CN108313994B - Preparation method of zinc phosphomolybdate containing keggin structure - Google Patents
Preparation method of zinc phosphomolybdate containing keggin structure Download PDFInfo
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- CN108313994B CN108313994B CN201810135999.9A CN201810135999A CN108313994B CN 108313994 B CN108313994 B CN 108313994B CN 201810135999 A CN201810135999 A CN 201810135999A CN 108313994 B CN108313994 B CN 108313994B
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- phosphomolybdate
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- 239000011701 zinc Substances 0.000 title claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 235000011837 pasties Nutrition 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000004821 distillation Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003063 flame retardant Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 10
- 229910020881 PMo12O40 Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011964 heteropoly acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to the field of phosphomolybdate preparation, and relates to a preparation method of keggin structure-containing zinc phosphomolybdate, which is synthesized by adopting a liquid phase method, takes phosphomolybdic acid and zinc oxide as raw materials, takes distilled water or ethanol as a solvent, controls the pH value to be 1.0-3.0, and reacts under the water bath condition of 55-65 ℃; and (3) carrying out reduced pressure distillation to obtain a pasty substance, and drying at 70-90 ℃ for 8-10 h to obtain orange zinc phosphomolybdate. The method has the advantages of simple process, cheap reactant raw materials, low impurity ion content, high yield and contribution to reducing the production cost; the prepared zinc phosphomolybdate with the Keggin structure meets the application requirements in the aspects of catalyst synthesis, drug synthesis, electrochemical application, flame retardant compounding and the like.
Description
Technical Field
The invention belongs to the field of phosphomolybdate preparation, and relates to a preparation method of zinc phosphomolybdate containing a keggin structure.
Background
With the successful synthesis of the first heteropolyacid salt, ammonium phosphomolybdate, polyacid chemistry has gradually become an important research area in inorganic chemistry. Early it was believed that polyacids were formed by condensation of inorganic oxyacids such as sulfuric acid, phosphoric acid, tungstic acid, and the like to form condensed acids. However, isopoly acid and heteropoly acid belong to different categories, the isopoly acid and heteropoly acid are two major chemical components of polyacid, and the isopoly acid is formed by condensing the same type of oxygen-containing acid radical ions; the heteropoly acid is a poly-state oxygen-containing ion formed by condensing different types of ions containing two or more types of oxygen acid radicals. Wherein the heteropoly compound has excellent properties: has a definite structure, is soluble in polar solvent, has acidity and oxidizability, can generate 'pseudo liquid phase' behavior in reaction to form a unique reaction field and adjust molecules or atoms to have multiple functions.
Due to the special configuration of the phosphomolybdate containing the keggin structure, the phosphomolybdate has great prospect in the aspects of catalyst synthesis, drug synthesis, electrochemical application, flame retardant compounding and the like. Meanwhile, the research content and the research in the related field are paid extensive attention, and the synthesis of phosphomolybdate containing keggin structure is still a great challenge in the chemical field.
Before the work of the patent application, no report on the keggin structure zinc phosphomolybdate compound exists, and no report on the aspect exists in the patent literature or scientific papers.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of Keggin structure-containing zinc phosphomolybdate, which adopts a liquid phase method for synthesis, takes phosphomolybdic acid and zinc oxide as raw materials, and performs reaction under the conditions of certain PH and temperature, and then performs reduced pressure distillation and drying to obtain Keggin structure-containing zinc phosphomolybdate.
A preparation method of zinc phosphomolybdate containing a keggin structure is characterized in that the zinc phosphomolybdate is synthesized by a liquid phase method, and comprises the following steps:
1) taking phosphomolybdic acid and zinc oxide as raw materials, dispersing the phosphomolybdic acid and the zinc oxide in a solvent, controlling the pH value to be 1.0-3.0, and reacting in a water bath at the temperature of 55-65 ℃;
2) carrying out reduced pressure distillation to obtain a pasty substance, and drying at 70-90 ℃ for 8-10 h to obtain orange zinc phosphomolybdate;
the solvent is distilled water or ethanol.
Specifically, the pH value is 1.0.
Specifically, the water bath temperature is 60 ℃.
Specifically, the termination condition of the reaction in the production method is that the bubbles are released and the zinc oxide is completely dissolved.
Specifically, the drying condition is 8 hours at 80 ℃.
The invention has the beneficial effects that: 1) the oxide is used as a raw material, the process is simple, the price is low, the content of impurity ions is low, the yield is high, and the production cost is favorably reduced; 2) the zinc phosphomolybdate with the Keggin structure prepared by the invention meets the application requirements in the aspects of catalyst synthesis, drug synthesis, electrochemical application, flame retardant compounding and the like.
Drawings
FIG. 1 is a chart of the infra-red spectrum of zinc phosphomolybdate prepared in example 1;
FIG. 2 is an EDS energy spectrum of zinc phosphomolybdate prepared in example 1.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and all the technical solutions of the present invention should be equally replaced or modified without departing from the technical principles and the spirit of the present invention, and the protection scope of the present invention is covered.
Example 1
Weighing 0.015mol of phosphomolybdic acid crystal, putting the phosphomolybdic acid crystal into a beaker, adding sufficient distilled water, stirring the phosphomolybdic acid crystal in a glass cup, and putting the phosphomolybdic acid crystal into a water bath at the temperature of 60 ℃ for continuous stirring until the turbid solution becomes yellow clear liquid; weighing 0.0221mol of zinc oxide, adding the zinc oxide into a phosphomolybdic acid solution, starting a stirrer, reacting under the condition of a water bath at 60 ℃, dropwise adding the phosphomolybdic acid solution to control the PH to be about 1.0 along with the occurrence of a small amount of bubbles in the reaction, continuously and fully stirring until the bubbles are released and the white powder is completely dissolved, and when the solution is completely dissolvedWhen the color of the solution became yellowish green, the solution was distilled under reduced pressure to obtain an orange-red paste, and finally dried at 80 ℃ for 8 hours to prepare an orange-colored zinc phosphomolybdate powder (24.76 g) in the form of Zn3[PMo12O40]2The yield was 84.85%.
As shown by the infrared spectrogram data of FIG. 1, 783.0cm-1，868.3cm-1，961.6cm-1And 1076.6cm-1The four absorption peaks are respectively [ PMo12O40]3-Four characteristic peaks of Mo-Oc-Mo, Mo-Ob-Mo, Mo ═ Od and P-Oa in the Keggin structure of (A), 585.3cm-1Is PO4 3-And contains a small amount of hetero-peaks.
As shown by the EDS spectrogram data of FIG. 2, wherein the calculated P/Zn molar ratio is 1.71 and the calculated Mo/Zn molar ratio is 9.28, the analysis results show that the P/Zn and Mo/Zn ratios are 0.67 and 8, respectively, which are lower than the actual ratios 1.04 and 1.28.
Example 2
Weighing 0.0128mol of phosphomolybdic acid crystal, putting into a beaker, adding sufficient distilled water, stirring in a glass cup, putting into a water bath condition of 60 ℃, and continuously stirring until the turbid solution becomes yellow clear liquid; weighing 0.0192mol of zinc oxide, adding the zinc oxide into a phosphomolybdic acid solution, starting a stirrer, reacting under a water bath condition of 65 ℃, adding a small amount of bubbles along with the reaction, dropwise adding the phosphomolybdic acid solution to control the pH to be about 2.0, continuously and fully stirring until the bubbles are completely released, completely dissolving white powder, distilling the solution under reduced pressure to obtain an orange-red pasty substance when the solution is changed into yellow green, and finally drying at 80 ℃ for 8 hours to prepare 22.07g of orange zinc phosphomolybdate powder, wherein the zinc phosphomolybdate powder is prepared by Zn3[PMo12O40]2The yield was 88.49%.
Example 3
Weighing 0.01mol of phosphomolybdic acid crystal, putting the phosphomolybdic acid crystal into a beaker, adding sufficient distilled water, stirring the phosphomolybdic acid crystal in a glass cup, and putting the phosphomolybdic acid crystal into a water bath at the temperature of 60 ℃ for continuous stirring until the turbid solution becomes yellow clear liquid; weighing 0.0271mol of zinc oxide, adding the zinc oxide into a phosphomolybdic acid solution, starting a stirrer, reacting in a water bath at 55 ℃, generating a small amount of bubbles along with the reaction, dropwise adding the phosphomolybdic acid solution, and controlling the pH to be 3Around 0, stirring was continued sufficiently until the bubbles were released and the white powder was completely dissolved, and when the solution became yellow-green, the solution was distilled under reduced pressure to obtain an orange-red pasty substance, which was finally dried at 70 ℃ for 10 hours to prepare 17.51g of orange zinc phosphomolybdate powder as Zn3[PMo12O40]2The yield was 85.04%.
Example 4
Weighing 0.0095mol of phosphomolybdic acid crystal, putting into a beaker, adding sufficient distilled water, stirring in a glass cup, putting into a water bath at 60 ℃, and continuously stirring until the turbid solution becomes yellow clear liquid; weighing 0.0312mol of zinc oxide, adding into a phosphomolybdic acid solution, starting a stirrer, reacting under a water bath condition of 65 ℃, adding a small amount of bubbles along with the reaction, dropwise adding the phosphomolybdic acid solution to control the pH to be about 2.0, continuously and fully stirring until the bubbles are completely released, completely dissolving white powder, distilling the solution under reduced pressure to obtain an orange-red pasty substance when the solution is yellow-green, and finally drying at 90 ℃ for 8 hours to prepare 16.81g of orange zinc phosphomolybdate powder, wherein Zn is used as the orange zinc phosphomolybdate powder3[PMo12O40]2The yield was 84.39%.
Example 5
Weighing 0.0177mol of phosphomolybdic acid crystal, putting the phosphomolybdic acid crystal into a beaker, adding sufficient distilled water, stirring the phosphomolybdic acid crystal in a glass cup, and putting the phosphomolybdic acid crystal into a water bath condition at the temperature of 60 ℃ for continuous stirring until the turbid solution becomes yellow clear liquid; weighing 0.0181mol of zinc oxide, adding the zinc oxide into a phosphomolybdic acid solution, starting a stirrer, reacting under a water bath condition at 70 ℃, adding a small amount of bubbles along with the reaction, dropwise adding the phosphomolybdic acid solution to control the pH to be about 3.0, continuously and fully stirring until the bubbles are completely released, completely dissolving white powder, distilling the solution under reduced pressure to obtain an orange-red pasty substance when the solution is changed into yellow green, and finally drying at 90 ℃ for 10 hours to prepare 27.62g of orange zinc phosphomolybdate powder, wherein the orange zinc phosphomolybdate powder is prepared by Zn3[PMo12O40]2The yield was 81.59%.
Claims (5)
1. A preparation method of zinc phosphomolybdate containing a keggin structure is characterized in that the zinc phosphomolybdate is synthesized by a liquid phase method, and comprises the following steps:
1) taking phosphomolybdic acid and zinc oxide as raw materials, taking distilled water or ethanol as a solvent, controlling p H to react at 1.0-3.0 ℃ in a water bath at 55-65 ℃;
2) and (3) carrying out reduced pressure distillation to obtain a pasty substance, and drying at 70-90 ℃ for 8-10 h to obtain orange zinc phosphomolybdate.
2. The preparation method of keggin structure-containing zinc phosphomolybdate according to claim 1, characterized in that: the p H value was 1.0.
3. The preparation method of keggin structure-containing zinc phosphomolybdate according to claim 1, characterized in that: the water bath temperature was 60 ℃.
4. The preparation method of keggin structure-containing zinc phosphomolybdate according to claim 1, characterized in that: the termination condition of the reaction in the preparation method is that the bubbles are released and the zinc oxide is completely dissolved.
5. The preparation method of keggin structure-containing zinc phosphomolybdate according to claim 1, characterized in that: the drying condition is at 80 ℃ for 8 h.
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| CN101423476B (en) * | 2004-12-30 | 2013-03-20 | 中国科学院成都有机化学有限公司 | Method for synthesizing diphenyl carbonate by transesterification |
| CN105504350A (en) * | 2015-12-23 | 2016-04-20 | 中国科学院宁波材料技术与工程研究所 | Polyoxometalate based flame retardant synergists and application thereof |
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