CN114075249A - Dissimilar metal niobium-oxygen cluster compound and preparation method and application thereof - Google Patents
Dissimilar metal niobium-oxygen cluster compound and preparation method and application thereof Download PDFInfo
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- BFRGSJVXBIWTCF-UHFFFAOYSA-N niobium monoxide Chemical compound [Nb]=O BFRGSJVXBIWTCF-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 title abstract description 11
- 239000002184 metal Substances 0.000 title abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000010955 niobium Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 150000001621 bismuth Chemical class 0.000 claims description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 150000002821 niobium Chemical class 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- ZREIPSZUJIFJNP-UHFFFAOYSA-K bismuth subsalicylate Chemical group C1=CC=C2O[Bi](O)OC(=O)C2=C1 ZREIPSZUJIFJNP-UHFFFAOYSA-K 0.000 claims description 6
- 229960000782 bismuth subsalicylate Drugs 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 238000004729 solvothermal method Methods 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 5
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 4
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SBSZUBUHOUKQMN-UHFFFAOYSA-K 1,2-dimethoxyethane;trichloroniobium Chemical compound Cl[Nb](Cl)Cl.COCCOC SBSZUBUHOUKQMN-UHFFFAOYSA-K 0.000 claims description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- 238000004523 catalytic cracking Methods 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 229910019804 NbCl5 Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- SMPAPEKFGLKOIC-UHFFFAOYSA-N oxolane;hydrochloride Chemical compound Cl.C1CCOC1 SMPAPEKFGLKOIC-UHFFFAOYSA-N 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/94—Bismuth compounds
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/08—Heat treatment
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
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Abstract
The invention belongs to the technical field of preparation of crystal materials, and particularly relates to BixNbyType (e.g. Bi)3Nb18Form and Bi4Nb16Form) and a method for preparing the polymeric crystalline substance. The invention realizes the purpose of constructing metal niobium-oxygen clusters with different nanometer sizes by regulating and controlling synthesis conditions and forming poly-crystalline substances with different sizes and structure types through the polycondensation reaction of secondary structure units in a synthesis system. By solvothermal synthesisThe materials are subjected to self-assembly reaction, the synthesis steps are simple, the requirement on the purity of the raw materials is low, the raw materials are easy to obtain and low in price, and further purification is not needed.
Description
Technical Field
The invention belongs to the technical field of crystal materials, and particularly relates to a dissimilar metal niobium oxygen cluster compound and a preparation method and application thereof.
Background
The polyacid is also called polyoxometallate, can form molecular structures with different nanometer sizes, high nuclear and high symmetry, and can be used for researching the relation between the structure and the performance. Among transition metals, some polyacids (such as V, W, Mo and the like) can obtain various structures simply by regulating and controlling the pH of a synthesis system, and many structures have stronger electron and proton transfer/storage capacities, thereby being beneficial to researching the internal structure-activity relationship of the polyacids. In fact, the polyacid also shows good synergistic effect after being compounded with different functional materials. However, these are based on good synthetic systems. Currently, some transition metals (e.g., Nb) are relatively slow to develop compared to adjacent metals (e.g., V, W, Mo, etc.) due to their intrinsic metal chemical inertness, a more basic environment, and limitations on selectivity of the corresponding soluble metal salts.
Therefore, it is necessary to search for an effective synthesis method for constructing niobium-oxygen clusters with different nanometer sizes. Research shows that the metal niobium salt cluster has good effect in the fields of nuclear waste treatment, catalysis (cracking water, organic catalytic reaction and the like) and the like.
Disclosure of Invention
In order to realize the purpose of constructing metal niobium oxygen clusters with different nano-scale sizes, the invention provides a dissimilar metal niobium oxygen cluster compound and a synthesis method thereof.
The present invention provides a BixNbyA type poly-crystalline substance, namely a heterometallic niobium-oxygen cluster compound constructed by modifying an organic ligand; wherein x is 3 or 4 and y is 16 or 18.
According to an embodiment of the invention, the polymeric crystalline substance is Bi3Nb18Form of the formula C126H90O88Cl3Bi3Nb18。
According to an embodiment of the invention, the polymeric crystalline substance has the crystal parameters shown in table 1 below:
TABLE 1
According to an embodiment of the invention, the polymeric crystalline substance has an X-ray powder diffraction pattern substantially as shown in figure 2 (a).
According to an embodiment of the invention, the polymeric crystalline substance is Bi4Nb16Form of the formula C172H126N2O96Bi4Nb16。
According to an embodiment of the invention, the polymeric crystalline substance has the crystal parameters shown in table 2 below:
TABLE 2
According to an embodiment of the invention, the polymeric crystalline substance has an X-ray powder diffraction pattern substantially as shown in figure 2 (b).
The invention also provides a preparation method of the poly-crystalline substance, which comprises the following steps: adding bismuth salt, niobium salt and ligand into a solvent, and carrying out solvothermal reaction to obtain the poly-crystalline substance.
According to an embodiment of the invention, the bismuth salt is selected from bismuth subsalicylate or other bismuth salts selected from at least one of bismuth acetate, bismuth nitrate, triphenylbismuth, bismuth trichloride; bismuth subsalicylate is preferred.
According to an embodiment of the present invention, when the bismuth salt is selected from other bismuth salts, salicylic acid may be added to the system; the molar ratio of the bismuth salt to the salicylic acid may be 1 (0.8-8), for example 1 (3-5).
According to an embodiment of the present invention, the niobium salt is at least one selected from niobium pentachloride, niobium pentafluoride, niobium ethoxide, 1, 2-dimethoxyethane-niobium trichloride (1:1), and niobium tetrachlorobis (tetrahydrofuran) chloride (IV), preferably niobium pentachloride.
According to an embodiment of the present invention, the ligand may be an organic ligand, for example, at least one selected from benzoic acid, methyl benzoic acid, ethyl benzoic acid, salicylic acid.
According to an embodiment of the invention, the niobium salt: bismuth salt: the molar ratio of the ligands is 1 (0.8-5) to 1-8, for example 1 (1-3) to 2-6.
According to the embodiment of the invention, the solvent is acetonitrile, an alcohol solvent or a mixed solvent of the acetonitrile and the alcohol solvent, and the volume ratio of the alcohol solvent to the acetonitrile in the mixed solvent is 1 (0.8-8), such as 1 (2-5); the selection of the kind and the proportion of the solvent is based on the increase of the solubility of the ligand and the metal salt, and the mixed solvent of acetonitrile and alcohols is preferred.
According to an embodiment of the present invention, the alcohol solvent may be selected from alcohol solvents having 1 to 40 carbon atoms (e.g., 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms), for example, any one selected from methanol, ethanol, n-propanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, neopentyl alcohol, n-hexanol, cyclohexanol. As an example, the mixed solvent may be a mixture of acetonitrile and one selected from methanol, ethanol, n-propanol, tert-butanol, n-butanol and isobutanol; preferably, the solvent is a mixed solvent of ethanol or n-propanol and acetonitrile.
According to an embodiment of the present invention, the solvothermal reaction is a heating reaction carried out under autogenous pressure of a glass bottle or a reaction vessel.
According to an embodiment of the present invention, the temperature of the solvothermal reaction may be 40 to 120 ℃; preferably 70-100 deg.C, such as 80-100 deg.C, 80 deg.C, 90 deg.C, 100 deg.C. The reason is that the reaction temperature is related to the reaction barrier and the crystallization speed, the lower the reaction temperature, the longer the product takes, and the slower the crystallization process, and vice versa, preferably 80 to 100 ℃.
According to an embodiment of the present invention, the reaction time may be 48 to 336 hours; further preferably 48 to 180 hours, such as 168 hours. The longer the reaction time, the larger the crystal size.
According to an embodiment of the invention, the preparation process further comprises a step of further purifying the product, comprising: and cooling the reaction liquid to room temperature, and then carrying out ultrasonic treatment, cleaning, separation and air drying to obtain the purified poly-crystalline substance.
According to the embodiment of the invention, the frequency of the ultrasonic wave is 30-80 Hz; the ultrasonic time is 3-10 minutes; preferably, sonication at 50 Hz for 5 minutes;
according to an embodiment of the present invention, the solvent used for the cleaning may be an alcohol solvent selected from alcohols having 1 to 40 carbon atoms (e.g., 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms) or a mixture of alcohols.
According to the embodiment of the invention, the yield of the poly-crystalline substance can reach more than 60%.
The invention also provides application of the poly-crystalline substance in nuclear waste treatment, catalytic water splitting and organic catalytic reaction.
Advantageous effects
The invention provides a method for forming poly-crystalline substances with different sizes and structure types by performing polycondensation reaction between secondary structural units in a synthesis system through regulating and controlling synthesis conditions (such as solvent, reaction temperature and the like). Specifically, through organic ligand modification, a secondary niobium-oxygen building unit is formed in a synthesis system, and then the simple niobium-oxygen unit is subjected to further condensation polymerization reaction to obtain Bi with different polymerization degreesxNbyForm polymeric crystalline material, e.g. C126H90O88Cl3Bi3Nb18And C172H126N2O96Bi4Nb16。
The invention is synthesized by a solvothermal one-step method, namely, the raw materials are simply mixed in a solvent and are subjected to self-assembly reaction after being heated. The method has the advantages of simple synthesis steps, low requirement on the purity of raw materials, cheap and easily-obtained raw materials and no need of further purification.
Drawings
FIG. 1(a) shows Bi prepared in example 13Nb18A schematic crystal structure of the form poly-crystalline substance; (b) is Bi prepared in example 24Nb16A schematic crystal structure of the form poly-crystalline substance;
FIG. 2(a) shows Bi prepared in example 13Nb18X-ray powder diffractogram of form polycrystals; (b) is Bi prepared in example 24Nb16X-ray powder diffractogram of form polycrystals;
FIG. 3(a) shows Bi prepared in example 13Nb18Product photographs of form polycrystals; (b) is Bi prepared in example 24Nb16Product photo of form polycrystals.
Detailed Description
In order to make the object and the synthetic process of the present invention more clear, the present invention will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the scope of the invention.
Unless otherwise indicated, reagents for use in the invention are commercially available.
The single crystal structure analysis of the present invention uses a Supernova single crystal diffractometer in japan.
The X-ray powder diffraction test uses Cu-K alpha ray as the radiation source.
Example 1
Bismuth subsalicylate (2.8mmol), NbCl5(1.4mmol), benzoic acid (4.9mmol), acetonitrile (5mL) and ethanol (5mL) are placed in a 20mL glass bottle, mixed uniformly at room temperature, placed in an oven at 80 ℃ for constant temperature, taken out after 7 days, naturally cooled to room temperature, separated out a solid phase, and washed by ethanol to obtain a yellow cubic crystalline target product.
Bi prepared in example 13Nb18The crystal parameters of the form polycrystals are shown in Table 3.
TABLE 3
Example 2
Bismuth subsalicylate (1.9mmol), NbCl5(0.7mmol), benzoic acid (4.9mmol), acetonitrile (5mL) and n-propanol (5mL) are placed in a 20mL glass bottle, mixed uniformly at room temperature, placed in a 100 ℃ oven for constant temperature, taken out after 7 days, naturally cooled to room temperature, separated out a solid phase and washed by ethanol to obtain an orange rod-shaped crystalline target product.
Bi prepared in example 24Nb16The crystal parameters of the form polycrystals are shown in Table 4.
TABLE 4
The present invention has been explained above. It should be understood that the invention is not limited to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. BixNbyA type poly-crystalline substance, namely a heterometallic niobium-oxygen cluster compound constructed by modifying an organic ligand; wherein x is 3 or 4 and y is 16 or 18.
3. The polymeric crystalline substance of claim 1 or 2, wherein the polymeric crystalline substance has an X-ray powder diffraction pattern substantially as shown in figure 2 (a).
5. The polymeric crystalline substance of claim 1 or 4, wherein the polymeric crystalline substance has an X-ray powder diffraction pattern substantially as shown in figure 2 (b).
6. A process for the preparation of the polymeric crystalline substance of any one of claims 1 to 5, comprising the steps of: adding bismuth salt, niobium salt and a ligand into a solvent, and carrying out solvothermal reaction to obtain the poly-crystalline substance;
preferably, the bismuth salt is selected from bismuth subsalicylate or other bismuth salts, and the other bismuth salts are selected from at least one of bismuth acetate, bismuth nitrate, triphenyl bismuth and bismuth trichloride; preferably bismuth subsalicylate;
preferably, when the bismuth salt is selected from other bismuth salts, salicylic acid can be added into the system; the molar ratio of the other bismuth salt to the salicylic acid can be 1 (0.8-8), such as 1 (3-5);
preferably, the niobium salt is at least one selected from niobium pentachloride, niobium pentafluoride, niobium ethoxide, 1, 2-dimethoxyethane-niobium trichloride (1:1), and niobium tetrachlorobis (tetrahydrofuran) and (IV), preferably niobium pentachloride;
preferably, the ligand may be an organic ligand, for example, at least one selected from benzoic acid, methylbenzoic acid, ethylbenzoic acid, salicylic acid;
preferably, the niobium salt: bismuth salt: the molar ratio of the ligands is 1 (0.8-5) to 1-8, for example 1 (1-3) to 2-6.
7. The preparation method according to claim 6, wherein the solvent is acetonitrile, an alcohol solvent or a mixed solvent of the two, and the volume ratio of the alcohol solvent to the acetonitrile in the mixed solvent is 1 (0.8-8), such as 1 (2-5); preferably a mixed solvent of acetonitrile and alcohols;
preferably, the alcohol solvent may be selected from alcohol solvents having 1 to 40 carbon atoms (e.g., 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms), for example, any one selected from methanol, ethanol, n-propanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, neopentyl alcohol, n-hexanol, cyclohexanol. As an example, the mixed solvent may be a mixture of acetonitrile and one selected from methanol, ethanol, n-propanol, tert-butanol, n-butanol and isobutanol; preferably, the solvent is a mixed solvent of ethanol or n-propanol and acetonitrile.
8. The preparation method according to claim 6 or 7, wherein the temperature of the solvothermal reaction is 40-120 ℃; preferably 70 to 100 ℃, such as 80 to 100 ℃;
preferably, the solvothermal reaction is a heating reaction carried out under autogenous pressure of a glass bottle or a reaction kettle.
9. The method according to any one of claims 6 to 8, wherein the reaction time is 48 to 336 hours; further preferably 48 to 180 hours;
preferably, the preparation method further comprises a step of further purifying the product, comprising: cooling the reaction liquid to room temperature, and then carrying out ultrasonic treatment, cleaning, separation and air drying to obtain a purified poly-crystalline substance;
preferably, the frequency of the ultrasound is 30-80 Hz; the ultrasonic time is 3-10 minutes;
preferably, the solvent used for the cleaning may be an alcohol solvent selected from alcohols having 1 to 40 carbon atoms (e.g., 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms) or mixtures of alcohols.
10. Use of the polymeric crystalline substance according to any one of claims 1 to 5 or obtained by the preparation process according to any one of claims 6 to 9 for nuclear waste treatment, catalytic cracking of water, organic catalytic reactions.
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