NaOH reaches 30-50 percent by weight. In the process of adding the NaOH solid, some sodium chloride solid can be separated out, and after the sodium chloride is removed by filtration, the NaClO-NaOH solution suitable for synthesizing the nano sodium bismuthate is obtained. Gradually and slowly adding the finely ground bismuth salt powder or bismuth salt solution into the solution under stirring, reacting for 30-160 minutes under strong stirring and room temperature, and finally injecting a proper amount of saturated sodium hydroxide solution into the solution until the nano sodium bismuthate is completely precipitated, wherein the reaction is controlled at 5-50 ℃, and preferably 15-40 ℃. The crude product is filtered and drained after centrifugal separation, washed by 0.1-3 mol/L NaOH, then washed by pure water until the pH value of the filtrate is less than 13, and finally the product is dried in vacuum at 20-60 ℃. Fe for purity of the obtained product 2+ The purity of the product is 92.1-95.7% by chemical titration.
Experimental data show that the bismuth salt solution is used as a bismuth source instead of bismuth oxide, and under the condition of strictly controlling synthesis, the sodium bismuthate crystal with nanometer size can be obtained, and the purity and the yield are higher. Experiments show that under the same synthesis conditions, bismuth salt solution is used to replace bismuth oxide as bismuth source, the product purity is improved by 4-7%, and the yield is improved by 5-11%. The bismuth salt solution is used as the bismuth source, and the bismuth source in an ion form exists in the bismuth salt solution, so that the sufficient contact between reactant ions is ensured to the maximum extent, and the incomplete reaction caused by the particle reason of the adopted bismuth oxide is avoided. In addition, in TG-DSC experiments, the high-purity nano sodium bismuthate crystal has high stability at normal temperature, crystal water in the crystal begins to be slowly lost when the ambient temperature rises to 183 ℃, and the process of slow decomposition and oxygen loss begins when the ambient temperature exceeds 211 ℃, so that the nano sodium bismuthate has high stability at normal temperature obviously.
4. Description of the drawings
FIG. 1 is a transmission photograph of a sample of nano sodium bismuthate crystals taken by particle photography on a Hitachi H-800 Transmission Electron Microscope (TEM), and the scale in the photograph is 100nm.
FIG. 2 is an XRD diagram of the phase crystal structure of the nano sodium bismuthate crystal analyzed by Rigaku D/max2500VB2+/PC X-ray diffractometer in Japan. The Cu target for testing has the tube voltage of 40kV, the current of 200mA, the scanning speed of 10 degrees/min and the scanning angle (2 theta) range of 10 degrees to 90 degrees. The abscissa in the figure represents the 2 θ angle of X-ray diffraction, and the ordinate represents the intensity of X-ray diffraction. In the figure, the curve A is a synthesized sample, and the curve B is JCPDS standard card of sodium bismuthate.
FIG. 3 is a TG-DSC curve of nano sodium bismuthate measured by a TGA-7 thermal gravimetric differential thermal analyzer of the American PE company, the measurement range is as follows: the temperature is 25-600 ℃, and the heating rate is 10 ℃/min. The abscissa of the graph is temperature (deg.C), the left ordinate represents the percentage of weight loss, and the right ordinate represents the amount of heat generated by the process.
Fifth, the detailed description of the invention
The invention will now be further illustrated by the following examples.
Example 1
80ml of 30 percent NaOH absorbs 20g of chlorine at the temperature of 15-30 ℃,50g of sodium hydroxide was added, and the precipitated sodium chloride was filtered off to obtain a mixture of sodium hypochlorite and sodium hydroxide. With 25 g Bi (NO) 3 ·5H 2 O crystal is bismuth source, after mechanically grinding, adding a small amount of the crystal into the sodium hypochlorite test solution for many times under strong stirring, controlling the reaction temperature at 25-40 ℃ and the reaction time at 60min to obtain yellow NaBiO 3 ·2H 2 And (4) precipitating O. Standing the precipitate for layering, transferring to glass filter funnel, washing with 1% NaOH and pure water, vacuum drying with filter flask, and drying in vacuum drying oven at 45 deg.C for 24 hr to obtain sodium bismuthate sample. The purity of the product was determined to be 92.5% by chemical analysis.
Example 2
80ml of 30% NaOH was used to absorb 21g of chlorine gas, and 66g of sodium hydroxide was added to the solution, and the precipitated sodium chloride was filtered off. Adding 100ml of 1mol/L bismuth nitrate solution into the solution, controlling the reaction temperature to be 20-30 ℃, fully reacting for 60 minutes, then injecting 20ml of saturated NaOH solution, filtering and separating to obtain a crude product of the nano sodium bismuthate, wherein the reaction is controlled at 30 ℃. Filtering and drying the crude product, washing the crude product with 0.5mlo/L, 0.1mol/L NaOH and pure water in sequence to obtain a nano sodium bismuthate product, and finally drying the product in vacuum at 80 ℃. The purity of the obtained product is 95.1%.
Example 3
120g of 35% NaOH absorbs 30g of chlorine at 15-25 ℃, 55g of sodium hydroxide is added, and the precipitated sodium chloride is filtered to obtain a mixed solution of sodium hypochlorite and sodium hydroxide. With 50ml1.8mol/L of Bi (NO) 3 ·5H 2 O crystal is bismuth source, under the condition of strong stirring it is added into the mixed liquor test solution of sodium hypochlorite and sodium hydroxide in the form of spray, the above-mentioned reaction temp. is controlled at 26-42 deg.C, and reaction time is 70min, so that the light yellow NaBiO can be obtained 3 ·2H 2 And (4) precipitating O. Standing the precipitate for layering, transferringWashing with 1% NaOH and pure water on glass filter funnel, vacuum drying with filter flask, and drying at 50 deg.C for 18 hr in vacuum drying oven to obtain final productTo a nano sodium bismuthate sample. The purity of the product was 93.1% by chemical analysis.
Claims (5)
1. A synthesis method of nano sodium bismuthate is characterized in that chlorine gas is led into sodium hydroxide solution with the weight percentage of 20-40% to obtain sodium hypochlorite solution saturated by the chlorine gas, then sodium hydroxide solid with the weight percentage of 30-50% relative to the solution is added to obtain mixed solution of the sodium hypochlorite and the sodium hydroxide to oxidize soluble bismuth salt to prepare the nano sodium bismuthate.
2. The method for synthesizing nano sodium bismuthate as claimed in claim 1, wherein the soluble bismuth salt is one bismuth salt selected from bismuth nitrate, bismuth chloride, bismuth sulfate and bismuth acetate, or a mixture of two or more of the above bismuth salts.
3. The method for synthesizing nano sodium bismuthate as claimed in claim 2, wherein the bismuth nitrate is an aqueous solution of bismuth salt or mechanically ground bismuth nitrate powder.
4. The method for synthesizing nano sodium bismuthate as claimed in claim 1, wherein the sodium hypochlorite solution has an available chlorine content of 10-25%.
5. The method for synthesizing sodium bismuthate as claimed in claim 1, which is characterized in that the sodium bismuthate is synthesized at a reaction temperature of 5-45 ℃.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270813A (en) * | 1992-03-23 | 1993-10-19 | Kawasaki Steel Corp | Production of polycrystalline silicon substrate |
| CN1116108C (en) * | 1996-08-23 | 2003-07-30 | 巴斯福股份公司 | Bismuth-containing catalysts |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270813A (en) * | 1992-03-23 | 1993-10-19 | Kawasaki Steel Corp | Production of polycrystalline silicon substrate |
| CN1116108C (en) * | 1996-08-23 | 2003-07-30 | 巴斯福股份公司 | Bismuth-containing catalysts |
Non-Patent Citations (3)
| Title |
|---|
| Neutron powder diffraction refinement of ilmenite-typebismuthoxides ABiO3 (A = Na, Ag). N. Kumada，A. W. Sleight et al.Materials research bulletin,Vol.30 . 2000 * |
| Preparation and Crystal Structure of a New LithiumBismuthOxide LiBiO3. N. Kumada，A. W. Sleight et al.Journal of solid state chemistry,Vol.126 . 1996 * |
| Sol－Gel 法合成 NaBiO3 多晶粉末. 李加新.广东化工，第5期. 1999 * |
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