CN110467641B - Anderson type polymolybdate alkoxy derivative and one-pot hydrothermal preparation method thereof - Google Patents
Anderson type polymolybdate alkoxy derivative and one-pot hydrothermal preparation method thereof Download PDFInfo
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- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005580 one pot reaction Methods 0.000 title abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical class [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004429 atom Chemical group 0.000 claims abstract description 11
- -1 trihydroxymethyl compound Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 5
- 150000001875 compounds Chemical class 0.000 claims description 39
- 239000011734 sodium Substances 0.000 claims description 9
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000002086 nanomaterial Substances 0.000 claims description 6
- 229910019501 NaVO3 Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical group [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002553 FeIII Inorganic materials 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OLQJQHSAWMFDJE-UHFFFAOYSA-N 2-(hydroxymethyl)-2-nitropropane-1,3-diol Chemical compound OCC(CO)(CO)[N+]([O-])=O OLQJQHSAWMFDJE-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a one-pot hydrothermal synthesis method of an Anderson type polymolybdate alkoxy derivative with vanadium or iron as a central heteroatom, which comprises the steps of mixing molybdate, central atom salt, a trihydroxymethyl compound and water, reacting for 24 hours in a closed reaction kettle at 160 ℃, cooling to room temperature, filtering reaction mixed liquid, and standing filtrate until crystals of the Anderson type polymolybdate alkoxy derivative compound are separated out; the central atomic salt is Fe3+、Cu2+、Mn3+Or V5+A salt. The invention expands the central element variety of Anderson type heteropoly acid; the product is directly separated out in a crystal form without complex purification; the synthetic preparation method has the advantages of simplicity, high yield, low synthetic cost, environmental friendliness and the like.
Description
Technical Field
The invention relates to an Anderson type polyacid alkoxy derivative and a preparation method thereof, belonging to the technical field of organic and inorganic hybrid materials.
Background
Polyacid, i.e., polyoxometallate, is a series of inorganic metal-oxygen clusters with compact coordination molecular structure formed by high-valence transition metal ions (such as Mo (VI), W (VI), V (V), Nb (V), Ta (V) and oxyanions, and the polyacid ions and organic molecules are subjected to covalent modification or coordination modification due to the diversity of chemistry, structure and electrons, so that the polyacid ions and the organic molecules have wide application in the fields of medicinal chemistry, magnetics, catalytic chemistry, electrochemistry and the like in the field of material chemistry. In these polyacid applications, it is important to exert the properties of the heteroatoms in the polyacid, such as the heteroatoms playing a crucial role in catalytic oxidation, degradation, photolysis, etc. The current classical polyacid structure types comprise six types, namely Keggin type, Dawson type, Waugh type, Lindqvist type, Anderson type and Silverton type, wherein the Anderson type polyacid is a polyacid with wide application, not only has stable structure, but also can introduce most of metal and nonmetal elements except rare gas in the periodic table of elements into the central heteroatom, and can regulate and control the property of the polyacid by changing the heteroatom, and in addition, the Anderson type polyacid can be combined with a trihydroxymethyl compound to introduce various organic functional groups, so that the polyacid has richer properties.
Despite the advantages of the Anderson type polyacid, the current methods of preparation have several disadvantages: (1) the synthesis method is complicated: the traditional Anderson type polyacid must synthesize a precursor or polyacid anion firstly, and has the disadvantages of multiple synthesis steps, long flow path, low yield and the like. Meanwhile, the synthesis environment is mostly organic solution, which is not in accordance with the concept of green chemistry; (2) central atom limitation: although many central atom types have been reported in the Anderson type heteropoly-acids, the valence of the heteroatom is relatively single, and is usually +2 or + 3. Furthermore, some important elements, such as vanadium, etc., cannot be introduced as heteroatoms into the Anderson-type heteropoly-acid.
Disclosure of Invention
In order to overcome the technical problems existing in the prior art, the invention provides an Anderson type poly (hydroxymethyl) molybdate derivative taking vanadium or iron as a central heteroatom and a preparation method thereof, wherein the Anderson type poly (hydroxymethyl) molybdate derivative is of a cage-shaped micro-nano structure, three bridge oxygen atoms which are arranged on a framework and are in a plane triangle shape are replaced by three hydroxyl oxygens of a trihydroxymethyl compound molecule, the central vanadium atom is positive 5-valent, and the central iron atom is positive 3-valent.
The technical scheme provided by the invention is as follows:
an Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom has the following structure: three central bridge oxygen atoms (mu) arranged in a plane triangle on the Anderson type framework2-O) is replaced by three hydroxyl oxygen of a trihydroxymethyl compound molecule, the central atom vanadium is in a positive pentavalent state, the coordinating atom molybdenum is in a positive hexavalent state, the whole polyacid anion is in a negative univalent state, and the counter cation is sodium ion or ammonium ion.
The trihydroxymethyl compound is one of trihydroxymethyl aminomethane, pentaerythritol, trimethylolethane, trimethylolpropane and trihydroxymethyl nitromethane.
The Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom specifically comprises the following structures:
Na0.7(NH4)0.3[VⅤMoⅥ 6O18{(OCH2)3CCH3}2] (1)
Na[VⅤMoⅥ 6O18{(OCH2)3CCH2OH}2] (2)
Na[VⅤMoⅥ 6O18{(OCH2)3CCH3}2] (3)
wherein:
the compound (1) belongs to a cubic crystal system, and has unit cell parameters as follows:
α＝90.00°，β＝90.00°，γ＝90.00°；
the compound (2) belongs to the triclinic system and has the following unit cell parameters:
α＝75.401(2)°，β＝67.087(2)°，γ＝88.977(2)°；
the compound (3) belongs to a cubic crystal system, and has unit cell parameters as follows:
α＝90.00°，β＝90.00°，γ＝90.00°；
the crystal structures of the compound (1) and the compound (3) are cage-shaped micro-nano structures.
An Anderson polymolybdate alkoxy derivative with iron as a central heteroatom has a molecular structure as follows:
FeⅢ[FeⅢMoⅥ 6O18{(OCH2)3CCH3}2] (4)
the compound (4) belongs to a cubic crystal system, the crystal structure of the compound is a cage-shaped micro-nano structure, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
A preparation method of Anderson type heteropoly acid alkoxy derivatives comprises the following steps: mixing molybdate, central atom salt, a trihydroxymethyl compound and water, reacting for 24 hours in a closed reaction kettle at 160 ℃, cooling to room temperature, filtering the reaction mixed solution, standing the filtrate until crystals are separated out, washing the crystals with deionized water and absolute ethyl alcohol in sequence, and naturally airing to obtain the Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom or the Anderson polymolybdate alkoxy derivative taking iron as a central heteroatom; the central atom salt is Fe-containing3+、Cu2+、Mn3+Or V5+A salt.
Said V-containing5+The salt is NaVO3The molybdate is (NH)4)6Mo7O24·H2O or Na2MoO4·2H2And O, wherein the trimethylol compound (Tris) includes Tris, pentaerythritol, trimethylolethane and trimethylolpropane, but is not limited to Tris, pentaerythritol, trimethylolethane and trimethylolpropane, and includes other Tris organic ligands such as Tris nitromethane.
The Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom or the Anderson polymolybdate alkoxy derivative taking iron as a central heteroatom is applied to the field of chemistry.
The invention has the following advantages and beneficial effects:
1. the invention solves the problem that the Anderson type polyacid taking vanadium as a central heteroatom cannot be obtained by the currently reported synthesis method, expands the central element types of the Anderson type heteropolyacid and synthesizes the cation which is not reported at present and is Na+Or NH4 +The Anderson-type trihydroxymethyl polymolybdate derivative of (a).
2. The method takes simple metal salts such as molybdate and the like as reaction starting materials, prepares the Anderson type polymolybdic acid by a hydrothermal one-pot method, and reduces the synthesis cost; only water is used as a solvent in the reaction process, so that the green chemical concept is met; after reaction conditions are optimized, the Anderson polyacid product can be obtained only by one step, and the product is directly separated out in a crystal form without complex purification, so that the defects of complex process, complex conditions and low yield of the traditional Anderson polyacid synthesis method are effectively overcome, and the efficiency is improved; (ii) a Besides the capability of synthesizing vanadium-centered heteroatom Anderson-type polymolybdic acid, the method can also synthesize most of the reported Fe3+、Cu2+、Mn3+The Anderson type polymolybdate alkoxy derivative with the same as the center has the advantages of simplified reaction steps, higher yield, cleanness, high efficiency, simple purification and the like compared with the traditional method.
Drawings
FIG. 1: the structural formulae of compound (1), compound (2), compound (3) and compound (4).
FIG. 2: crystal stacking diagrams of the compound (1), the compound (2), the compound (3) and the compound (4).
FIG. 3: crystal cage patterns of the compound (1), the compound (3) and the compound (4).
FIG. 4: structural diagram of the trimethylol compound used.
FIG. 5: the synthetic process of the invention is shown schematically.
Detailed Description
The present invention will be described more fully with reference to the following examples:
example 1 Synthesis of Compound (1)
2.47g (NH) are weighed4)6Mo7O24·H2O(2mmol)，0.36g NaVO3(3mmol), dissolving 2.4g (3mmol) of trimethylolethane in 20mL of water, pouring the solution into a 50mL hydrothermal reaction kettle inner container, reacting for 24h at 160 ℃, cooling to room temperature, filtering the reaction mixed solution, standing the filtrate for 7 days to precipitate orange crystals, washing the crystals with 20mL of deionized water and 20mL of absolute ethyl alcohol, and naturally drying to obtain the compoundNa0.7(NH4)0.3[VⅤMoⅥ 6O18{(OCH2)3CCH3}2]The compound belongs to a cubic crystal system, and the unit cell parameters of the compound are as follows:
α＝90.00°，β＝90.00°，γ＝90.00°。
example 2 Synthesis of Compound (2)
2.47g (NH) are weighed4)6Mo7O24·H2O(2mmol)，0.36g NaVO3(3mmol), 2.7g (3mmol) pentaerythritol is dissolved in 20mL water and poured into a 50mL hydrothermal reaction kettle inner container, the mixture reacts for 24 hours at 160 ℃, after the mixture is cooled to room temperature, the reaction mixture is filtered, the filtrate is kept stand for 7 days to precipitate orange crystals, the crystals are washed by 20mL deionized water and 20mL absolute ethyl alcohol and then naturally dried to obtain Na [ V ]ⅤMoⅥ 6O18{(OCH2)3CCH2OH}2]The compound belongs to a triclinic system, and the unit cell parameters of the compound are as follows:
α＝75.401(2)°，β＝67.087(2)°，γ＝88.977(2)°。
example 3 Synthesis of Compound (3)
3.38g (14mmol) Na were weighed2MoO4·2H2O，0.36g NaVO3(3mmol), dissolving 2.4g (3mmol) of trimethylolethane in 20mL of water, pouring the solution into a 50mL hydrothermal reaction kettle inner container, reacting for 24h at 160 ℃, cooling to room temperature, filtering the reaction mixed solution, standing the filtrate for 7 days to separate orange yellow crystals, washing the crystals with 20mL of deionized water and 20mL of absolute ethyl alcohol, and naturally drying to obtain Na [ V ]ⅤMoⅥ 6O18{(OCH2)3CCH3}2]The compound belongs to a cubic crystal system, and the unit cell parameters of the compound are as follows:
α＝90.00°，β＝90.00°，γ＝90.00°。
example 4 Synthesis of Compound (4)
2.47g (NH) are weighed4)6Mo7O24·H2O(2mmol)，0.48g FeCl3(3mmol), dissolving 2.4g (3mmol) of trimethylolethane in 20mL of water, pouring the solution into a 50mL hydrothermal reaction kettle inner container, reacting for 24h at 160 ℃, cooling to room temperature, filtering the reaction mixed solution, standing the filtrate for 7 days to separate out light yellow crystals, washing the crystals with 20mL of deionized water and 20mL of absolute ethyl alcohol, and naturally drying to obtain FeⅢ[FeⅢMoⅥ 6O18{(OCH2)3CCH3}2]The compound belongs to a cubic crystal system, the crystal structure of the compound is a cage-shaped micro-nano structure, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention.
Claims (2)
1. A preparation method of Anderson type heteropoly acid alkoxy derivatives is characterized in that: mixing molybdate, central atom salt, a trihydroxymethyl compound and water, reacting for 24 hours in a closed reaction kettle at 160 ℃, cooling to room temperature, filtering the reaction mixed solution, standing the filtrate until crystals are separated out, washing the crystals with deionized water and absolute ethyl alcohol in sequence, and naturally airing to obtain an Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom or an Anderson polymolybdate alkoxy derivative taking iron as a central heteroatom; the central atom salt is Fe-containing3+Or V5+A salt of (NH) said molybdate4)6Mo7O24·H2O or Na2MoO4·2H2O, wherein the trihydroxymethyl compound is pentaerythritol or trimethylolethane;
the Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom has the following structure: three central bridge oxygen atoms arranged in a plane triangle on the Anderson type framework are replaced by three hydroxyl oxygen of a trihydroxymethyl compound molecule, the central atom vanadium is positive pentavalent, the coordinated atom molybdenum is positive hexavalent, the whole polyacid anion is negative univalent, and the counter cation is sodium ion or ammonium ion;
the Anderson type polymolybdate alkoxy derivative taking vanadium as a central heteroatom specifically comprises the following structure:
Na0.7(NH4)0.3[VⅤMoⅥ 6O18{(OCH2)3CCH3}2] (1)
Na[VⅤMoⅥ 6O18{(OCH2)3CCH2OH}2] (2)
Na[VⅤMoⅥ 6O18{(OCH2)3CCH3}2] (3)
wherein:
the compound (1) belongs to a cubic crystal system, and has unit cell parameters as follows:
α＝90.00°，β＝90.00°，γ＝90.00°；
the compound (2) belongs to the triclinic system and has the following unit cell parameters:
α＝75.401(2)°，β＝67.087(2)°，γ＝88.977(2)°；
the compound (3) belongs to a cubic crystal system, and has unit cell parameters as follows:
α＝90.00°，β＝90.00°，γ＝90.00°；
the crystal structures of the compound (1) and the compound (3) are cage-shaped micro-nano structures;
the Anderson polymolybdate alkoxy derivative taking iron as a central heteroatom has a molecular structure as follows:
FeⅢ[FeⅢMoⅥ 6O18{(OCH2)3CCH3}2] (4)
the compound (4) belongs to a cubic crystal system, the crystal structure of the compound is a cage-shaped micro-nano structure, and the unit cell parameter is
α＝90°，β＝90°，γ＝90°。
2. The method of claim 1, wherein: said V-containing5+The salt is NaVO3。
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| CN106831854A (en) * | 2017-03-06 | 2017-06-13 | 湖北工业大学 | Vanadic acid alcoxyl derivative of a kind of mixed valence six and preparation method thereof |
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