CN106976888A - A kind of many Boratex pore passage structure materials and preparation method thereof - Google Patents
A kind of many Boratex pore passage structure materials and preparation method thereof Download PDFInfo
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- CN106976888A CN106976888A CN201710176991.2A CN201710176991A CN106976888A CN 106976888 A CN106976888 A CN 106976888A CN 201710176991 A CN201710176991 A CN 201710176991A CN 106976888 A CN106976888 A CN 106976888A
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- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/121—Borates of alkali metal
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- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
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- C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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Abstract
The invention belongs to borate poromerics preparing technical field, it is related to a kind of many Boratex pore passage structure materials and preparation method thereof, by Li2B4O7, borax be blended in ethylenediamine and water, the crystallization under 180 DEG C of water (solvent) thermal environment realizes two-dimentional " boron oxygen " oversubscription sublayer and the assembling of " sodium oxygen " metal-layer structure, prepares many Boratex poromerics of un-densified structure three-dimensional；Its synthesis technique is simple, it is easy to operate, and raw material is easy to get, and the borate material of diverse microcosmic structure is well used in fields such as semi-conducting material, nonlinear optics, ferroelectric material, laser crystals.
Description
Technical field：
The invention belongs to borate poromerics preparing technical field, be related to a kind of many Boratex pore passage structure materials and its
Preparation method, particularly a kind of many Boratex poromerics of un-densified three-dimensional structure and preparation method thereof.
Background technology：
Pore passage structure material is due to unique architectural feature and excellent absorption, Industrial Catalysis and ion exchange etc.
Performance receives much concern.With socio-economic development, the research and application of unconventional aluminosilicate molecular sieves material are increasingly active.
Borate has rich and varied crystal structure, the research heat as nonlinear optics, laser crystal and field of semiconductor materials
One of point.So far, alkali metal, the research of alkaline earth metal borate still occupies leading position, a large amount of nature mineral and
Alkali-alkaline earth metal borate of laboratory synthesis is characterized, and this kind of compound is synthesized using high temperature solid-state method mostly, is generally had
Fine and close phase structure.Relatively low from the most concentration class of structural analysis alkali (soil) metal borate, majority is containing 1~6 boron atom, synthesis tool
The very big difficulty of B-O clusters and challenge, such as separate structure K with the presence of larger aggregation extent7{(BO3)Mn[B12O18(OH)6]}
H2O、Li3KB4O8,、iNa2Sr8B12O24F6Cl and Li3NaBaB6O12Deng.Water (solvent) process for thermosynthesizing should borate salt system
Possibility is provided with to prepare larger concentration class, Vaculating antigen material.Therefore, a kind of new many Boratex pore passage structure materials are sought
Material and preparation method thereof, using organic ethylenediamine and water strong basicity environment, promotes BO3、BO4The common summit of unit, which assembles to be formed, to be had
[the B of 12 B atoms12O18(OH)6] cluster module, while realizing NaO in the structure first6、NaO7Polyhedron is total to summit from group
Fill as alkali metal " sodium-oxygen " layer.On this basis, [the B based on hydrogen bond action12O18(OH)6] module formation " boron-oxygen " oversubscription
Sublayer further links with above-mentioned alkali metal " sodium-oxygen " layer and forms many Boratex materials of un-densified structure three-dimensional, the material and
It is prepared still belongs to the first time in the synthesis of inorganic microporous borate material, to the further crystallization assembling process of understanding borate and rule
Rule has important theory significance.
The content of the invention：
It is an object of the invention to overcome the shortcoming that prior art is present, seek design and provide one kind under the conditions of solvent heat
Many Boratex pore passage structure materials are prepared, by Li2B4O7, borax be blended in ethylenediamine and water, 180 DEG C of water (solvent) heat
Crystallization under environment, realizes two-dimentional " boron-oxygen " oversubscription sublayer and the assembling of " sodium-oxygen " metal-layer structure, prepares the first un-densified
The many Boratex poromerics of structure three-dimensional.
To achieve these goals, the molecular formula of many Boratex pore passage structure materials of the present invention is [H3O]
[Na5B12O18(OH)6]·2H2O, molecular weight is 689.77, and crystallographic data is α=β=90 °, γ=120 °,Z=6；The material has one-dimensional regular pore canal
Structure (as shown in Figure 1), is trigonal system, R-3c space groups, and the Na of 1.5 crystallography independence is included in minimum asymmetric cell
Atom, 2 boron atoms, 4 oxygen atoms and dissociating water molecule etc..B atoms take common BO3Plane triangle and BO4Tetrahedron
Pattern, Na atoms take NaO6And NaO7Two kinds of coordination environments (as shown in Figure 2), 6 BO4Tetrahedron and 6 BO2(OH) plane
Triangle polymerize to form [the B with larger concentration class12O18(OH)6] cluster anions, adjacent [B12O18(OH)6] cluster anions
Two-dimentional supermolecule " boron-oxygen layer ", 9 NaO are formed in ab planes by hydrogen bond action6With 3 NaO7Polyhedron is existed by common summit
Two dimension " sodium-oxygen " metal level that the formation of ab planes had not been found, two-dimentional supermolecule " boron-oxygen " layer and two-dimentional " sodium-oxygen " metal level
Link to form micropore Boratex three-dimensional structure along c-axis direction alternating stacking.
The present invention prepares the detailed processes of many Boratex pore passage structure materials：
(1), metal sodium source, boron source, organic amine and solvent are well mixed, wherein metal sodium source and the mol ratio of organic amine
For 1：36~37, the mol ratio of boron source and organic amine is 1：18~19, the mol ratio of organic amine and solvent is 2.5：1, at room temperature
It is sufficiently stirred for obtaining mixture；
(2), the mixture for obtaining step (1) is transferred to the stainless steel high-pressure reaction vessel with cup in polytetrafluoroethylene (PTFE)
In, in 170-180 DEG C of crystallization 9~12 days, obtain the colourless bulk crystals with good crystallinity；
(3), colourless bulk crystals obtained by step (2) are washed with deionized, suction filtration, and be dried at room temperature for, prepare
Obtain many boric acid sodium crystals with three-dimensional micropore structure.
Metal sodium source of the present invention is sodium tetraborate；Boron source is Li2B4O7It is (0.7- with sodium tetraborate mol ratio
1.0):The mixture of (1.0-2.0)；Organic amine is ethylenediamine；Solvent is deionized water；The volume of stainless steel cauldron is 25mL
Or 30mL.
The present invention compared with prior art, synthesizes based on two-dimentional " boron-oxygen " oversubscription sublayer and " sodium-oxygen " Rotating fields first
The many Boratex materials of three-dimensional micropore formed are assembled, thermally-stabilised test, material skeleton are carried out to compound under the conditions of air atmosphere
With higher heat endurance, its UV-Vis DRS spectrum test shows that the band gap of the compound is about 5.28eV, can
As wide-band-gap semiconductor material, its synthesis technique is simple, it is easy to operate, raw material is easy to get, the borate material of diverse microcosmic structure
It is well used in fields such as semi-conducting material, nonlinear optics, ferroelectric material, laser crystals.
Brief description of the drawings：
Fig. 1 is the mono-crystalline structures schematic diagram of many Boratex pore passage structure materials of the present invention, wherein (a) is [B12O18
(OH)6]6-The two-dimentional supermolecule boron-oxygen Rotating fields schematic diagram of cluster unit formation, (b) is 12 yuan of rings " honeycomb " shape along c-axis direction
Two-dimentional sodium-oxygen layer structural representation, (c) replaces stacking with sodium-oxygen layer for the boron-oxygen layer of two dimension and links the three-dimensional micropore knot to be formed
Structure schematic diagram.
Fig. 2 is the dissymmetrical structure unit figure of many Boratex pore passage structure materials of the present invention.
Fig. 3 is the XRD spectra of many Boratex pore passage structure material powders of the present invention.
Fig. 4 is the infrared spectrogram of many Boratex pore passage structure materials of the present invention.
Fig. 5 is the UV-Vis DRS spectrum of many Boratex pore passage structure materials of the present invention.
Fig. 6 is the thermogravimetic analysis (TGA) figure of many Boratex pore passage structure materials of the present invention.
Embodiment：
Below by embodiment and the invention will be further described with reference to accompanying drawing.
Embodiment 1：
The present embodiment is by 0.169g Li2B4O7With 0.381g Na4B4O7·10H2O is separately added into 30mL polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, 2mL deionized waters and 3mL ethylenediamines are then added, will be stainless after mixed liquor is sufficiently stirred for
Steel reactor is sealed and put into be reacted 10 days in 180 DEG C of baking oven, and stainless steel cauldron then is taken out into naturally cold at room temperature
But, the crystal for reacting generation is removed and cleaned repeatedly with deionized water, drying at room temperature obtains colourless block many Boratex lists
It is brilliant.
Colourless block many boric acid sodium crystals manufactured in the present embodiment have three-dimensional un-densified structure (as shown in Figure 1), thirdly
Dimension structure is to be formed by two-dimentional " boron-oxygen " oversubscription sublayer with " sodium-oxygen " metal level alternate links.Wherein, in ab planes,
[B12O18(OH)6] the two-dimentional supermolecule " boron-oxygen layer " that is formed by hydrogen bond of cluster anions, NaO6And NaO7Polyhedron forms novelty
Cellular " sodium-oxygen " metal level, can be observed one-dimensional cellular duct in terms of c-axis, its molecular formula is [H3O][Na5B12O18
(OH)6]·2H2O, molecular weight is 689.77, and crystallographic parameter isα=β=
90 °, γ=120 °, V=Z=6；.Property test shows that the band gap of the compound is about 5.28eV, can be made
For wide-band-gap semiconductor material.
Embodiment 2：
The present embodiment is by 0.169g Li2B4O7With 0.381g Na4B4O7·10H2It is lining that O, which is added to 25mL polytetrafluoroethylene (PTFE),
In stainless steel cauldron in, then add 0.5mL deionized waters, 3mL ethylenediamines, stir half an hour, finally will be equipped with anti-
The stainless steel cauldron of liquid is answered to seal, crystallization obtains colourless bulk crystals in 170 DEG C of baking oven after 12 days, by such as embodiment
The method cooled down in 1, being filtered, washed and dried, obtained target product items are characterized and result is same as Example 1.
Embodiment 3：
The present embodiment uses 2mL deionized waters, 3mL second in a 30mL polytetrafluoroethylene (PTFE) is the stainless steel cauldron of lining
Two amine solvent 0.169g Li2B4O7And 0.720gNa4B4O7·10H2O, is stirred at room temperature half an hour formation homogeneous reaction liquid,
Then the stainless steel cauldron sealing of reaction solution is will be equipped with, crystallization obtains colourless bulk crystals in 180 DEG C of baking oven after 9 days,
Method by cooling down, being filtered, washed and dried in such as embodiment 1, obtained target product items are characterized and result and implementation
Example 1 is identical.
Embodiment 4：
The present embodiment a 25mL polytetrafluoroethylene (PTFE) for lining stainless steel cauldron in 1.5mL deionized waters,
2.5mL ethylenediamines dissolving 0.128g Li2B4O7And 0.381gNa4B4O7·10H2O, is sufficiently stirred at room temperature, by above-mentioned reaction
Liquid is sealed with stainless steel cauldron, and crystallization obtains colourless bulk crystals in 175 DEG C of baking oven after 10 days, by such as embodiment 1
Middle cooling, the method being filtered, washed and dried, obtained target product items are characterized and result is same as Example 1.
Claims (3)
1. a kind of many Boratex pore passage structure materials, it is characterised in that its molecular formula is [H3O][Na5B12O18(OH)6]·2H2O,
Molecular weight is 689.77, and crystallographic data is α=β=90 °, γ=
120 °,Z=6；The material has one-dimensional regular pore canal structure, is trigonal system, R-3c space groups, most
Na atoms, 2 boron atoms, 4 oxygen atoms and dissociating water molecule comprising 1.5 crystallography independence in small asymmetric cell etc..B
Atom takes common BO3Plane triangle and BO4Four sides bulk-mode, Na atoms take NaO6And NaO7Two kinds of coordination environments, 6
Individual BO4Tetrahedron and 6 BO2(OH) plane triangle polymerize to form [B12O18(OH)6] cluster anions, adjacent [B12O18
(OH)6] cluster anions form two-dimentional supermolecule " boron-oxygen layer ", 9 NaO by hydrogen bond action in ab planes6With 3 NaO7Multiaspect
Body forms two-dimentional " sodium-oxygen " metal level, two-dimentional supermolecule " boron-oxygen " layer and two-dimentional " sodium-oxygen " gold by common summit in ab planes
Category layer links to form micropore Boratex three-dimensional structure along c-axis direction alternating stacking.
2. a kind of preparation method of many Boratex pore passage structure materials as claimed in claim 1, it is characterised in that specifically prepared
Cheng Wei：
(1), metal sodium source, boron source, organic amine and solvent are well mixed, wherein metal sodium source and the mol ratio of organic amine are 1：
36~37, the mol ratio of boron source and organic amine is 1：18~19, the mol ratio of organic amine and solvent is 2.5：1, at room temperature fully
Stirring obtains mixture；
(2), the mixture for obtaining step (1) is transferred in the stainless steel high-pressure reaction vessel with cup in polytetrafluoroethylene (PTFE),
170-180 DEG C of crystallization 9~12 days, obtains the colourless bulk crystals with good crystallinity；
(3), colourless bulk crystals obtained by step (2) are washed with deionized, suction filtration, and be dried at room temperature for, prepare
Many boric acid sodium crystals with three-dimensional micropore structure.
3. the preparation method of many Boratex pore passage structure materials according to claim 1, it is characterised in that described metallic sodium
Source is sodium tetraborate；Boron source is Li2B4O7It is (0.7-1.0) with sodium tetraborate mol ratio:The mixture of (1.0-2.0)；Organic amine
For ethylenediamine；Solvent is deionized water；The volume of stainless steel cauldron is 25mL or 30mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433156A (en) * | 2018-02-07 | 2020-07-17 | 国立大学法人东京工业大学 | Boron atomic layer sheet, laminated sheet, method for producing same, and liquid crystal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1270624A1 (en) * | 1984-10-31 | 1986-11-15 | Норильский Ордена Ленина И Ордена Трудового Красного Знамени Горно-Металлургический Комбинат Им.А.П.Завенягина | Method of preparing specimens for analysis by x-ray spectrometry |
| CN102191547A (en) * | 2010-03-02 | 2011-09-21 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium zinc triskaideca-borate hydrate, and preparation and application thereof |
| CN105347354A (en) * | 2015-11-16 | 2016-02-24 | 贵州师范学院 | Alkaline-earth metal borate and synthetic method thereof |
-
2017
- 2017-03-22 CN CN201710176991.2A patent/CN106976888A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1270624A1 (en) * | 1984-10-31 | 1986-11-15 | Норильский Ордена Ленина И Ордена Трудового Красного Знамени Горно-Металлургический Комбинат Им.А.П.Завенягина | Method of preparing specimens for analysis by x-ray spectrometry |
| CN102191547A (en) * | 2010-03-02 | 2011-09-21 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium zinc triskaideca-borate hydrate, and preparation and application thereof |
| CN105347354A (en) * | 2015-11-16 | 2016-02-24 | 贵州师范学院 | Alkaline-earth metal borate and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LI WEI等，: "A novel mixed-metal borate with large [B12O18(OH)6]6-motif:Synthesis, structure and property", 《SOLID STATE SCIENCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111433156A (en) * | 2018-02-07 | 2020-07-17 | 国立大学法人东京工业大学 | Boron atomic layer sheet, laminated sheet, method for producing same, and liquid crystal |
| CN111433156B (en) * | 2018-02-07 | 2023-12-19 | 国立大学法人东京工业大学 | Boron atomic layer sheet, laminated sheet, method for producing same, and liquid crystal |
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Application publication date: 20170725 |