CN113401943B - Transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound and preparation method thereof - Google Patents
Transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transition-rare earth dissimilar metal cluster doped multi-niobium oxide compound, which has the molecular formula: na (Na)6H20{TM2[Dy3O(μ3‑OH)3(H2O)3]2(Nb6O19)5}·nH2O, 6 Dy in the interior of cluster anion in the crystal structure of the compound3+Ion and 2 TM3+The ions form an 8-nucleus transition-rare earth dissimilar metal cluster, a regular triangular bipyramid configuration is formed along the direction of a three-dimensional axis, and 5 pieces of Nb are successfully captured by the upper end and the lower end of the dissimilar metal cluster and the equatorial plane of the dissimilar metal cluster6O19}(Nb6) Cluster units, forming rare transition-rare earth metalloid cluster doped polyniobate cluster anions. The method combines the conventional hydrothermal method and the room-temperature volatilization method, takes the sodium carbonate-sodium bicarbonate buffer solution as the solvent, has simple preparation process, can maintain the pH value of the reaction system in a proper and stable range, simultaneously solves the problem of incompatibility of the niobate precursor and two dissimilar metals when coexisting, and avoids a great deal of precipitate from premature precipitation of transition metal and rare earth ions.
Description
Technical Field
The invention relates to the field of magnetic materials and crystal materials, in particular to a transition-rare earth dissimilar metal cluster doped multi-niobium oxyacid compound, a preparation method and application.
Background
The polyoxometallate is a metal oxo-cluster anion formed by dehydrating and polycondensing pre-transition metal oxides such as Mo, W, V, Nb, Ta and the like, and has interesting structural characteristics such as high negative charge, oxygen-enriched surface, oxygen-enriched redox performance, nano-scale size and the like. Due to their potential applications in the fields of catalysis, medicine, magnetism, and material science, researchers are continually striving to synthesize new metal-doped polyoxometallates. Metal-substituted polyoxometalates have attracted attention from a wide range of researchers due to their structural diversity and interesting applications in magnetic fields as one of the more rapidly developing branches of the polyacid field.
Metal substituted polyoxometalates are ideal models for studying the magnetic coupling of metal clusters, since they represent a well-insulated cluster with a defined number of nuclei and a special model. The metal-substituted polyoxometalates include transition metal, rare earth metal, transition-rare earth metalloid substituted polyacids. To date, much effort has been devoted to the study of transition metal-substituted polyoxometalates and rare earth-substituted polyoxometalates, resulting in a large number of isometal-substituted polyoxometalates with an attractive structure and unique properties. However, transition-rare earth heterometal cluster doped polyacids continue to evolve with lag and the number of such materials remains limited, as compared to the rapidly evolving transition metal substituted polyoxometalates and rare earth substituted polyoxometalates. The main reasons are due to the variable coordination numbers and geometries of the different metal ions, the competition between the transition and rare earth metals of different radii and oxophilic characteristics and the vacancy mass of the precursor, and therefore, usually only one metal crystallizes in the final product. It is to be noted that, in the compounds reported to contain both transition metal ions and rare earth metal ions, the transition metal ions and rare earth ions are mostly separated by vacancy blocks or organic ligands of the polyacid, so that no heterometallic oxygen cluster can be formed to intercalate the polyacid. The possibility of hybrid coupling and relaxation channels is provided by combining the transition metal and the rare earth metal in the same molecule; the transition metal can provide obvious spin, and the rare earth ions can provide obvious magnetic anisotropy to avoid the possibility of spin reversal, so that the intrinsic advantages of the transition metal and the rare earth metal are combined at the same time, and an ideal model is provided for the monomolecular magnetic behavior of polyacid chemistry. The main research value in this field has therefore focused on exploring the magnetic properties of such materials. So far, the reported transition-rare earth doped polyacid mainly focuses on the field of polytungstate, and the configuration thereof is gradually diversified, including dimer, trimer, tetramer and hexamer, and the number of nuclei of the metalloid cluster is also gradually progressed from low nuclei to high nuclei.
Polyoxoniobate has attracted a great deal of attention because of its unique structure and potential applications in the fields of photocatalysis, base catalysis, and degradation of warfare agents and nerve agents. However, transition-rare earth doped poly-niobates are still in the early stages compared to transition-rare earth metalloid cluster doped poly-tungstates. In several cases of the so far reported polyniobate containing both transition metal and rare earth metal, the transition metal and rare earth metal are separated from each other by the polyniobate, and no hetero-metal cluster is formed. Therefore, the synthesis of transition-rare earth dissimilar metal cluster doped niobium polyacid clusters has not been reported, and the main reasons for this are the following: (1) a niobium polyacid precursor lacking solubility; (2) the niobium polyacid cluster has lower reactivity; (3) the working environment of the strong basicity of the niobate is incompatible with transition metal ions and rare earth metal ions. Under higher alkaline conditions, rare earth ions and transition metal ions are easy to hydrolyze to form precipitates and are not easy to crystallize. The combination of the transition-rare earth dissimilar metal oxygen cluster and the polyoxometallate not only enriches the configuration of the dissimilar metal oxygen cluster doped polyoxometallate, but also provides possibility for exploring the influence of different metal ions on the performance (magnetism, luminescence and the like) of the final niobium polyacid material. Therefore, the exploration and synthesis of novel transition-rare earth dissimilar metal cluster doped polyoxobioates is a very challenging and scientifically significant topic.
Disclosure of Invention
In order to solve the problems, the invention provides a transition-rare earth dissimilar metal cluster doped niobium-oxygen-acid compound and a preparation method thereof.
The invention adopts the following technical scheme:
a transition-rare earth dissimilar metal cluster doped niobium oxide compound has a molecular formula as follows: na (Na)6H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2O, wherein: TM is transition metal Cr3+、Mn3+、Fe3+Or Co3+Ions, corresponding to n being 40,44,43,36 protonated ligands, respectively; the compound crystal belongs to a trigonal system, and the space group is
6 Dy in the interior of cluster anion in crystal structure3+Ion and 2 TM3+Ions form an 8-nuclear transition-rare earth dissimilar metal cluster with 6 Dy3+Ions and two TMs at the upper and lower ends thereof3+The ions form a regular triangular bipyramid configuration, and the 8-nuclear transition-rare earth dissimilar metal cluster is connected with two Nb at the upper end and the lower end6A cell having three Nb connected in the equatorial direction6A unit forming a transition-rare earth dissimilar metal cluster doped polyNb oxide cluster anion with a triangular bipyramid configuration, and having a hexanuclear [ Na ] outside the cluster anion along the direction of the cubic axis6(H2O)24]6+As a counter cation of the cluster anion, it has a hexagonal close-packed 3D structure in the c-axis direction thereof.
Preferably, the unit cell parameters of the compound are:
TM is transition metal Cr3+When the temperature of the water is higher than the set temperature,
calculated density was 2.347g/cm3；
TM is transition metal Mn3+When the temperature of the water is higher than the set temperature,
the calculated density is 2.339g/cm3；
TM is transition metal Fe3+When the temperature of the water is higher than the set temperature,
the calculated density was 2.354g/cm3；
TM is transition metal Co3+When the temperature of the water is higher than the set temperature,
the calculated density was 2.329g/cm3；
The method for preparing the transition-rare earth dissimilar metal cluster doped niobium-oxygen-containing compound is characterized by comprising the following steps:
sequentially weighing niobium precursor potassium tridecanoate trihydrate, dysprosium nitrate hexahydrate, trihydroxymethylaminomethane and transition metal salt, wherein the molar ratio of the niobium precursor potassium tridecanoate trihydrate, the dysprosium nitrate hexahydrate and the trihydroxymethylaminomethane is 2:1:4, the transition metal salt is chromium chloride hexahydrate, manganese chloride tetrahydrate, ferrous sulfate heptahydrate or cobalt chloride hexahydrate, and the molar ratio of the transition metal salt to the dysprosium nitrate hexahydrate is 2:1, 2.35:1, 1.64:1 and 1.92:1 respectively;
uniformly stirring weighed precursors of potassium niobate tridecanoate hydrate, dysprosium nitrate hexahydrate, trihydroxymethyl aminomethane and transition metal salt in a sodium carbonate-sodium bicarbonate buffer solution, performing hydrothermal reaction, and filtering to obtain a mother solution, wherein the temperature of the hydrothermal reaction is 90 ℃, and the reaction time is 72 hours;
and slowly volatilizing the mother liquor at room temperature to obtain the transition-rare earth dissimilar metal cluster doped niobium-oxygen acid compound.
The compound is used as a magnetic material, shows better magnetic anisotropy under different temperature conditions, and has slow magnetic relaxation characteristics in different frequency ranges; the doping of four different transition-rare earth dissimilar metal clusters enables the poly-niobic acid clusters to show controllable magnetic behaviors.
After adopting the technical scheme, compared with the background technology, the invention has the following advantages:
the transition-rare earth dissimilar metal cluster doped niobium-oxygen-acid compound has a novel structure, and the compound contains a rare elementThe 8-core transition-rare earth dissimilar metal oxygen cluster, which forms a regular triangular bipyramid configuration along the cubic axis direction. The upper and lower ends of the dissimilar metal cluster and the equatorial plane thereof successfully capture 5 Nb6Cluster units, thereby forming rare clusters of niobium cluster-wrapped transition-rare earth metalloid clusters, having a hexagonal sodium cluster in the direction of the cubic axis as the counter cation of the cluster anion in addition to its cluster anion, thereby having a hexagonal close-packed 3D structure in the direction of the c-axis thereof. The configuration of the dissimilar metal oxygen cluster is successfully introduced into a multi-niobate cluster system for the first time, so that the configuration of the metal-doped niobate cluster is enriched, and the application of niobium polyacid in the aspect of magnetic performance is endowed. The invention provides an effective strategy for preparing the transition-rare earth dissimilar metal cluster-doped multi-niobium oxyacid compound by using a sodium carbonate-sodium bicarbonate buffer solution as a solvent and combining a conventional hydrothermal method and a room temperature volatilization method, the preparation process is simple, and the obtained transition-rare earth dissimilar metal cluster-doped multi-niobium oxyacid compound has better stability and is easy to store. The main problems of the synthesis of the materials are successfully solved by taking a sodium carbonate-sodium bicarbonate buffer solution as a solvent: (1) the pH value of the reaction system is maintained in a proper and stable range; (2) successfully solves the problem that the niobate precursor is incompatible when two dissimilar metals coexist, and avoids the premature precipitation of a large amount of precipitates of transition metals and rare earth ions. The room temperature volatilization method not only provides an environment for oxidizing divalent transition metal salt, but also is beneficial to the precipitation of crystalline target products when the concentration reaches a saturation value.
The prepared heteropolyniobium oxyacid compounds doped with different transition metal-rare earth dissimilar metal clusters have different magnetic properties due to different contributions of d-orbital electrons of the transition metal, so that the heteropolyniobium oxyacid compounds have potential application in the field of magnetic materials. In particular, due to the trivalent manganese ion (d)4Electronic configuration, with distortion due to the ginger taylor effect) has the possibility of single-molecule magnet behavior, and introduction thereof into the field of niobic acid will be of interest to a large number of researchers. The results show that the compounds show better magnetic anisotropy under different temperature conditions and different frequenciesWith varying degrees of slow magnetic relaxation behavior over the range of rates. The manganese-dysprosium heterometallic cluster doped polyoxobiobate compound has the most obvious phenomenon of slow magnetic relaxation and the highest effective energy barrier, so that the manganese-dysprosium heterometallic cluster doped compound has more excellent magnetic performance than other transition metal-dysprosium heterometallic cluster doped isomorphic materials in the compound.
Drawings
FIG. 1 shows Na which is a product obtained in examples 1 to 46H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2A crystal photograph of O;
FIG. 2 shows Na as a product obtained in examples 1 to 46H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2A coordination mode diagram of a transition-rare earth dissimilar metal cluster of a triangular bipyramid in O;
FIG. 3 shows Na as the product obtained in examples 1 to 46H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2A club and polyhedron schematic of cluster anions of O;
FIG. 4 shows Na as a product obtained in examples 1 to 46H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2A three-dimensional stacking diagram of O;
FIG. 5 is an XRD pattern of transition-rare earth metalloid cluster doped polyniobium oxide compounds obtained in examples 1-4;
FIG. 6 is a graph of the variable temperature susceptibility, variable field susceptibility and alternating current susceptibility of the product obtained in example 2;
FIG. 7 is a graph of the temperature and field-variable magnetic susceptibility of the products of examples 1, 3 and 4;
FIG. 8 is a graph of the AC magnetic susceptibility of the products obtained in examples 1, 3 and 4;
FIG. 9 is an energy barrier diagram of the products obtained in examples 1-4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1: na (Na)6H20{Cr2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·40H2Preparation of O transition-rare earth dissimilar metal cluster doped polyniobate cluster 0.27mmol potassium niobate tridecahydrate, 0.14mmol dysprosium nitrate hexahydrate, 0.24mmol chromium chloride hexahydrate and 0.53mmol tris (hydroxymethyl) aminomethane were added to 8mL sodium carbonate-sodium bicarbonate solution and mixed uniformly, the obtained mixture was put into a 25mL glass bottle, stirred for 1 hour and then put into an oven for hydrothermal reaction. Keeping the temperature at 90 ℃ for 72 hours, cooling to room temperature, filtering, and naturally volatilizing the obtained mother liquor at room temperature to obtain Na6H20{Cr2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·40H2O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster.
Example 2: na (Na)6H20{Mn2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·44H2Preparation of O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster
0.27mmol of potassium niobate tridecahydrate, 0.14mmol of dysprosium nitrate hexahydrate, 0.33mmol of manganese chloride dihydrate and 0.53mmol of tris (hydroxymethyl) aminomethane are added into 8mL of sodium carbonate-sodium bicarbonate solution to be uniformly mixed, the obtained mixture is put into a 25mL glass bottle, stirred for 1 hour and then put into an oven for hydrothermal reaction. Keeping the temperature at 90 ℃ for 72 hours, cooling to room temperature, filtering, and naturally volatilizing the obtained mother liquor at room temperature to obtain Na6H20{Mn2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·40H2O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster.
Example 3: na (Na)6H20{Fe2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·43H2Preparation of O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster
0.27mmol of potassium niobate tridecahydrate, 0.14mmol of dysprosium nitrate hexahydrate, 0.23mmol of ferrous sulfate heptahydrate and 0.53mmol of tris (hydroxymethyl) aminomethane are added into 8mL of sodium carbonate-sodium bicarbonate solution to be uniformly mixed, the obtained mixture is put into a 25mL glass bottle, stirred for 1 hour and then put into an oven for hydrothermal reaction. Maintaining at 90 deg.C for 72 hr, cooling to room temperature, filtering, and naturally volatilizing the mother liquor at room temperature to obtain Na6H20{Fe2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·43H2O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster.
Example 4: na (Na)6H20{Co2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·36H2Preparation of O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster
0.27mmol of potassium niobate tridecahydrate, 0.14mmol of dysprosium nitrate hexahydrate, 0.27mmol of cobalt chloride hexahydrate and 0.53mmol of tris (hydroxymethyl) aminomethane were added to 8mL of a sodium carbonate-sodium bicarbonate solution and uniformly mixed, and the obtained mixture was put into a 25mL glass bottle, stirred for 1 hour and then put into an oven for hydrothermal reaction. Keeping the temperature at 90 ℃ for 72 hours, cooling to room temperature, filtering, and naturally volatilizing the obtained mother liquor at room temperature to obtain Na6H20{Co2[Dy3O((μ3-OH)3(H2O)3]2(Nb6O19)5}·36H2O transition-rare earth dissimilar metal cluster doped poly-niobic acid cluster.
A photograph of a crystal of the resulting compound was taken, as shown in fig. 1; resolving the structure of the obtained product sample by SHELX-97, wherein transition-rare earth dissimilar metal cluster in the compound is shown in figure 2, and cluster anion unit is shown in figure 3; the three-dimensional stacking diagram of the resulting product is shown in FIG. 4; the XRD pattern of the obtained product is shown in figure 5; the temperature-changing magnetic susceptibility, the field-changing magnetic susceptibility and the alternating-current magnetic susceptibility of the product obtained in example 2 are shown in fig. 6; the temperature and field changeable susceptibility of the products obtained in examples 1, 3 and 4, as shown in FIG. 7; the ac magnetic susceptibility of the products obtained in examples 1, 3 and 4, as shown in fig. 8; the energy barriers of the products obtained in examples 1-4 are shown in FIG. 9.
Products obtained in examples 1 to 4 Na6H20{TM2[Dy3O(μ3-OH)3(H2O)3]2(Nb6O19)5}·nH2The crystallographic parameters of O are specified below:
TABLE 1
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A transition-rare earth dissimilar metal cluster doped niobium oxide compound is characterized in that the molecular formula of the compound is as follows: na (Na)6H20{TM2[Dy3O(μ 3-OH)3(H2O)3]2(Nb6O19)5}∙nH2O, wherein: TM is transition metal Cr3+、Mn3+、Fe3+Or Co3+Ions, corresponding to n being 40,44,43,36 protonated ligands, respectively; the compound crystal belongs to a trigonal system, and the space group is
The interior of the cluster anion in the crystal structure is 6 Dy3+Ion and 2 TM3+Ions form an 8-nuclear transition-rare earth dissimilar metal cluster with 6 Dy3+Ions and two TMs at the upper and lower ends thereof3+The ions form a regular triangular bipyramid configuration, and the 8-nuclear transition-rare earth dissimilar metal cluster is connected with two Nb at the upper end and the lower end6A cell having three Nb connected in the equatorial direction6A unit forming a transition-rare earth dissimilar metal cluster doped polyNb oxide cluster anion with a triangular bipyramid configuration, and having a hexanuclear [ Na ] outside the cluster anion along the direction of the cubic axis6(H2O)24]6+As a counter cation to the cluster anion, thereby forming a counter cation theretocThe axial direction has a hexagonal close-packed 3D structure.
2. The transition-rare earth metalloid cluster doped niobium monoxide compound of claim 1 having unit cell parameters of:
TM is transition metal Cr3+When the temperature of the water is higher than the set temperature,a=b=18.9817(6)Å，c =28.8986(15)Å， V = 9017.3(7)Å3calculated density was 2.347g/cm3；
TM is transition metal Mn3+When the temperature of the water is higher than the set temperature,a=b=19.0042(7)Å，c=28.9507(17)Å， V= 9055.0(9)Å3calculated density of 2.339g/cm3；
TM is transition metal Fe3+When the temperature of the water is higher than the set temperature,a=b =18.9931(3)Å，c=29.0291(7) Å， V= 9068.9(4)Å3calculated density is 2.354g/cm3；
TM is transition metal Co3+When the temperature of the water is higher than the set temperature,a=b=19.0037(3)Å，c=28.6076(11) Å， V= 8947.2(4)Å3calculated density of 2.329g/cm3。
3. A method of making the transition-rare earth metalloid cluster doped niobium oxo compound of claim 1 or 2, comprising the steps of:
sequentially weighing niobium precursor potassium tridecanoate hydrate, dysprosium nitrate hexahydrate, trihydroxymethylaminomethane and transition metal salt, wherein the molar ratio of the niobium precursor potassium tridecanoate hydrate, the dysprosium nitrate hexahydrate and the trihydroxymethylaminomethane is 2:1:4, the transition metal salt is chromium chloride hexahydrate, manganese chloride tetrahydrate, ferrous sulfate heptahydrate or cobalt chloride hexahydrate, and the molar ratio of the transition metal salt to the dysprosium nitrate hexahydrate is 2:1, 2.35:1, 1.64:1 and 1.92:1 respectively;
uniformly stirring weighed precursors of potassium niobate tridecanoate hydrate, dysprosium nitrate hexahydrate, trihydroxymethyl aminomethane and transition metal salt in a sodium carbonate-sodium bicarbonate buffer solution, performing hydrothermal reaction, and filtering to obtain a mother solution, wherein the temperature of the hydrothermal reaction is 90 ℃, and the reaction time is 72 hours;
and slowly volatilizing the mother liquor at room temperature to obtain the transition-rare earth dissimilar metal cluster doped niobium-oxygen acid compound.
4. Use of the transition-rare earth metalloid cluster doped polyoxioniobate compound of claim 1 or 2 as a magnetic material.
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| 多铌氧酸盐的合成、结构及其性质研究;梁志结;《中国博士学位论文全文数据库》;20210531(第5期);全文 * |
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