WO2019168420A1 - Method for manufacturing of inorganic salts with monovalent cation and anion of transition metal acid, in particular in the form of micro- and nanocrystals - Google Patents
Method for manufacturing of inorganic salts with monovalent cation and anion of transition metal acid, in particular in the form of micro- and nanocrystals Download PDFInfo
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- WO2019168420A1 WO2019168420A1 PCT/PL2019/000009 PL2019000009W WO2019168420A1 WO 2019168420 A1 WO2019168420 A1 WO 2019168420A1 PL 2019000009 W PL2019000009 W PL 2019000009W WO 2019168420 A1 WO2019168420 A1 WO 2019168420A1
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- vanadium pentoxide
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- molybdenum trioxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Definitions
- the invention relates to a method of preparation of inorganic salts comprising monovalent cation and anion of transition metal acids such as vanadates and molybdates of general structure A x M y O z , where A: NH 4 + or K + or Rb + or Cs + ; M: V or Mo or O: oxygen, wherein the salts are in particular in the form of micro- and nanocrystals.
- the invention relates to the method of manufacturing of compounds such ammonium molybdates or potassium molybdates or rubidium molybdates or cesium molybdates and ammonium vanadates or potassium or rubidium vanadates or cesium vanadates.
- Vanadates are vanadic(V) acids salts.
- alkali metal and ammonium metavanadates are industrially used.
- Potassium metavanadate, KVO3 is used as a catalyst, coiTOsion inhibitor, anti-lime agent and in chemical synthesis, among others in crude oil processing.
- RbVCb and CsVCb are studied as potential materials for optoelectronic devices, as for example LEDs.
- Ammonium metavanadate with formula of NH 4 VO 3 is an inorganic compound well soluble in hot water and diluted ammonium hydroxide. It is a white or yellowish solid. Ammonium metavanadate plays an important role in vanadium oxides manufacturing (as V 2 O 5 ) and some other chemical, e.g. luminescent materials.
- NH 4 VO 3 calcined in 500-550°C gives V 2 0 5 of the highest purity. It is also used in dye industry, in varnishes and indelible inks production, or as a moisture absorber for paints and inks.
- Molybdates the molybdic(VI) acid salts, with formula M 2 Mo0 4 (where M - NH 4 + or alkali metals) are used in the pigments production and as fertilizer, being a source of molybdenum - one of the essential micronutrients.
- Ammonium molybdate is used in catalysts manufacturing, in analytical chemistry, and in phosphomolybdic acid production, which is used in the production of catalysts, as thin layer chromatography reagent and staining agent in histopathological tests. Molybdates are also used in the ceramics.
- Ammonium metavanadate is normally prepared in an elaborate chemical process, which generates high cost.
- G. Brauer Ammonium Metavanadate
- Ammonium Metavanadate in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1.
- p. 1272 the method of NH4VO3 preparation was disclosed, where treating NaV0 3 aqueous solution with ammonium chloride caused ammonium metavanadate precipitation.
- NaV03 is obtained in a complicated, multi-step process. Firstly, V2O5 and Na 2 C03 solution is boiled until complete release of C0 2 occurs, followed by addition of KMn0 4 .
- US3063795 discloses a method of production of pure ammonium metavanadate directly from acidic solvent extraction strip solutions in a single precipitation step.
- vanadyl solution is formed containing impurities such as alumina oxide, phosphates, arsenates with addition of sodium chlorate at least sufficient to oxidize the vanadium.
- the solution of sodium carbonate and ammonia is added.
- the solution is stirred at 80-85°C for impurities precipitation which is then filtered off.
- sufficient ammonium chloride is added to precipitate the ammonium metavanadate.
- the described method requires the use of elevated temperature and an oxidant harmful to the health and the environment.
- US365381 discloses a method of preparation of pure ammonium metavanadate from contaminated NH4VO3 solution.
- contaminated NH4VO3 solution of pH 9 is kept at 90-95°C.
- the precipitation of pure ammonium metavanadate is accomplished by cooling down the mixture to 16°C.
- the disadvantage of the method is the need of energy consuming heating and cooling down the reaction mixture.
- ammonium metavanadate production described in CN 104973626 consists of mixing polyvinyl alcohol and soluble ammonium inorganic salts (as ammonium chloride, ammonium nitrate(V), ammonium carbonate) with sodium vanadate solution. Solids are separated at 40-60°C. The usage of expensive polyvinyl alcohol significantly increases costs of the production.
- CN 103420416 the method of ammonium metvanadate is disclosed.
- ammonium metavanadate is precipitated from vanadium(V) solution by inorganic ammonium salt as ammonium sulphate(VI), ammonium chloride, ammonium nitrate(V), or the mixture of thereof. Described process is carried out at 60-90°C. The key disadvantage is requirement of heating the reaction mixture.
- ammonium metavanadate precipitation using inorganic ammonium salts.
- C 104058456 ammonium oxalate is used in NH 4 VO 3 synthesis.
- Vanadium(V) solution of pH>7, kept at the temperature between 25-80°C is treated with ammonium oxalate.
- ammonium metavanadate precipitation the usage of low-molecular mass alcohol, e.g. methanol, ethanol, propanol, butanol is required.
- the key disadvantage of the approach is requirement of heating, and pH controlling, and usage of alcohols for ammonium metavanadate precipitation.
- Boiling of V2O5 with concentrated KOH solution is a known method of KVO3 preparation, described by McGraw-Hill in Inorganic synthesis, 1974. As a result, number of hydrates is formed (2KV0 3 -3H 2 0; KV0 3 .2H 2 0; 2KV0 3 .5H 2 0; KV0 3 -3H 2 0), which release water while heated, giving anhydrous KV0 3 .
- KV0 3 can be obtained by heating of K 2 C0 3 and V 2 05 solution for 2-3 h at 90°C.
- the key disadvantage of this approach is requirement of multiplicity of purification steps and intense foaming during heating. Alternate approach of method is disclosed in publication Trypuc, Ind. Eng.
- the method of KV0 3 production also is disclosed in CN105236483. According to the method, aqueous solution of potassium carbonate, potassium bicarbonate or potassium hydroxide with ammonium metavanadate is heated in the microwave reactor for 15-30 min at temperature of 50-70°C.
- the advantage of this method is a short time and moderate temperature, however it requires specialized equipment and therefore, the possibility of the large scale production is limited.
- Molybdic acid salts are obtained in similar reactions as described above. Materials and Technology, Longmans, Green and Co Ltd. J.H. de Bussy, 1968, Amsterdam oraz Comprehensive Inorganic Chemistry, Pergamon Press 1975, UK, Oxford. R.J.H. Clark (vanadium); C.L. Rollinson (Molibdenium) discloses the method of molybdates preparation.
- the compounds of general formula M2M0O4 or M 2 Mo0 4 xH 2 0, where M - alkali metals, can be obtained in the sintering process of Mo0 3 with adequate carbonate or oxide of alkali metals.
- the key disadvantage is requirements of high temperature required for melting of solid compounds.
- the invention provides an improved process for preparing compounds of general formula A x M y O z , where A: NH 4 + , K + , Rb + , Cs + ; M: V or Mo and O: oxygen, preferably compounds in the form of micro- and nanocrystals.
- the method according to the invention involves mixing of respective oxide M0O3 or V O with aqueous or non-aqueous solution of organic salt of ammonium, potassium, rubidium or cesium, preferably ammonium, potassium, rubidium or cesium formate or acetate.
- the present invention provides a method for preparing molybdates of general formula A x M y O z , where A: NH 4+ or K + or Rb + or Cs + ; M: Mo and O: oxygen.
- A NH 4+ or K + or Rb + or Cs + ; M: Mo and O: oxygen.
- potassium or rubidium or cesium or ammonium salt at least one organic potassium or rubidium or cesium or ammonium salt is used, which is dissolved in at least one solvent.
- the resulting solution is mixed with molybdenum trioxide, keeping the weight ratio of the potassium or rubidium or cesium or ammonium salt or the mixture of thereof to molybdenum trioxide at least 1: 1.
- an excess of organic salt is used.
- the present invention provides a method for preparing vanadates of general formula A x M y O z , where A: NH 4+ or K + or Rb + or Cs + ; M: V and O: oxygen.
- A NH 4+ or K + or Rb + or Cs + ; M: V and O: oxygen.
- potassium or rubidium or cesium or ammonium salt at least one organic potassium or rubidium or cesium or ammonium salt is used, which is dissolved in at least one solvent.
- the resulting solution is mixed with vanadium pentoxide, keeping the weight ratio of the potassium or rubidium or cesium or ammonium salt or the mixture of thereof to vanadium pentoxide at least 1 : 1. Then the resulting solution is left to precipitate vanadate.
- an excess of organic salt is used.
- water and/or organic solvent is used.
- the ratio of potassium, rubidium, cesium or ammonium salt to vanadium pentoxide or molybdenum trioxide is 1 : 1 to 200: 1 (w/w).
- the nanocrystal form of vanadium pentoxide or molybdenum trioxide is advantageously used.
- ammonium, potassium, rubidium or cesium formate or acetate is advantageously used.
- precipitation occurs at room temperature up to the boiling points of the solvents or the mixture of thereof.
- an excess of organic salt to vanadate pentoxide or molybdenum trioxide is used, whereas to the supernatant obtained after precipitation of vanadates or molybdates, containing the organic salt of ammonium, rubidium, potassium or cesium, vanadium pentoxide or molybdenum trioxide is added, keeping the ratio of salt to vanadium pentoxide or molybdenum oxide at least 1 :1.
- the advantages of the method according to the invention are: a one-step course of the manufacturing; running the method at room temperature, in contrast to known methods, which consist of melting salts and oxides carried out at temperature of several hundred Celsius degrees; no requirements of stilling during the reaction; no need of pH control; the ability to control the morphology of the obtained structures by changing reaction parameters; the possibility of using the obtained supernatant in the next synthesis.
- Cesium formate (0.5 g) is dissolved in 20 mL of water and 200 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. Ultrasonication speeds up the process. The reaction is earned out at room temperature, up to the boiling point of the solvent. Yellowish precipitate of CsV 3 0 8 is formed. Diffractogram presented in fig. 1 confirms its crystal structure.
- vanadium pentoxide e.g. Alfa Aesar
- Cesium formate (0.5 g) is dissolved in 20 mL of formamide and 200 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of salt to oxide as 10:4.
- the solution is mixed at room temperature for several minutes. Ultrasonication speeds up the process.
- the reaction is carried out at room temperature, up to the boiling point of the solvent. Yellowish precipitate of CS 2 V 4 O 11 is formed.
- Diffractogram presented in fig. 2 confirms its crystal structure.
- Cesium formate (1 g) is dissolved in 20 mL of formamide and 100 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the cesium formate to vanadium pentoxide ratio as 10:1.
- the solution is stirred at room temperature for several minutes and left for 24 h.
- Yellowish precipitate of CS 2 V 4 O 11 is collected by known methods.
- Fig. 4 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 6, CS 2 V 4 O 11 microcfystals not bigger than 3 pm can be prepared.
- Cesium formate (2.7 g) is dissolved in 20 mL of form amide and 1 g of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the cesium formate to vanadium pentoxide ratio as 27: 10. The solution is stirred at room temperature for several minutes. Ultrasonication speeds up the process. Yellowish precipitate of CS 2 V 4 O 11 is collected by known methods. Fig. 5 presents ciystal structure of obtained material.
- vanadium pentoxide e.g. Alfa Aesar
- Example 9 To 50 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure descibed in Example 6 is added, keeping the weight ratio of cesium formate to vanadium pentoxide as at least 1 :1. The solution is left to precipitate solid CS 2 V 4 O 11 . The collected product is dried overnight at vacuum dryer at RT.
- Example 9 To 50 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure descibed in Example 6 is added, keeping the weight ratio of cesium formate to vanadium pentoxide as at least 1 :1. The solution is left to precipitate solid CS 2 V 4 O 11 . The collected product is dried overnight at vacuum dryer at RT.
- Example 9 To 50 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure descibed in Example 6 is added, keeping the weight ratio of cesium formate to vanadium pentoxide as at least 1 :1. The
- Nanostmctural V2O5 is obtained in sol-gel method by mixing 1.5 mL of vanadium(V) oxytripropoxide and 10 mL of anhydrous ethanol and 0.5 pL of acetyl acetone. The obtained sol is dried at 50°C to obtain xerogel. The xerogel is calcined at 600-650°C in oxidative atmosphere, giving 1 g of nanostmctural V2O5.
- Example 11 The procedure is similar as in Example 11, with the exception that 1 g of nanostmctural V2O5 is used, which can be obtained by known procedure.
- Example 18 The procedure is similar as in Example 16, with the exception that cesium formate to molybdenum trioxide ratio is 1 : 1 (w/w).
- Example 18
- rubidium formate 2 g is dissolved in 20 mL of formamide and 500 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the rubidium formate to vanadium pentoxide ratio as 4: 1.
- vanadium pentoxide e.g. Alfa Aesar
- the solution is mixed at room temperature for several minutes, and solid RbV0 3 is collected by known methods.
- Diffractogram presented at fig. 8 confirms the crystal structure of the obtained material.
- nanostmctural V2O5 is used, which can be obtained by known procedure.
- Example 23 The procedure is similar as in Example 23, with the exception that 500 mg of nano structural V O is used, which can be obtained by known procedure, keeping the mass ratio of rubidium fomiate to vanadium pentoxide as 4: 1.
- SEM image presented in fig. 11 confirms, that by method described in Example 25, nanosheets of RbV 3 0 8 are obtained.
- rubidium formate 0.5 g is dissolved in 50 mL of 2-propanol and 0.5 g of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of rubidium formate to molybdenum trioxide as 1 : 1 Solution is stirred for several minutes at RT. The reaction is carried out at room temperature, up to the boiling point of the solvent. The yellowish solid Rb 2 Mo 3 Oio is obtained, which is dried overnight at RT in a vacuum dryer.
- molybdenum trioxide e.g. Alfa Aesar
- Example 32 The procedure is similar as in Example 30, with the exception that rubidium formate to molybdenum trioxde ratio is 1 : 1 (w/w).
- Example 32
- Example 36 The procedure is similar as in Example 33, with the exception that potassium acetate to vanadium pentoxide ratio is 1 : 1 (w/w).
- Example 36 The procedure is similar as in Example 33, with the exception that potassium acetate to vanadium pentoxide ratio is 1 : 1 (w/w).
- nanostmctural V O is used, which can be obtained by known procedure, keeping the weight ratio of potassium acetate to vanadium pentoxide as 15:1.
- mixture of organic salt of ammonium or potassium or cesium or rubidium can be used in a preparation method of other inorganic salts, disclosed in the invention.
- Example 59
- Nanostructural V 2 O 5 is obtained in sol-gel method by mixing 1.5 mL of vanadium(V) oxytripropoxide and 10 mL of anhydrous ethanol and 0.5 pL of acetyl acetone. The obtained sol is dried at 50°C to obtain xerogel. The xerogel is calcined at 600-650°C in oxidizing atmosphere, giving 1 g of nanostructural V2O5.
- Fig. 18 presents FTIR spectrum of ammonium metavanadate obtained by procedure described in Example 62. The presented spectmm is identical with the reference spectrum in NIST database.
- Fig. 19 shows SEM image of obtained material. Presented image reveals, that by method disclosed in Example 62, urchin-like nanostructural NH 4 VO 3 can be prepared.
- Example 62 The procedure is similar as in Example 62, with the exception that nanostructural vanadium pentoxide is used.
- Fig. 20 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 64, NH 4 VO 3 nanocrystals of average dimension 100-300 nm are obtained.
- ammonium formate 50 mg is dissolved in 50 mL of N-methylpirrolidone and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of ammonium formate to vanadium pentoxide as 1: 1.
- vanadium pentoxide e.g. Alfa Aesar
- the solution is mixed at room temperature for complete dissolution of vanadium pentoxide.
- the reaction is carried out at room temperature.
- the white solid is collected and dried overnight at RT in vacuum dryer.
- Example 67 The procedure is similar as in Example 65, with the exception that ammonium formate to vanadium pentoxide ratio is 2: 1 (w/w).
- Example 67
- Fig. 21 presents confocal microscope image of obtained material. Presented image reveals, that by method disclosed in Example 67, the flower-like NH 4 VO 3 microcrystals can be prepared.
- Example 67 To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 67 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 :1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT.
- ammonium acetate 2.5 g is dissolved in 50 mL of formamide and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the ammonium acetate to vanadium pentoxide ratio as 50: 1.
- vanadium pentoxide e.g. Alfa Aesar
- the solution is stirred at room temperature for several minutes and left to precipitate solid ammonium metavanadate.
- the precipitated solid is collected and dried overnight at RT.
- Example 71 To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 69 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT.
- Example 71 To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 69 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT.
- Example 71 To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 69 is added, keeping the weight ratio of ammonium acetate to van
- Fig. 22 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 72, elongated microcrystals of NH4VO3 can be prepared.
- 1.6 g of ammonium acetate and 1.6 g of ammonium formate is dissolved in 25 mL of water, then 300 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of ammonium acetate and ammonium formate to vanadium pentoxide as 10: 1.
- the solution is stirred, and left overnight to precipitate NH 4 VO 3 .
- the collected solid is dried at RT.
- Fig. 24 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 74, desert rose-like microcrystals of NH 4 VO 3 can be prepared.
- Fig. 25 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 75, NH 4 VO 3 microcrystals of polygon prism shape can be prepared.
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Abstract
Invention relates to a method for manufactming of inorganic salt of general formula AxMyOz, where A: NH4
+ or K+ or Rb+ or Cs+; M: Mo or V, O: oxygen, comprising precipitation of solids from molybdenum trioxide or vanadium pentoxide solution by potassium or rabidium or cesium or ammonium salt. According to the invention, the used salt is at least one organic salt of potassium or rabidium or cesium or ammonium. The salt is being dissolved in at least one solvent and the obtained solution is being mixed with molybdenum trioxide or vanadium pentoxide, keeping the weight ratio of potassium or rubidium or cesium or ammonium salt to molybdenum trioxide or vanadium pentoxide as at least 1:1.
Description
Method for manufacturing of inorganic salts with monovalent cation and anion of transition metal acid, in particular in the form of micro- and nanocrystals
The invention relates to a method of preparation of inorganic salts comprising monovalent cation and anion of transition metal acids such as vanadates and molybdates of general structure AxMyOz, where A: NH4 + or K+ or Rb+ or Cs+; M: V or Mo or O: oxygen, wherein the salts are in particular in the form of micro- and nanocrystals.
The invention relates to the method of manufacturing of compounds such ammonium molybdates or potassium molybdates or rubidium molybdates or cesium molybdates and ammonium vanadates or potassium or rubidium vanadates or cesium vanadates.
Vanadates are vanadic(V) acids salts. In particular, alkali metal and ammonium metavanadates are industrially used. Potassium metavanadate, KVO3 is used as a catalyst, coiTOsion inhibitor, anti-lime agent and in chemical synthesis, among others in crude oil processing.
RbVCb and CsVCb are studied as potential materials for optoelectronic devices, as for example LEDs. Ammonium metavanadate with formula of NH4VO3, is an inorganic compound well soluble in hot water and diluted ammonium hydroxide. It is a white or yellowish solid. Ammonium metavanadate plays an important role in vanadium oxides manufacturing (as V2O5) and some other chemical, e.g. luminescent materials. NH4VO3 calcined in 500-550°C gives V205 of the highest purity. It is also used in dye industry, in varnishes and indelible inks production, or as a moisture absorber for paints and inks. Recently, compounds as NH4V3O8 (anhydrous and hydrates), (NH4)2V308 and NH4V4O10 have gained much attention as they reveal desired properties for lithium-ion and sodium- ion batteries. In the production process of the compounds mentioned above, ammonium metavanadate is used as a precursor. The purity and size of the particles of NH4VO3 determine the properties of obtained materials.
Molybdates, the molybdic(VI) acid salts, with formula M2Mo04 (where M - NH4 + or alkali metals) are used in the pigments production and as fertilizer, being a source of molybdenum - one of the essential micronutrients. Ammonium molybdate is used in catalysts manufacturing, in analytical chemistry, and in phosphomolybdic acid production,
which is used in the production of catalysts, as thin layer chromatography reagent and staining agent in histopathological tests. Molybdates are also used in the ceramics.
Therefore, methods of vanadates and molybdates production, in particular in the form of controllable size and shape of particles, are of great importance for the industrial usage and for the development of chemistry of such compounds.
Ammonium metavanadate is normally prepared in an elaborate chemical process, which generates high cost. In publication by G. Brauer "Ammonium Metavanadate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1272 the method of NH4VO3 preparation was disclosed, where treating NaV03 aqueous solution with ammonium chloride caused ammonium metavanadate precipitation. However, NaV03 is obtained in a complicated, multi-step process. Firstly, V2O5 and Na2C03 solution is boiled until complete release of C02 occurs, followed by addition of KMn04. The formed, insoluble by-products (V205 and Mn02) are removed by suction filtration and H202 is added into the clear supernatant. Such mixture is heated up to 60°C and then it is poured into the boiling aqueous NH4CI. The solution is left for several hours for NH4VO3 precipitation. The white or nearly white solid is filtered and washed to obtain NH4VO3 contaminated with V205 and sodium and potassium cations. In order to obtain high purity material, the procedure described above is repeated several times. The yield of one sequence is 80%. The reaction between KM11O4 and H202 is vigorous and requires special security practices, which is a key disadvantage of the process.
US3063795 discloses a method of production of pure ammonium metavanadate directly from acidic solvent extraction strip solutions in a single precipitation step. In the method, vanadyl solution is formed containing impurities such as alumina oxide, phosphates, arsenates with addition of sodium chlorate at least sufficient to oxidize the vanadium. Then, the solution of sodium carbonate and ammonia is added. The solution is stirred at 80-85°C for impurities precipitation which is then filtered off. In the next step, sufficient ammonium chloride is added to precipitate the ammonium metavanadate. The
described method requires the use of elevated temperature and an oxidant harmful to the health and the environment.
US365381 discloses a method of preparation of pure ammonium metavanadate from contaminated NH4VO3 solution.. In the method contaminated NH4VO3 solution of pH 9 is kept at 90-95°C. The precipitation of pure ammonium metavanadate is accomplished by cooling down the mixture to 16°C. The disadvantage of the method is the need of energy consuming heating and cooling down the reaction mixture.
The method of ammonium metavanadate production described in CN 104973626 consists of mixing polyvinyl alcohol and soluble ammonium inorganic salts (as ammonium chloride, ammonium nitrate(V), ammonium carbonate) with sodium vanadate solution. Solids are separated at 40-60°C. The usage of expensive polyvinyl alcohol significantly increases costs of the production.
In CN 103420416 the method of ammonium metvanadate is disclosed. In method, ammonium metavanadate is precipitated from vanadium(V) solution by inorganic ammonium salt as ammonium sulphate(VI), ammonium chloride, ammonium nitrate(V), or the mixture of thereof. Described process is carried out at 60-90°C. The key disadvantage is requirement of heating the reaction mixture.
Many protocols for ammonium metavanadate precipitation using inorganic ammonium salts are known. In C 104058456 ammonium oxalate is used in NH4VO3 synthesis. Vanadium(V) solution of pH>7, kept at the temperature between 25-80°C is treated with ammonium oxalate. For ammonium metavanadate precipitation the usage of low-molecular mass alcohol, e.g. methanol, ethanol, propanol, butanol is required. The key disadvantage of the approach is requirement of heating, and pH controlling, and usage of alcohols for ammonium metavanadate precipitation.
Boiling of V2O5 with concentrated KOH solution is a known method of KVO3 preparation, described by McGraw-Hill in Inorganic synthesis, 1974. As a result, number of hydrates is formed (2KV03-3H20; KV03.2H20; 2KV03.5H20; KV03-3H20), which release water while heated, giving anhydrous KV03. Similarly, KV03 can be obtained by heating of K2C03 and V205 solution for 2-3 h at 90°C. The key disadvantage of this approach is requirement of multiplicity of purification steps and intense foaming during heating.
Alternate approach of method is disclosed in publication Trypuc, Ind. Eng. Chem. Res. 2001, 40, 1022-1025. It describes preparation of KV03 in the reaction of solid KC1 and V2O5 in the presence of steam or oxygen. HC1 and Cl2 are formed as by-products, when steam or oxygen is used, respectively, which is the key disadvantage of the process. RbV03 and CsV03 can be obtained by grinding of Rb2C03 or Cs2C03 with V205, followed by calcination at 400-600°C for 12-24 h. High crystallinity of the material is obtained by re-grinding and further calcining for 24 h. [Muller, Journal of Solid State Chemistry 156, 379-389 (2001); Jin, Res Chem Intermed.] The key disadvantage of this approach is requirement of high temperature calcining.
The method of KV03 production also is disclosed in CN105236483. According to the method, aqueous solution of potassium carbonate, potassium bicarbonate or potassium hydroxide with ammonium metavanadate is heated in the microwave reactor for 15-30 min at temperature of 50-70°C. The advantage of this method is a short time and moderate temperature, however it requires specialized equipment and therefore, the possibility of the large scale production is limited.
Molybdic acid salts are obtained in similar reactions as described above. Materials and Technology, Longmans, Green and Co Ltd. J.H. de Bussy, 1968, Amsterdam oraz Comprehensive Inorganic Chemistry, Pergamon Press 1975, UK, Oxford. R.J.H. Clark (vanadium); C.L. Rollinson (Molibdenium) discloses the method of molybdates preparation. The compounds of general formula M2M0O4 or M2Mo04 xH20, where M - alkali metals, can be obtained in the sintering process of Mo03 with adequate carbonate or oxide of alkali metals. The key disadvantage is requirements of high temperature required for melting of solid compounds. In the second approach, Mo03 is reacted with lye MOH, where M - alkali metals. The disadvantage is the usage of caustic alkali metal hydroxides. Sintering of CsCl and Ag2Mo04 is also known as a method of Cs2Mo04 manufacturing.
In publication H. Shigematsu Ferroelectrics 414 (2011) 195-200 the method of Rb2Mo04 preparation is disclosed. Powdered Rb2C03 and Mo03 are heated in air at 627°C for 24 h. In the second approach disclosed in this paper, the solution of Rb2C03 and Mo03 in the concentrated ammonia is heated to solvent evaporation, followed by calcination for 4 h at 227°C. In both protocols, the key disadvantage is the need of calcining.
New methods of vanadates and molybdates manufacturing are required that enable to eliminate disadvantages of known methodology, in particular method enables micro- or nanostructure in expected foi and structure to be obtained.
The invention provides an improved process for preparing compounds of general formula AxMyOz, where A: NH4 +, K+, Rb+, Cs+; M: V or Mo and O: oxygen, preferably compounds in the form of micro- and nanocrystals.
Unexpectedly, it has been shown that addition of organic salt of the monovalent cations of the product eliminates the disadvantages of known approaches. It was surprisingly found out, that addition of organic salts of ammonium, potassium, rubidium or cesium, in particular formates or acetates, precipitates the respective vanadates or molybdates in a crystal form at room temperature, without requirements of stirring. Type of the organic salt and the solvent affects the vanadate or molybdate structure.
The method according to the invention involves mixing of respective oxide M0O3 or V O with aqueous or non-aqueous solution of organic salt of ammonium, potassium, rubidium or cesium, preferably ammonium, potassium, rubidium or cesium formate or acetate.
The present invention provides a method for preparing molybdates of general formula AxMyOz, where A: NH4+ or K+ or Rb+ or Cs+; M: Mo and O: oxygen. In one embodiment, as potassium or rubidium or cesium or ammonium salt at least one organic potassium or rubidium or cesium or ammonium salt is used, which is dissolved in at least one solvent. In an embodiment, the resulting solution is mixed with molybdenum trioxide, keeping the weight ratio of the potassium or rubidium or cesium or ammonium salt or the mixture of thereof to molybdenum trioxide at least 1: 1. Then the resulting solution is left to precipitate molybdate. Preferably, an excess of organic salt is used.
The present invention provides a method for preparing vanadates of general formula AxMyOz, where A: NH4+ or K+ or Rb+ or Cs+; M: V and O: oxygen. In an embodiment, as potassium or rubidium or cesium or ammonium salt at least one organic potassium or rubidium or cesium or ammonium salt is used, which is dissolved in at least one solvent. In an embodiment, the resulting solution is mixed with vanadium pentoxide,
keeping the weight ratio of the potassium or rubidium or cesium or ammonium salt or the mixture of thereof to vanadium pentoxide at least 1 : 1. Then the resulting solution is left to precipitate vanadate. Preferably, an excess of organic salt is used.
In preferred embodiment, water and/or organic solvent is used.
In preferred embodiment, the ratio of potassium, rubidium, cesium or ammonium salt to vanadium pentoxide or molybdenum trioxide is 1 : 1 to 200: 1 (w/w).
In preferred embodiment, the nanocrystal form of vanadium pentoxide or molybdenum trioxide is advantageously used.
In preferred embodiment, ammonium, potassium, rubidium or cesium formate or acetate is advantageously used.
In preferred embodiment, precipitation occurs at room temperature up to the boiling points of the solvents or the mixture of thereof.
In preferred embodiment, an excess of organic salt to vanadate pentoxide or molybdenum trioxide is used, whereas to the supernatant obtained after precipitation of vanadates or molybdates, containing the organic salt of ammonium, rubidium, potassium or cesium, vanadium pentoxide or molybdenum trioxide is added, keeping the ratio of salt to vanadium pentoxide or molybdenum oxide at least 1 :1.
The advantages of the method according to the invention are: a one-step course of the manufacturing; running the method at room temperature, in contrast to known methods, which consist of melting salts and oxides carried out at temperature of several hundred Celsius degrees; no requirements of stilling during the reaction; no need of pH control; the ability to control the morphology of the obtained structures by changing reaction parameters; the possibility of using the obtained supernatant in the next synthesis.
The following examples further and the accompanying drawing disclose the embodiments of the invention, , in which following are disclosed: fig.1 - diffractogram of CsV308 obtained as described in Example 1, fig.2 - diffractogram of Cs2V40n obtained as described in Example 2, fig 3 - SEM image of CS2V4O11 crystals obtained as described in
Example 4, fig.4- SEM image of CS2V4O11 crystals obtained as described in Example 6, fig. 5- diffractogram of CS2V4O11 obtained as described in Example 7, fig. 6 - diffractogram of Cs2Mo3Oio H20 obtained as described in Example 13, fig. 7 - SEM image of CS2M09O28 crystals obtained as described in Example 16, fig.8 - diffractogram of RbV03 obtained as described in Example 19, fig. 9 - SEM image of RbV03 crystals obtained as described in Example 22, fig. 10 - SEM image of RbV308 crystals obtained as described in Example 23, fig. 11 - SEM image of RbV308 ciystals obtained as described in Example 25, fig. 12 - diffractogram of Rb2Mo30io-H20 obtained as described in Example 27, fig. 13- diffractogram of KV03 obtained as described in Example 33, fig. 14 - diffractogram of K2(MO3OIO)-(H20)3 obtained as described in Example 43, fig. 15 - diffractogram of (NH4)6(MO7024) (H20)4 obtained as described in Example 51, fig. 16 - diffractogram of ammonium metavanadate obtained as described in Example 59, fig. 17 - SEM image of NH4V03 microcrystals obtained as described in Example 59, fig. 18 - FTIR spectrum of NH4V03 obtained as described in Example 62, fig. 19 - SEM image of NH4V03 microcrystals obtained as described in Example 62, fig. 20 - SEM image of NH4V03 nanocrystals obtained as described in Example 64, fig. 21 - confocal microscope image of NH4V03 obtained as described in Example 67, fig. 22 - SEM image of NH4V03 microcrystals obtained as described in Example 72, fig. 23 - SEM image of NH4V03 microcrystals obtained as described in Example 73, fig. 24 - SEM image of NH4V03 nanocrystals obtained as described in Example 74, fig. 25 - SEM image of NH4V03 microcrystals obtained as described in Example 75
Example 1
Preparation of cesium vanadate
Cesium formate (0.5 g) is dissolved in 20 mL of water and 200 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. Ultrasonication speeds up the process. The reaction is earned out at room temperature, up to the boiling point of the solvent. Yellowish precipitate of CsV308 is formed. Diffractogram presented in fig. 1 confirms its crystal structure.
Example 2
Preparation of cesium vanadate
Cesium formate (0.5 g) is dissolved in 20 mL of formamide and 200 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of salt to oxide as 10:4. The solution is mixed at room temperature for several minutes. Ultrasonication speeds up the process. The reaction is carried out at room temperature, up to the boiling point of the solvent. Yellowish precipitate of CS2V4O11 is formed. Diffractogram presented in fig. 2 confirms its crystal structure.
Example 3
The procedure is similar as in Example 2, with the exception that cesium formate to vanadium pentoxide ratio is 1 : 1 (w/w).
Example 4
Preparation of cesium vanadate
Cesium formate (1 g) is dissolved in 20 mL of water and 100 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. After 24 h yellowish precipitate of CS2V4O11 is collected by known methods. Fig. 3 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 4, Cs2V40i 1 microcrystals not bigger than 50 pm can be prepared.
Example 5
The procedure is similar as in Example 4, with the exception that cesium formate to vanadium pentoxide ratio is 1 : 1 (w/w).
Example 6
Preparation of cesium vanadate
Cesium formate (1 g) is dissolved in 20 mL of formamide and 100 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the cesium formate to vanadium pentoxide ratio as 10:1. The solution is stirred at room temperature for several minutes and left for 24 h. Yellowish precipitate of CS2V4O11 is collected by known methods. Fig. 4 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 6, CS2V4O11 microcfystals not bigger than 3 pm can be prepared.
Example 7
Preparation of cesium vanadate
Cesium formate (2.7 g) is dissolved in 20 mL of form amide and 1 g of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the cesium formate to vanadium pentoxide ratio as 27: 10. The solution is stirred at room temperature for several minutes. Ultrasonication speeds up the process. Yellowish precipitate of CS2V4O11 is collected by known methods. Fig. 5 presents ciystal structure of obtained material.
Example 8
Preparation of cesium vanadate
To 50 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure descibed in Example 6 is added, keeping the weight ratio of cesium formate to vanadium pentoxide as at least 1 :1. The solution is left to precipitate solid CS2V4O11. The collected product is dried overnight at vacuum dryer at RT.
Example 9
Preparation of cesium vanadate
To 20 mL of 3% mol. solution of cesium formate 1 g of commercially available vanadium pentoxide is added, keeping the weight ratio of cesium formate to vanadium pentoxide as 60:1. The solution is stirred for several minutes. The precipitated CS2V4O11 is collected and dried.
Example 10
The procedure is similar as in Example 6, with the exception that 1 g of nanostmctural V2O5 is used, which can be obtained by known procedure. Nanostmctural V2O5 is obtained in sol-gel method by mixing 1.5 mL of vanadium(V) oxytripropoxide and 10 mL of anhydrous ethanol and 0.5 pL of acetyl acetone. The obtained sol is dried at 50°C to obtain xerogel. The xerogel is calcined at 600-650°C in oxidative atmosphere, giving 1 g of nanostmctural V2O5.
Example 11
Preparation of cesium vanadate
In 50 mL of formamide and deionized water in volume ratio as 4:1, 2.7 g of cesium formate is dissolved and 1 g of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of cesium formate to vanadium pentoxide as 27:10. The solutionis stirred for several minutes. Ultrasonication speeds up the process. Yellowish solid of CS2V4O11 is obtained, which is dried in vacuum dryer overnight at rt.
Example 12
The procedure is similar as in Example 11, with the exception that 1 g of nanostmctural V2O5 is used, which can be obtained by known procedure.
Example 13
Preparation of cesium molybdate
1 g of cesium formate is dissolved in 20 mL of deionized water and 100 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of cesium formate to molybdenum trioxide as 10: 1. Solution is stirred for several
minutes at RT. Ultrasonication speeds up the reaction. The yellowish solid CS2MO3OIO-H20 is obtained. Diffractogram presented in fig. 6 confirms its ciystal structure.
Example 14
The procedure is similar as in Example 13, with the exception that cesium formate to molybdenum trioxide ratio is 1 : 1 (w/w).
Example 15
Preparation of cesium molybdate
To 50 mg of commercially available molybdenum trioxide 20 mL of supernatant obtained in the procedure descibed in Example 13 is added, keeping the weight ratio of cesium formate to molybdenum trioxide at least 1 :1. The solution is left to precipitate solid CS2M03O10 H2O. The collected product is dried overnight at vacuum dryer at RT.
Example 16
Preparation of cesium molybdate
1.16 g of cesium formate is dissolved in 50 mL of 2-propanol and 100 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of cesium formate to molybdenum trioxide as 1 16:10. Solution is stirred for several minutes at RT. Ultrasonication speeds up the reaction. The reaction is carried out at room temperature, up to the boiling point of the solvent. The yellowish solid CS2M09O28 is obtained. SEM image presented in fig. 7 confirms, that by method described in Example 16 elongated CS2M09O28 microcrystals are obtained.
Example 17
The procedure is similar as in Example 16, with the exception that cesium formate to molybdenum trioxide ratio is 1 : 1 (w/w).
Example 18
Preparation of cesium molybdate
0.5 g of cesium formate is dissolved in 20 mL of 1 -propanol and 100 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of cesium formate to molybdenum trioxide as 10:4. Solution is stirred for several minutes at RT. Ultrasonication speeds up the reaction. The reaction is carried out at room temperature, up to the boiling point of the solvent. The yellowish solid CS2M09O28 is obtained, which is dried overnight in the vacuum diyer at RT.
Example 19
Preparation of rubidium vanadate
2 g of rubidium formate is dissolved in 20 mL of formamide and 500 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the rubidium formate to vanadium pentoxide ratio as 4: 1. The solution is mixed at room temperature for several minutes, and solid RbV03 is collected by known methods. Diffractogram presented at fig. 8 confirms the crystal structure of the obtained material.
Example 20
The procedure is similar as in Example 19, with the exception that rubidium formate to vanadium pentoxide ratio is 1: 1 (w/w).
Example 21
The procedure is similar as in Example 19, with the exception that 500 mg of
nanostmctural V2O5 is used, which can be obtained by known procedure.
Example 22
Preparation o rubidium vanadate
To 200 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure described in Example 19 is added, keeping the weight ratio of rubidium formate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid RbV03. The collected product is dried overnight at vacuum dryer at RT. The SEM image,
presented in fig. 9 conforms, that by method described in Example 22, RbV0 nanoplateles are obtained.
Example 23
Preparation o rubidium vanadate
To 20 mL of 1.5% mol. aqueous solution of rubidium formate 500 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of rubidium formate to vanadium pentoxide as 4:1. The solution is stirred for several minutes. The precipitated RbV 0 is collected and dried. Diffractogram presented in fig. 10 confirms the ciystal structure of obtained material.
Example 24
The procedure is similar as in Example 23, with the exception that rubidium formate to vanadium pentoxide ratio is (w/w).
Example 25
The procedure is similar as in Example 23, with the exception that 500 mg of nano structural V O is used, which can be obtained by known procedure, keeping the mass ratio of rubidium fomiate to vanadium pentoxide as 4: 1. SEM image presented in fig. 11 confirms, that by method described in Example 25, nanosheets of RbV308 are obtained.
Example 26
Prepartion of rubidium vanadate
In 50 mL of formamide and deionized water in volume ratio as 3:2, 3 g of rubidium formate is dissolved and 1 g of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of rubidium formate to vanadium pentoxide as 3:1. The solution is stirred for several minutes at RT. The solid RbV3Og is obtained, which is dried in vacuum dryer overnight at rt.
Example 27
Preparation of rubidium molybdate
To 20 mL of 1.5% mol. aqueous solution of rubidium formate 500 mg of commercially available molybdenum trioxide is added, keeping the weight ratio of rubidium fonnate to molybdenum trioxide as 4: 1. The solution is stiixed for several minutes. The precipitated Rb2Mo3Oi0-H2O is collected and dried. Diffractogram presented in fig. 12 confirms the crystal structure of the obtained material.
Example 28
The procedure is similar as in Example 27, with the exception that rubidium formate to molybdenum trioxde ratio is 1 :1 (w/w).
Example 29
Preparation of rubidium molybdate
To 100 mg of commercially available molybdenum tioxide 20 mL of supernatant obtained in the procedure described in Example 27 is added, keeping the weight ratio of rubidium formate to molybdenum trioxide at least 1 : 1. The solution is left at RT to precipitate solid RbiMoaOio fEO. The collected product is dried overnight at vacuum dryer at RT.
Example 30
Preparation of rubidium molybdate
0.5 g of rubidium formate is dissolved in 50 mL of 2-propanol and 0.5 g of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of rubidium formate to molybdenum trioxide as 1 : 1 Solution is stirred for several minutes at RT. The reaction is carried out at room temperature, up to the boiling point of the solvent. The yellowish solid Rb2Mo3Oio is obtained, which is dried overnight at RT in a vacuum dryer.
Example 31
The procedure is similar as in Example 30, with the exception that rubidium formate to molybdenum trioxde ratio is 1 : 1 (w/w).
Example 32
Preparation of rubidium molybdate
1 g of rubidium formate is dissolved in 20 mL of 1 -propanol and 200 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of cesium formate to molybdenum trioxide as 10:2. Solution is stirred for several minutes at RT. The reaction is carried out at room temperature, up to the boiling point of the solvent. The yellowish solid Rb2Mo3Oi0 is obtained, which is dried overnight in the vacuum dryer at RT.
Example 33
Preparation of potassium vanadate
To 20 mL of 3% mol. aqueous solution of potassium acetate 200 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of potassium acetate to vanadium pentoxide as 15:1. The solution is stirred for several minutes. The reaction is earned out at room temperature, up to the boiling point of the solvent. The white solid KVO3 is collected and dried overnight at RT in vacuum dryer. Diffractogram presented in fig. 13 confirms the crystal structure of obtained material.
Example 34
Preparation of potassium vanadate
To 200 mg of commercially available vanadium pentoxide 20 mL of supernatant obtained in the procedure described in Example 33 is added, keeping the weight ratio of potassium acetate to vanadium pentoxide at least 1: 1. The solution is left to precipitate solid KV03. The collected product is dried overnight at vacuum dryer at RT.
Example 35
The procedure is similar as in Example 33, with the exception that potassium acetate to vanadium pentoxide ratio is 1 : 1 (w/w).
Example 36
The procedure is similar as in Example 33, with the exception that 200 mg of
nanostmctural V O is used, which can be obtained by known procedure, keeping the weight ratio of potassium acetate to vanadium pentoxide as 15:1.
Example 37
Preparation of potassium vanadate
To 50 mL of 5% mol. aqueous solution of potassium formate 1 g of commercially available vanadium pentoxide is added, keeping the weight ratio of potassium formate to vanadium pentoxide as 12:1. The solution is stirred for several minutes. The reaction is earned out at room temperature, up to the boiling point of the solvent. The white solid KVO3 is collected and dried overnight at RT in vacuum dryer.
Example 38
The procedure is similar as in Example 37, with the exception that potassium formate to vanadium pentoxide ratio is (w/w).
Example 39
Preparation of potassium vanadate
2 g of potassium acetate and 1 g of potassium formate is dissolved in 25 mL of water, then 500 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of potassium acetate and potassium formate to vanadium pentoxide as 6: 1. The solution is stirred, and left overnight at 40-65°C to precipitate KV03. The collected solid is dried at RT.
Example 40
Preparation of potassium vanadate
3 g of potassium acetate is dissolved in 50 mL of formamide and 1 g of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the potassium acetate to vanadium pentoxide ratio as 3: 1. The solution is mixed at room temperature for several
minutes, and white solid KVO3 is collected by known methods. Ultrasonication speeds up the process.
Example 41
Preparation of potassium vanadate
To 500 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 40 is added, keeping the weight ratio of potassium acetate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid KV03. The collected product is dried overnight at vacuum dryer at RT.
Example 42
The procedure is similar as in Example 40, with the exception that potassium acetate to
Example 43
Preparation of potassium molybdate
To 50 mL of 5% mol. aqueous solution of potassium formate 1 g of commercially available molybdenum trioxide is added, keeping the weight ratio of potassium formate to molybdenum trioxide as 12: 1. The solution is stirred for several minutes at RT. The white solid K2(MO3OIO)-(H20)3 is collected and dried overnight at RT in vacuum dryer. Diffractogram presented in fig. 14 confirms the crystal structure of the material.
Example 44
The procedure is similar as in Example 43, with the exception that potassium formate to molybdenum trioxide ratio is 1 : 1 (w/w).
Example 45
Preparation of potassium molybdate
To 500 mg of commercially available molybdenum trioxide 20 mL of supernatant obtained in the procedure descibed in Example 43 is added, keeping the weight ratio of potassium
formate to molybdenum trioxide at least 1:1. The solution is left to precipitate solid K2(Mq3qio)·(H20)3 The collected product is dried overnight at vacuum dryer at RT.
Example 46
Preparation of potassium molybdate
1 g of potassium formate is dissolved in 50 mL of 2-propanol and 100 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of potassium formate to molybdenum trioxide as 10: 1. Solution is stirred for several minutes at RT. The reaction is earned out at room temperature, up to the boiling point of the solvent. The yellowish solid K2M03O10 is obtained, which is dried overnight at RT in a vacuum dryer.
Example 47
The procedure is similar as in Example 46, with the exception that potassium formate to molybdenum trioxide ratio is 1 :1 (w/w).
Example 48
Preparation of potassium molybdate
To 20 mL of 3% mol. aqueous solution of potassium acetate 500 mg of commercially available molybdenum trioxide is added, keeping the weight ratio of potassium formate to molybdenum trioxide as 16: 1. The solution is stirred for several minutes at RT. The white solid K2(Mq3qio)·(H20)3 is collected and dried overnight at RT in vacuum dryer.
Example 49
The procedure is similar as in Example 48, with the exception that potassium acetate to molybdenum trioxide ratio is 1 : 1 (w/w).
Example 50
Preparation of potassium molybdate
2 g of potassium acetate and 1 g of potassium formate is dissolved in 25 mL of water, then 200 mg of commercially available molybdenum trioxide is added, keeping the weight ratio of potassium acetate and potassium formate to molybdenum trioxide as 15: 1. The solution
is stirred, and left overnight at 40-65°C to precipitate K2(Mq3qio)·(H20)3. The collected solid is dried at RT.
Example 51
Preparation of ammonium molybdate
4 g of ammonium acetate is dissolved in 50 mL of water and 200 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of ammonium acetate to molybdenum trioxide as 20: 1. Solution is stirred for several minutes at RT. The reaction is earned out at room temperature, up to the boiling point of the solvent. The solid (NH4)6(Mq7q24)·(H20)4 is obtained, which is dried overnight at 40°C in a vacuum dryer. Diffractogram presented in fig. 15 confirms the crystal structure of the material.
Example 52
The procedure is similar as in Example 51 , with the exception that ammonium acetate to molybdenum trioxide ratio is 1 :1 (w/w).
Example 53
Preparation of ammonium molybdate
To 500 mg of commercially available molybdenum trioxide 50 mL of supernatant obtained in the procedure descibed in Example 51 is added, keeping the weight ratio of ammonium formate to molybdenum trioxide at least 1 :1. The solution is left to precipitate solid (NH4)6(MO7024)·(H20)4. The collected product is dried overnight at vacuum dryer at RT.
Example 54
Preparation of ammonium molybdate
1 g of ammonium acetate is dissolved in 50 mL of 2-propanol and 100 mg of commercially available molybdenum trioxide (e.g. Alfa Aesar) is added, keeping the mass ratio of ammonium acetate to molybdenum trioxide as 10: 1 Solution is stirred for several minutes at RT. The reaction is carried out at room temperature, up to the boiling point of the
solvent. The yellowish solid (NH4)6(Mo7024) is obtained, which is dried overnight at RT in a vacuum dryer.
Example 55
The procedure is similar as in Example 54, with the exception that ammonium acetate to molybdenum trioxide ratio is 1 :1 (w/w).
Example 56
Preparation of ammonium molybdate
To 20 mL of 3% mol. aqueous solution of ammonium formate 500 mg of commercially available molybdenum trioxide is added, keeping the weight ratio of ammonium acetate to molybdenum trioxide as 4: 1. The solution is stirred for several minutes at RT. The white solid (NH4)6(MO7024)·(H20)4 is collected and dried overnight at 40°C in vacuum dryer.
Example 57
The procedure is similar as in Example 56, with the exception that ammonium fonnate to molybdenum trioxide ratio is 1:1 (w/w).
Example 58
Preparation of ammonium molybdate
1.8 g of ammonium acetate and 1.7 g of ammonium formate is dissolved in 25 mL of water, then 500 mg of commercially available molybdenum trioxide is added, keeping the weight ratio of ammonium acetate and ammonium formate to molybdenum trioxide as 7:1. The solution is stirred, and left overnight at 40-65°C to precipitate (NH4)6(Mo7024) •(H20)4. The collected solid is dried at RT.
In analogous way as described in the examples, mixture of organic salt of ammonium or potassium or cesium or rubidium can be used in a preparation method of other inorganic salts, disclosed in the invention.
Example 59
Preparation of ammonium metavanadate
3.9 g of ammonium formate is dissolved in 50 mL of water and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of ammonium formate to vanadium pentoxide as 78:1. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. The reaction is earned out at room temperature, up to the boiling point of the solvent. In the next step, the volume of the solution is reduced by evaporation of the solvent and the ammonium metavanadate crystals precipitates. Diffractogram presented in fig. 16 confirms the crystal structure of ammonium metavanadte. Fig. 17 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 59 NH4VO3 microcrystals not bigger than 50 pm can be prepared.
Example 60
The procedure is similar as in Example 59, with the exception that 50 mg of nanostructural vanadium pentoxide, obtained by known method is used. Nanostructural V2O5 is obtained in sol-gel method by mixing 1.5 mL of vanadium(V) oxytripropoxide and 10 mL of anhydrous ethanol and 0.5 pL of acetyl acetone. The obtained sol is dried at 50°C to obtain xerogel. The xerogel is calcined at 600-650°C in oxidizing atmosphere, giving 1 g of nanostructural V2O5.
Example 61
The procedure is similar as in Example 59, with the exception that ammonium formate to vanadium pentoxide ratio is 1: 1 (w/w).
Example 62
Preparation of ammonium metavanadate
4 g of ammonium formate is dissolved in 50 mL of formamide and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of ammonium formate to vanadium pentoxide as 80: 1. The solution is stirred at room temperature for complete dissolution of vanadium pentoxide. The reaction is carried out at
room temperature. The white solid is collected and dried overnight at RT in vacuum dryer. Fig. 18 presents FTIR spectrum of ammonium metavanadate obtained by procedure described in Example 62. The presented spectmm is identical with the reference spectrum in NIST database. Fig. 19 shows SEM image of obtained material. Presented image reveals, that by method disclosed in Example 62, urchin-like nanostructural NH4VO3 can be prepared.
Example 63
The procedure is similar as in Example 62, with the exception that ammonium formate to vanadium pentoxide ratio is 1: 1 (w/w).
Example 64
The procedure is similar as in Example 62, with the exception that nanostructural vanadium pentoxide is used. Fig. 20 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 64, NH4VO3 nanocrystals of average dimension 100-300 nm are obtained.
Example 65
Preparation of ammonium metavanadate
50 mg of ammonium formate is dissolved in 50 mL of N-methylpirrolidone and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of ammonium formate to vanadium pentoxide as 1: 1. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. The reaction is carried out at room temperature. The white solid is collected and dried overnight at RT in vacuum dryer.
Example 66
The procedure is similar as in Example 65, with the exception that ammonium formate to vanadium pentoxide ratio is 2: 1 (w/w).
Example 67
Preparation of ammonium metavanadate
10 g of ammonium acetate is dissolved in 50 mL of water and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the actetate to vanadium pentoxide ratio as 200: 1. The solution is mixed at room temperature for complete dissolution of vanadium pentoxide. The precipitated solid is collected and dried overnight at RT. Fig. 21 presents confocal microscope image of obtained material. Presented image reveals, that by method disclosed in Example 67, the flower-like NH4VO3 microcrystals can be prepared.
Example 68
To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 67 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 :1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT.
Example 69
Preparation of ammonium metavanadate
2.5 g of ammonium acetate is dissolved in 50 mL of formamide and 50 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the ammonium acetate to vanadium pentoxide ratio as 50: 1. The solution is stirred at room temperature for several minutes and left to precipitate solid ammonium metavanadate. The precipitated solid is collected and dried overnight at RT.
Example 70
Preparation of ammonium metavanadate
To 50 mg of commercially available vanadium pentoxide 50 mL of supernatant obtained in the procedure descibed in Example 69 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT.
Example 71
The procedure is similar as in Example 69, with the exception that ammonium acetate to vanadium pentoxide ratio is 1 : 1 (w/w).
Example 72
Preparation of ammonium metavanadate
1.4 g of ammonium acetate and 1.6 g of ammonium formate is dissolved in 25 mL of formamide, then 300 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of ammonium acetate and ammonium formate to vanadium pentoxide as 10: 1. The solution is stirred, and left overnight at 40-65°C to precipitate NFI4VO3. The collected solid is dried at RT. Fig. 22 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 72, elongated microcrystals of NH4VO3 can be prepared.
Example 73
Preparation of ammonium metavanadate
To 300 mg of nanostructural vanadium pentoxide 25 mL of supernatant obtained in the procedure described in Example 72 is added, keeping the weight ratio of ammonium acetate to vanadium pentoxide at least 1 : 1. The solution is left to precipitate solid ammonium metavanadte, which is dried in a vaccum dryer at RT. Fig. 23 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 73, urchin-like nanostructural NH4VO3 can be prepared.
Example 74
Preparation of ammonium metavanadate
1.6 g of ammonium acetate and 1.6 g of ammonium formate is dissolved in 25 mL of water, then 300 mg of commercially available vanadium pentoxide is added, keeping the weight ratio of ammonium acetate and ammonium formate to vanadium pentoxide as 10: 1. The solution is stirred, and left overnight to precipitate NH4VO3. The collected solid is dried at RT. Fig. 24 presents SEM image of obtained material. Presented image reveals,
that by method disclosed in Example 74, desert rose-like microcrystals of NH4VO3 can be prepared.
Example 75
Preparation of ammonium metavanadate
In 25 mL of formamide and deionized water in a volume ratio as 1 : 1, 3.2 g of ammonium formate is dissolved and 300 mg of commercially available vanadium pentoxide (e.g. Alfa Aesar) is added, keeping the weight ratio of ammonium formate to vanadium pentoxide as 10:1. The solution is stirred for several minutes at RT. The precipitated ammonium metavandate is dried in vacuum dryer overnight at rt. Fig. 25 presents SEM image of obtained material. Presented image reveals, that by method disclosed in Example 75, NH4VO3 microcrystals of polygon prism shape can be prepared.
Claims
1. Method for manufacturing of inorganic salt of general formula AxMyOz, where A: .NH4 + or K+ or Rb+ or Cs+; M: Mo or V, O: oxygen, comprising precipitation of solids from molybdenum trioxide or vanadium pentoxide solution by potassium or rubidium or cesium or ammonium salt, characterized in that, the salt is at least one organic salt of potassium or rubidium or cesium or ammonium, which is being dissolved in at least one solvent and the obtained solution is being mixed with molybdenum trioxide or vanadium pentoxide, keeping the weight ratio of potassium or rubidium or cesium or ammonium salt to molybdenum trioxide or vanadium pentoxide as at least 1 : 1, and then the obtained mixture is left until molybdates or vanadates is precipitated.
2. The method according to claim 1, wherein water and/or organic solvent is used.
3. The method according to claim 1, wherein weight ratio of organic salt of potassium or rubidium or cesium or ammonium to molybdenum trioxide or vanadium pentoxide is from 1 :1 to 200: 1.
4. The method according to claim 1, wherein molybdenum trioxide or vanadium pentoxide in nanocrystalline form is used.
5. The method according to claim 1 or 2 or 3 or 4, wherein potassium or rubidium or cesium or ammonium formate and/or acetate is used.
6. The method according to claim 1 or 2 or 3 or 4 or 5, wherein the precipitation is being earned out at room temperature up to the boiling point of the solvent or the mixture of thereof.
7. The according to claim 1 or 2 or 3 or 4 or 5 or 6, wherein an excess of organic salt to molybdenum trioxide or vanadium pentoxide is used, and the supernatant obtained after first precipitation of molybdates or vanadates, containing potassium or rubidium or cesium or ammonium salt is further used in the second precipitation of molybdates or vanadates by adding to the supernatant molybdenum trioxide or vanadium pentoxide, keeping the weight ratio of organic salt to molybdenum oxide or vanadium pentoxide at least 1 :1.
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PL428580A PL243490B1 (en) | 2019-01-14 | 2019-01-14 | Method for manufacturing of inorganic salts with monovalent cation and anion of transition metal acid, in particular in the form of micro- and nanocrystals |
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CN116102062A (en) * | 2021-11-11 | 2023-05-12 | 中国科学院过程工程研究所 | Method for continuously precipitating ammonium polyvanadate and method for establishing mathematical model of ammonium polyvanadate |
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