CN109467715B - Synthesis method of cobalt phosphate inorganic-organic hybrid material - Google Patents
Synthesis method of cobalt phosphate inorganic-organic hybrid material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 229910000152 cobalt phosphate Inorganic materials 0.000 title claims abstract description 46
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 45
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- LKKFBCXZHOATNA-UHFFFAOYSA-N cobalt(3+) phosphite Chemical compound [Co+3].[O-]P([O-])[O-] LKKFBCXZHOATNA-UHFFFAOYSA-N 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 13
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000003760 magnetic stirring Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a synthesis method of a cobalt phosphate inorganic-organic hybrid material, which comprises the steps of adopting a hydrothermal method, mixing phosphorous acid, 1, 4-butanediamine, cobalt acetate and deionized water according to a certain molar ratio under magnetic stirring to obtain sol, filling the sol into a 20ml polytetrafluoroethylene reaction kettle, and crystallizing for 3 days at 160 ℃ under autogenous pressure to obtain the cobalt phosphate inorganic-organic hybrid material; then directly converting the cobalt phosphate into the cobalt phosphate inorganic-organic hybrid material by a method of controlling temperature by program and controlling heating in atmosphere on the premise of keeping the framework structure. The method provides a new method for synthesizing the inorganic-organic hybrid material of cobalt phosphate, can synthesize the inorganic-organic hybrid material of cobalt phosphate, is synthesized by directly sintering and converting the inorganic-organic hybrid material of cobalt phosphite, and does not contain other impurity phases.
Description
Technical Field
The invention belongs to the technical field of preparation of inorganic-organic hybrid materials of phosphate, and particularly relates to a synthesis method of inorganic-organic hybrid materials of cobalt phosphate.
Background
Inorganic-organic hybrid metal phosphates have been extensively studied by researchers during the past decades due to their abundant structural and regular pore channel applications in the fields of ion exchange, gas separation, industrial catalysis, electromagnetism, photoluminescence, and the like. Recently, researchers have found that the synthesis of phosphorous acid containing pseudo-tetrahedral configuration instead of phosphoric acid containing regular tetrahedral configuration has generated a great deal of research interest and has achieved a great deal of research effort. Such substitution can reduce M-O-P connection, generate more blocking structures, and form novel open skeleton compounds, especially large-pore and extra-large-pore phosphite open skeletons.
Since the first example of organic amine-containing cobalt phosphite was synthesized by t.rojo et al in 2001, various structures having a zero-dimensional (0D) cluster, a one-dimensional (1D) chain, a two-dimensional (2D) layer, and a three-dimensional (3-day) open skeleton were sequentially synthesized and reported. As is well known, properties of cobalt-containing compounds are related to coordination environments and connection modes thereof in structures, and in open-framework cobalt phosphite compounds, cobalt atoms form a CoOn (n ═ 4, 5, 6) polyhedron in three modes of four coordination, five coordination and six coordination, and have a plurality of connection modes such as common vertex, common side or common plane, so that cobalt phosphite compounds with various special structures and properties are synthesized.
The synthesis and performance research of the phosphorous acid inorganic-organic hybrid material are greatly advanced, and a pore channel structure which is richer and larger than silicate and phosphate is obtained, but the application of the phosphorous acid inorganic-organic hybrid material in the aspects of industrial catalysis, gas separation and the like is limited due to the problem of the thermal stability of phosphorous acid groups; phosphate inorganic-organic hybrid materials have excellent performance in the aspect of thermal stability, however, phosphate groups have poor performance in the aspect of synthesizing a macroporous structure compared with phosphorous acid groups, so that how to synthesize a structure by using phosphorous acid and have the stability of phosphate becomes the direction of efforts of researchers, and is a key problem to be solved in the field.
Disclosure of Invention
Based on the defects of the prior art, the technical problem to be solved by the invention is to provide a method for synthesizing a cobalt phosphate inorganic-organic hybrid material, which can synthesize the cobalt phosphate inorganic-organic hybrid material, is synthesized by directly sintering and converting the cobalt phosphite inorganic-organic hybrid material, and does not contain other impurity phases.
In order to solve the technical problems, the invention is realized by the following technical scheme: the invention provides a synthesis method of a cobalt phosphate inorganic-organic hybrid material, which comprises the following steps:
s10: mixing a cobalt source and water, magnetically stirring for 0.5h, adding a template agent into the solution, continuously stirring for 0.5h, adding a phosphorus source, and finally stirring for 2h to obtain uniform sol;
s20: putting the sol obtained in the step S10 into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into an oven for crystallization, and separating, washing and drying a solid product to obtain a crystal with a long block shape;
s30: and (4) heating the crystal obtained in the step (S20) to 200 ℃ in a tubular furnace under the protection of an industrial nitrogen atmosphere with the oxygen content of less than or equal to 0.5 percent in the tubular furnace for 30 minutes, sintering and preserving heat at the temperature of 200 ℃ for 2 hours, heating to 250 ℃ in 30 minutes, preserving heat at the temperature of 250 ℃ for 2 hours, heating to 300 ℃ in 30 minutes, preserving heat at the temperature of 300 ℃ for 5 hours, and naturally cooling, wherein the escape speed of nitrogen gas is about 90 bubbles per minute, thereby finally obtaining the inorganic-organic hybrid material of cobalt phosphate.
Preferably, the cobalt source is cobalt acetate, calculated as Co; the phosphorus source is solid phosphorous acid, counted as P; the template agent is 1, 4-butanediamine; the water is deionized water.
Further, the molar ratio of the sol is Co: p: 1, 4-butanediamine: h2O＝1.0:8.0-9.0:15.0-19.0:444。
Optionally, the reaction temperature in the oven is 160 ℃ and the crystallization time is 3 days.
According to the method, a hydrothermal method is adopted, phosphorous acid, 1, 4-butanediamine, cobalt acetate and deionized water are stirred under magnetic force according to a certain molar ratio to obtain sol, the sol is filled into a polytetrafluoroethylene reaction kettle of 20ml, and the sol is crystallized for 3 days under the autogenous pressure at 160 ℃ to obtain the cobalt phosphite inorganic-organic hybrid material; then directly converting the cobalt phosphate into the cobalt phosphate inorganic-organic hybrid material by a method of controlling temperature by program and controlling heating in atmosphere on the premise of keeping the framework structure. The method provides a new method for synthesizing the inorganic-organic hybrid material of cobalt phosphate, can synthesize the inorganic-organic hybrid material of cobalt phosphate, is synthesized by directly sintering and converting the inorganic-organic hybrid material of cobalt phosphite, and does not contain other impurity phases.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments, together with the accompanying drawings.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a diagram of an asymmetric structural unit of a cobalt phosphite inorganic-organic hybrid material prepared by the present invention;
FIG. 2 is an XRD experiment and a simulated spectrum of the cobalt phosphite inorganic-organic hybrid material obtained by the invention;
FIG. 3 is a temperature-variable XRD map of the cobalt phosphite inorganic-organic hybrid material obtained by the present invention, wherein (a) represents 25 ℃, (b) represents 100 ℃, (c) represents 200 ℃, (d) represents 300 ℃, (e) represents 400 ℃, (f) represents 500 ℃, (g) represents 600 ℃, (h) represents 700 ℃;
FIG. 4 is an SEM spectrogram of the cobalt phosphite inorganic-organic hybrid material prepared by the invention;
FIG. 5 is a schematic structural diagram of a cobalt phosphite inorganic-organic hybrid material prepared by the present invention;
FIG. 6 is an infrared spectrum of the inorganic-organic hybrid cobalt phosphite material prepared by the present invention;
FIG. 7 is a comparative diagram of XRD experiment of inorganic-organic hybrid materials of cobalt phosphite and cobalt phosphate prepared by the present invention;
FIG. 8 is an XRD comparison graph of the inorganic-organic hybrid cobalt phosphate material prepared by the present invention at different temperatures;
FIG. 9 is an SEM spectrogram of the inorganic-organic hybrid cobalt phosphate material prepared by the present invention;
FIG. 10 is an infrared spectrum of the inorganic-organic hybrid cobalt phosphate material prepared according to the present invention;
FIG. 11 is a thermal process diagram of the conversion of cobalt phosphite to cobalt phosphate inorganic-organic hybrid material according to the present invention;
FIG. 12 is a flow chart of the method for synthesizing the inorganic-organic hybrid cobalt phosphate material of the present invention.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which form a part of this specification, and which illustrate, by way of example, the principles of the invention. In the referenced drawings, the same or similar components in different drawings are denoted by the same reference numerals.
The method comprises the steps of uniformly mixing a cobalt source, a phosphorus source, an organic template and water, stirring at room temperature to prepare uniform sol, pouring the sol into a stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal crystallization for 3 days under the autogenous pressure of 160 ℃, washing obtained crystals with distilled water, and drying at 60 ℃ to obtain an intermediate product, wherein the obtained intermediate product is a well-crystallized crystal in a long block shape. The synthetic cobalt phosphate microporous material is characterized in that on the premise of keeping a framework structure, a cobalt phosphite inorganic-organic hybrid material is directly converted into a cobalt phosphate inorganic-organic hybrid material, the shape of the cobalt phosphate inorganic-organic hybrid material is a long block, the crystal length is about 100 micrometers, and the section length is between 10 and 20 micrometers.
Example 1:
mixing cobalt acetate and deionized water, magnetically stirring for 0.5h, adding template agent 1, 4-butanediamine into the solution, continuously stirring for 0.5h, adding phosphorous acid, and finally stirring for 2h to obtain uniform sol. The molar ratio of the sol is Co: p: 1, 4-butanediamine: h2O ═ 1.0:8.0-9.0:15.0-19.0: 444. Standing the obtained sol for 0.5h, placing into a 20ml polytetrafluoroethylene reaction kettle, placing in a 160 ℃ oven for crystallization for 3 days, separating, washing and drying the solid product to obtain crystals with a long block shape, wherein the crystals do not contain other amorphous substances, and the crystal is shown in figure 4. Heating the obtained crystal to 200 ℃ in a tube furnace under the protection of industrial nitrogen (oxygen content is less than or equal to 0.5%) atmosphere for 30 minutes, sintering and preserving heat for 2 hours at 200 ℃, then heating to 250 ℃ in 30 minutes, preserving heat for 2 hours at 250 ℃, then heating to 300 ℃ in 30 minutes, preserving heat for 5 hours at 300 ℃, and then naturally cooling, wherein the escape speed of nitrogen gas is about 90 bubbles per minute, and the maximum escape speed isThen obtaining the cobalt phosphate inorganic-organic hybrid material with a long block shape, and the whole flow is shown in figure 12.
Example 2:
mixing cobalt acetate and deionized water, magnetically stirring for 0.5h, adding template agent 1, 4-butanediamine into the solution, continuously stirring for 0.5h, adding phosphorous acid, and finally stirring for 2h to obtain uniform sol. The molar ratio of the sol is Co: p: 1, 4-butanediamine: h2O ═ 1.0:8.0-9.0:15.0-19.0: 444. Standing the obtained sol for 0.5h, placing into a 20ml polytetrafluoroethylene reaction kettle, placing in a 160 ℃ oven for crystallization for 3 days, separating, washing and drying the solid product to obtain crystals with a long block shape, wherein the crystals do not contain other amorphous substances, and the crystal is shown in figure 4. Heating the obtained crystal to 200 ℃ in a tube furnace under the protection of pure nitrogen (oxygen content is less than or equal to 0.01%) atmosphere for 30 minutes, sintering and preserving heat for 2 hours at the temperature of 200 ℃, then heating to 250 ℃ in 30 minutes, preserving heat for 2 hours at the temperature of 250 ℃, then heating to 300 ℃ in 30 minutes, preserving heat for 5 hours at the temperature of 300 ℃, and then naturally cooling, wherein the escape speed of nitrogen gas is about 90 bubbles per minute, finally obtaining the material with the shape of a long block, and performing infrared test on the material, wherein the crystal also has an H-P bond characteristic peak, which shows that under the protection of pure nitrogen, the oxygen content is relatively low, and cobalt phosphite is not oxidized into the inorganic-organic hybrid material of cobalt phosphate.
Example 3:
mixing cobalt acetate and deionized water, magnetically stirring for 0.5h, adding template agent 1, 4-butanediamine into the solution, continuously stirring for 0.5h, adding phosphorous acid, and finally stirring for 2h to obtain uniform sol. The molar ratio of the sol is Co: p: 1, 4-butanediamine: h2O ═ 1.0:8.0-9.0:15.0-19.0: 444. Standing the obtained sol for 0.5h, placing into a 20ml polytetrafluoroethylene reaction kettle, placing in a 160 ℃ oven for crystallization for 3 days, separating, washing and drying the solid product to obtain crystals with a long block shape, wherein the crystals do not contain other amorphous substances, and the crystal is shown in figure 4. Heating the obtained crystal to 200 ℃ in a tubular furnace under the protection of industrial nitrogen (oxygen content is less than or equal to 0.5%) atmosphere for 30 minutes, sintering and preserving heat for 2 hours at the temperature of 200 ℃, then heating to 250 ℃ in 30 minutes, and heating to 250 ℃ in a tubular furnaceAnd (3) preserving the temperature for 5H at the temperature of 250 ℃, then naturally cooling, wherein the escape speed of nitrogen gas is about 90 bubbles per minute, and finally obtaining the material with the shape of a long block, wherein the crystal also has a characteristic peak of an H-P bond through an infrared test, which shows that the cobalt phosphite is not oxidized into the cobalt phosphate inorganic-organic hybrid material at the temperature of 250 ℃.
As shown in fig. 1, it contains one crystallographically non-equivalent P atom, two crystallographically non-equivalent Co atoms, and a half organic amine molecule. The P (1) atom coordinates with the surrounding three oxygen atoms and one hydrogen atom to form HPO3Pseudo-tetrahedron, the Co (1) atom forming a CoO with six surrounding oxygen atoms6Octahedron, Co (2) atoms coordinated with five surrounding oxygen atoms and nitrogen atom in organic amine to form CoO5An N octahedron.
As shown in FIG. 2, the diffraction peak positions of the powder spectrogram of the cobalt phosphite inorganic-organic hybrid material sample obtained by the invention and the spectrogram simulated according to the single crystal structure are basically consistent, which shows that the synthesized substance is pure phase.
The variable temperature XRD of the cobalt phosphite inorganic-organic hybrid material obtained by the invention is shown in figure 3, and has a characteristic peak at 300 ℃, and the structure completely collapses at 400 ℃. At 500 deg.C, there is absorption peak, and with the rise of temperature, when reaching 700 deg.C, it can be found that the absorption peak is correspondent to the compact phase cobalt phosphate Co3(PO4)2The channel structure is completely changed.
FIG. 4 is a scanning electron micrograph of the cobalt phosphite inorganic-organic hybrid material obtained by the present invention, from which it can be seen that the material is a crystal in the shape of a long block, the length of the crystal grain is about 100um, the length of the cross section is between 10-20 um, and no other amorphous material and impurity phase are contained.
As shown in fig. 5a, the cobalt phosphite inorganic-organic hybrid material is composed of an inorganic two-dimensional layer skeleton and 1, 4-butanediamine organic molecules; the inorganic two-dimensional layer skeleton is formed by connecting a Co chain and HPO through infinite common edges3Pseudo-tetrahedron construction, the infinite coterminous Co chain being formed of Co (1) O6/Co(2)O5The N octahedron is formed by common edge connection, and the cobalt chain is different from a common single cobalt chain and is formed by a trinuclear cobalt clusterCo3O11N2And linked together in a side-by-side stacking (fig. 5 b).
FIG. 6 shows the IR spectrum of inorganic-organic hybrid cobalt phosphite material. 2840cm-1-3570cm-1The absorption peak band can be classified as the stretching vibration peak of C-H, N-H and O-H, 2320cm-1Has a sharp absorption peak which can be attributed to the characteristic stretching vibration peak of P-H bond, 1060cm-1、989cm-1、636cm-1And 570cm-1The sharp absorption peaks at (a) can be attributed to the stretching vibration and bending vibration of P-O.
As shown in FIG. 7, the diffraction peak positions of the inorganic-organic hybrid materials of cobalt phosphite and cobalt phosphate prepared by the invention are basically consistent, and the hybrid materials have characteristic peaks of the pore channels, which indicates that the pore channel structure is maintained. Wherein the individual peaks have a shift to the right due to the fact that the P-O bond length is longer than the P-H bond length in the structure, i.e., PO4Occupied space ratio HPO3The occupied space is large and the voids become small, so the characteristic diffraction peak of the hole is shifted to the right.
As shown in fig. 8, characteristic diffraction peaks of the cobalt phosphate inorganic-organic hybrid material still exist at room temperature and 500 ℃, which indicates that the channel structure is maintained, and the intensity of the diffraction peak is reduced at 500 ℃, which indicates that the crystallization degree is reduced; at 600 ℃, the characteristic diffraction peak disappears, which indicates that the cobalt phosphate inorganic-organic hybrid material structure collapses.
FIG. 9 is a scanning electron micrograph of the hybrid cobalt phosphate inorganic-organic material prepared by the present invention, from which it can be seen that the hybrid cobalt phosphate inorganic-organic material is a long bulk crystal, and does not contain other amorphous materials and impurity phases, but has surface defects compared with phosphorous acid, because of the result of high temperature sintering during the preparation process, and other testing means show that the framework structure is maintained.
As shown in FIG. 10, 2800cm-1-3300cm-1The absorption peak band can be classified as the stretching vibration peak of C-H, N-H and O-H, 1070cm-1、1010cm-1、876cm-1And 600cm-1The sharp absorption peaks at (a) can be attributed to the stretching vibration and bending vibration of P-O. 2400cm-1If there is no absorption peak, it indicates that the cobalt phosphate inorganic-organic hybrid material does not contain PThe characteristic stretching vibration peak of the H bond proves that the cobalt phosphite has been oxidized into the prepared cobalt phosphate inorganic-organic hybrid material.
As shown in FIG. 11, the heat treatment process for converting cobalt phosphite into cobalt phosphate inorganic-organic hybrid material comprises the steps of raising the temperature from room temperature to 200 ℃ within 30 minutes, maintaining the temperature at 200 ℃ for 2 hours, then raising the temperature to 250 ℃ within 30 minutes, maintaining the temperature at 250 ℃ for 2 hours, then raising the temperature to 300 ℃ within 30 minutes, then maintaining the temperature at 300 ℃ for 5 hours, and then naturally cooling to room temperature.
The cobalt phosphate inorganic-organic hybrid material is synthesized by directly converting a cobalt phosphite inorganic-organic hybrid material, and the cobalt phosphate inorganic-organic hybrid material is prepared by putting phosphorous acid, 1, 4-butanediamine, cobalt acetate and deionized water according to a certain molar ratio under magnetic stirring to obtain sol, putting the sol into a 20ml polytetrafluoroethylene reaction kettle, and crystallizing for 3 days at 160 ℃ under autogenous pressure to obtain the cobalt phosphite inorganic-organic hybrid material; then directly converting the cobalt phosphate into the cobalt phosphate inorganic-organic hybrid material by a method of controlling temperature by program and controlling heating in atmosphere on the premise of keeping the framework structure. The invention can synthesize the inorganic-organic hybrid material of cobalt phosphate, which is synthesized by directly sintering and converting the inorganic-organic hybrid material of cobalt phosphite and does not contain other impurity phases.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (1)
1. A synthetic method of a cobalt phosphate inorganic-organic hybrid material is characterized by comprising the following steps:
s10: mixing a cobalt source and water, magnetically stirring for 0.5h, adding a template agent into the solution, continuously stirring for 0.5h, adding a phosphorus source, and finally stirring for 2h to obtain uniform sol;
s20: putting the sol obtained in the step S10 into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into an oven for crystallization, and separating, washing and drying a solid product to obtain a crystal with a long block shape; the reaction temperature in the oven is 160 ℃, and the crystallization time is 3 days;
s30: heating the crystal obtained in the step S20 to 200 ℃ in 30 minutes under the protection of industrial nitrogen atmosphere with the oxygen content of less than or equal to 0.5% in a tubular furnace, sintering and preserving heat at the temperature of 200 ℃ for 2 hours, then heating to 250 ℃ in 30 minutes, preserving heat at the temperature of 250 ℃ for 2 hours, then heating to 300 ℃ in 30 minutes, preserving heat at the temperature of 300 ℃ for 5 hours, and then naturally cooling, wherein the escape speed of nitrogen gas is 90 bubbles per minute, thereby finally obtaining the inorganic-organic hybrid material of cobalt phosphate;
the cobalt source is cobalt acetate, calculated as Co; the phosphorus source is solid phosphorous acid, counted as P; the template agent is 1, 4-butanediamine; the water is deionized water;
the molar ratio of the sol is Co: p: 1, 4-butanediamine: h2O＝1.0:8.0-9.0:15.0-19.0:444。
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Application publication date: 20190315 Assignee: Liaoning Sunshine Stone science and Technology Park Co.,Ltd. Assignor: LIAONING TECHNICAL University Contract record no.: X2023210000320 Denomination of invention: A synthesis method of cobalt phosphate inorganic organic hybrid material Granted publication date: 20210518 License type: Common License Record date: 20231227 |