CN112342620A - Dissimilar metal substituted Dawson type polyacid-based crystal material and preparation method thereof - Google Patents
Dissimilar metal substituted Dawson type polyacid-based crystal material and preparation method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title abstract description 10
- 239000002184 metal Substances 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- 239000007853 buffer solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910002251 LaCl3·6H2O Inorganic materials 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000007974 sodium acetate buffer Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 239000002178 crystalline material Substances 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims 2
- 238000011049 filling Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 229910002249 LaCl3 Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910002589 Fe-O-Fe Inorganic materials 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
A heterometallic substituted Dawson type polyacid-based crystal material and a preparation method thereof belong to the technical field of inorganic chemistry polyacid. The chemical formula of the dissimilar metal substituted Dawson type polyacid-based crystal material prepared by the invention is as follows: KH [ Fe ]2La2(H2O)12(α‑P2W16O60)]·21H2And O. The preparation method of the heterometallic substituted Dawson type polyacid-based crystal material comprises the steps of firstly preparing acetic acid and sodium acetate buffer solution, and adding FeCl3Dissolving in the buffer solution for later use; then preparing a sodium hydroxide solution with the concentration of 1M for later use; then K is put12[α‑H2P2W12O48]·24H2Adding O into a water system, and sequentially adding prepared FeCl into the water system under the condition of continuous stirring3Solution of, K2CO31M NaOH solution and LaCl3·6H2O or La (NO)3)3·6H2And O, finally, filling the mixture into a reaction kettle, heating the mixture at 90-105 ℃, filtering the product, washing the product with distilled water, and drying the product at room temperature to obtain brown yellow columnar crystals. The polyacid crystal material of the invention has simple preparation method, easy operation and good repeatability.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry polyacid, and particularly relates to a preparation method of a dissimilar metal modified Dawson type phosphotungstic acid crystal material.
Background
Polyoxometalates, abbreviated as Polyacids (POMs), are widely sought by polyacid chemists, because a large number of oxygen atoms on the surface of polyoxometalates can be easily combined with most of transition metals or rare earth metals to form a series of POMs derivatives substituted by transition or rare earth metals with potential application prospects in the fields of electricity, light, catalysis, magnetism and the like (coord. chem. rev.,2020,414,213260; Nanoscale,2020,12,5705). To date, a large number of transition metal substituted polyacid materials have been extensively studied (coord. chem.rev.,2019,392, 49; inorg. chem.2019,58,2372), and rare earth substituted polyacid derivatives have been reported continuously (acc. ch. em.res.,2017,50,9,2205; Nanoscale,2020,12,10842) because of the high coordination, oxygen affinity and multiple physical and chemical properties of rare earth ions themselves, however, when rare earth and transition metal react with POMs simultaneously, there is often reaction competition, and thus reports of polyacid derivatives substituted simultaneously with rare earth and transition metal are relatively limited (coord. chem.rev.,2020,143,213271; chem. commu., 2016,52,4418). Meanwhile, the transition-rare earth dissimilar metal polyoxometallate derivative attracts more and more people to pay attention due to the complex and various anion units, topological structures and special performances in the fields of optics, catalysis, magnetism and the like.
Since the first rare earth-transition metal structured Keggin-type polyoxotungstate was reported by muller et al in 2007 (j.cluster sci.,2007,18,711), although some transition-rare earth metal structured polyoxotungstate materials have been synthesized in succession, it is known in the literature that there are relatively many reports of transition-rare earth dissimilar metal-based substitution of K eggin-structured tungsten oxygen clusters (cryst. growth des.,2020,20,2706; RSC Ad v.,2019,9,13543; New j. chem.,2019,43,3011; cryst engcomm,2015,17, 5002), while there are very few reports on dissimilar metal-modified Dawson-type polyoxotcrystalline materials (ornig.ch em.,2019,58,12534; cryst engcomm, 16,2230; Dalton trans, 42, 16328).
Disclosure of Invention
Aiming at the defects, the invention provides the dissimilar metal substituted polyacid based crystal material and the preparation method thereof, and the obtained material has a novel structure and the preparation method is simple and easy to implement.
The chemical formula of the dissimilar metal substituted Dawson type polyacid-based crystal material prepared by the invention is as follows: KH [ Fe ]2L a2(H2O)12(α-P2W16O60)]·21H2O。
The crystal belongs to a triclinic system, P-1 space group, and the unit cell parameters are as follows:
α＝70.251(2)°,β＝69.933(2)°,γ＝85.273(2)°，
Z＝2。
the invention also provides a preparation method of the dissimilar metal substituted Dawson type polyacid-based crystal material, which comprises the following steps:
1) preparing acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH-4.8, and adding 27-30 parts by weight of FeCl3Dissolving in the above buffer solution for use.
2) Preparing a sodium hydroxide solution with the concentration of 1M for later use.
3) 39-43 parts by weight of K12[α-H2P2W12O48]·24H2Adding O into a water system, and sequentially adding prepared FeCl into the water system under the condition of continuous stirring3Solution, 6-7 parts by weight of K2CO31M NaOH solution and 10-13 parts by weight of LaCl3·6H2O or La (NO)3)3·6H2And O, continuously stirring for 60-180 minutes.
4) Putting into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and putting into an oven at 90-105 ℃ for heating for 40-60 hours.
5) Taking out, naturally cooling to room temperature, filtering the product, washing with distilled water for 3-5 times, and drying at room temperature to obtain green columnar crystals.
Further, the adding amount of the buffer solution in the step 1) is 2.7-3.0g of FeCl correspondingly added in each 10ml of the buffer solution3。
Further, step 3) of H2K with 1g of O12[α-H2P2W12O48]·24H2O15-21 mL of water was added.
Further, FeCl in step 3)3The amount of solution added was 1g of K12[α-H2P2W12O48]·24H2Adding 2.0-2.6mL of prepared FeCl into O3And (3) solution.
Further, the amount of NaOH solution added in step 3) was 1g of K12[α-H2P2W12O48]·24H2And adding 2.9-3.2mL of prepared NaOH solution into the O.
Further, [ alpha-H ]2P2W12O48]12–Is K12[α-H2P2W12O48]·24H2O precursor, rare earth and transition metal salt are respectively LaCl3·6H2O and FeCl3The pH value is adjusted by using K2CO3， NaOH,CH3COOH-CH3COONa solution.
Has the advantages that:
(1) the polyacid crystal material of the invention has simple preparation method, easy operation and good repeatability.
(2) The polyacid crystal material is the first pure inorganic Fe-La dissimilar metal modified Dawson type polyacid compound, enriches the types of polyacid-based crystal materials, and has potential application prospects in the fields of photoelectrocatalysis, magnetism and the like.
Drawings
FIG. 1 is a schematic diagram of an asymmetric unit structure of a cluster compound
FIG. 2 is a diagram showing a structure of cluster dimer
FIG. 3 is a one-dimensional chain structure diagram of a cluster compound
FIG. 4 is a two-dimensional layered structure diagram of a cluster compound
FIG. 5 is a three-dimensional network structure diagram of a cluster
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Preparing acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH-4.8, and adding FeCl3(2.986g) was dissolved in the above 10mL of buffer solution and was used.
2) Preparing a sodium hydroxide solution with the concentration of 1M for later use.
3) Will K12[α-H2P2W12O48]·24H2O (0.391g) is added into a 6mL water system, and FeCl which is prepared is added into the water system in turn under the condition of continuous stirring3Solution (1mL), K2CO3(0.065g), 1M NaOH solution (1.25mL) and LaCl3·6H2And O (0.109g), continuously stirring for 60 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in an oven at 100 ℃ for 48 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product with distilled water, and drying the product at room temperature to obtain brown yellow columnar crystals.
Comparative example 1
By selecting salt compounds of other rare earth elements Sm, Eu, Tb, Dy and Ce to replace La salt of the application and carrying out experiments according to the reaction conditions of the embodiment 1, products with the same structure as that of the embodiment 1 can be obtained.
Comparative example 2
With La (NO)3)3·6H2O instead of LaCl3·6H2O, an experiment was conducted under the reaction conditions of example 1, and a product having the same structure as in example was obtained.
Comparative example 3
Salt compounds of other transition elements Mn or Co are selected to replace Fe salt in the application, experiments are carried out according to the reaction conditions of the example 1, and products with the same structure as the example 1 are not obtained.
Comparative example 4
With Na12[α-P2W15O56]·24H2O or K10[α2-P2W17O61]·20H2O instead of K12[α-H2P2W12O48]·24H2O (0.0422g), and adjusting the reactant ratio range, a product having the same structure as in example was not obtained.
Comparative example 5
In the reaction system of example 1, carbonate and acetate ions were added without entering the final crystal structure, but if none of the four reactants were added to the reaction system, a product having the same structure as that of example 1 could not be obtained.
Comparative example 6
The reaction time was shortened to 1 day, and other reaction conditions were not changed, and a product having the same structure as in example 1 was not obtained.
Example 2
1) Preparing acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH-4.8, and adding FeCl3(2.780g) was dissolved in the above 10mL of buffer solution and was used.
2) Preparing a sodium hydroxide solution with the concentration of 1M for later use.
3) Will K12[α-H2P2W12O48]·24H2O (0.400g) is added into 8mL of water system, and prepared FeCl is added into the water system in turn under the condition of continuous stirring3Solution (1mL), K2CO3(0.070g), 1M NaOH solution (1.25mL) and La (NO)3)3·6H2And O (0.124g), continuously stirring for 60 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in an oven at 100 ℃ for 48 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product with distilled water, and drying the product at room temperature to obtain brown yellow columnar crystals.
Example 3
1) Preparing acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH-4.8, and adding FeCl3(2.986g) was dissolved in the above 10mL of buffer solution and was used.
2) Preparing a sodium hydroxide solution with the concentration of 1M for later use.
3) Will K12[α-H2P2W12O48]·24H2O (0.391g) is added into a 6mL water system, and FeCl which is prepared is added into the water system in turn under the condition of continuous stirring3Solution (1mL), K2CO3(0.064g), 1M NaOH solution (1.25mL) and LaCl3·6H2And O (0.119g), continuously stirring for 60 minutes, then putting the mixture into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, heating the reaction kettle in an oven at 100 ℃ for 48 hours, taking the reaction kettle out, naturally cooling the reaction kettle to room temperature, filtering and washing the product with distilled water, and drying the product at room temperature to obtain brown yellow columnar crystals.
The product prepared by the invention is detected, and the asymmetric molecular structural unit of the detected polyacid-based crystalline material contains a tetranuclear iron embedded substituted tetranuclear Dawson type P2W14O54]14-Four defect sites of the cluster block, wherein Fe in the tetranuclear iron unit is disordered, and the occupancy rates of Fe and W are respectively 0.5, so that the molecular formula of the cluster block is [ Fe [ ]2(α-P2W16O56)]，Fe3+All present a hexa-coordinated octahedral configuration, the bond length of the Fe-O bond being in the range
(Table 1).
TABLE 1 data table of partial bond lengths in clusters
*Symmetry transformations used to generate equivalent atoms:#1＝-x+1,-y,-z+ 1；#2＝x,y+1,z；#3＝-x+1,-y+1,-z；#4＝-x+1,-y,-z；#5＝x-1,y,z；#6＝x+1,y, z；#7＝x,y-1,z.
In addition, there are two crystallographically independent dangling [ Fe ] in this compound2(α-P2W16O60)]The rare earth lanthanum ions on the cluster block are all in a nine-coordination configuration: la13+Coordinated with two oxygens (O10, O51) from different vacancy polyacid cluster blocks and seven water molecules, and La23+Coordinated with four oxygens (O21, O32, O42 and O48) from different vacancy polyacid cluster blocks and five water molecules (FIG. 1), the bond length of the La-O bond ranges from
Transition metal substituted [ Fe2(α-P2W16O56)]The polyacid cluster blocks are connected together through O10-La1-O51 bonds and Fe-O-Fe bonds to form a sandwich cluster block (figure 2) of a sandwich type. The two cluster blocks are connected by La2-O21 and La2-O32 to form a one-dimensional chain structure (figure 3). The chains are further linked by La2-O42, forming a two-dimensional layered pattern structure (FIG. 4). The layers are further bonded through La2-O48 to form a three-dimensional network structure (figure 5). It is worth noting that the compound is a rare La-Fe heterometallic modified Dawson type pure inorganic phosphotungstic acid compound.
The process parameters and routes of the present invention are not limited to the specific embodiments listed above, which are merely illustrative of the present invention and are not limited to the process parameters and routes described in the examples of the present invention. It should be understood by those skilled in the art that the present invention can be modified or substituted with equivalents in practical applications to achieve the same technical effects. As long as the application requirements are met, the invention is within the protection scope.
Claims (8)
1. A heterometallic substituted Dawson type polyacid-based crystal material, characterized in thatThe chemical formula of the crystal material is as follows: KH [ Fe ]2La2(H2O)12(α-P2W16O60)]·21H2O；
The crystal belongs to a triclinic system, P-1 space group, and the unit cell parameters are as follows:
α＝70.251(2)°,β＝69.933(2)°,γ＝85.273(2)°，
Z＝2。
2. a method for preparing the heterometallic substituted Dawson-type polyacid-based crystalline material of claim 1, comprising the steps of:
1) preparing acetic acid and sodium acetate buffer solution with the concentration of 0.5M, pH-4.8, and adding 27-30 parts by weight of FeCl3Dissolving in the buffer solution for later use;
2) preparing a sodium hydroxide solution with the concentration of 1M for later use;
3) 39-43 parts by weight of K12[α-H2P2W12O48]·24H2Adding O into a water system, and sequentially adding prepared FeCl into the water system under the condition of continuous stirring3Solution, 6-7 parts by weight of K2CO31M NaOH solution and 10-13 parts by weight of LaCl3·6H2O or La (NO)3)3·6H2O, continuously stirring for 60-180 minutes;
4) putting the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, sealing and putting the reaction kettle into an oven for heating;
5) taking out, naturally cooling to room temperature, filtering the product, washing with distilled water for 3-5 times, and drying at room temperature to obtain brown yellow columnar crystal.
3. The method for preparing a heterometallic substituted Dawson-type polyacid-based crystalline material according to claim 2, wherein the buffer in step 1) is added in an amount of 2.7-3.0g of F eCl per 10ml of buffer3。
4. The method for preparing a heterometallic substituted Dawson-type polyacid-based crystalline material according to claim 2, wherein H in step 3) is2K with 1g of O12[α-H2P2W12O48]·24H2O15-21 mL of water was added.
5. The method for preparing a heterometallic substituted Dawson-type polyacid-based crystalline material according to claim 2, wherein FeCl is used in step 3)3The amount of solution added was 1g of K12[α-H2P2W12O48]·24H2Adding 2.0-2.6mL of prepared FeCl into O3And (3) solution.
6. The method for preparing a heterometallic substituted Dawson-type polyacid-based crystalline material according to claim 2, wherein the NaOH solution is added in step 3) in an amount of 1g of K12[α-H2P2W12O48]·24H2And adding 2.9-3.2mL of prepared NaOH solution into the O.
7. The method for preparing a heterometallic substituted Dawson-type polyacid-based crystalline material according to claim 2, wherein the heating temperature in step 4) is 90 to 105 ℃ and the heating time is 40 to 60 hours.
8. The method of claim 2, wherein [ α -H ] is a unit of a crystal of a polymetallic polyacid type of Dawson type2P2W12O48]12–Is K12[α-H2P2W12O48]·24H2O precursor, rare earth and transition metal salt are respectively LaCl3·6H2O and FeCl3The pH value is adjusted by using K2CO3，NaOH,CH3COOH-CH3COONa solution.
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