CN115353634A - Viologen nickel complex modified octamolybdate crystalline material, synthesis method and application - Google Patents
Viologen nickel complex modified octamolybdate crystalline material, synthesis method and application Download PDFInfo
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- CN115353634A CN115353634A CN202111289781.7A CN202111289781A CN115353634A CN 115353634 A CN115353634 A CN 115353634A CN 202111289781 A CN202111289781 A CN 202111289781A CN 115353634 A CN115353634 A CN 115353634A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002178 crystalline material Substances 0.000 title claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 125000003564 m-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(C#N)=C1[H])C([H])([H])* 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- -1 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-ium Chemical compound 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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Abstract
The invention discloses a viologen nickel complex modified octamolybdate based crystalline material, which is characterized in that the molecular formula of a compound of the viologen nickel complex modified octamolybdate based crystalline material is as follows: ni II (3cbbp)(β‑Mo 8 O 26 ) (ii) a Wherein 3cbbp is 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-ium. The present invention uses octamolybdate as inorganic building block, and connects it with viologen nickel complex to form one-dimensional crystalline material. Wherein: ni II (3cbbp)(β‑Mo 8 O 26 ) The structure is a two-dimensional layer structure, the synthesis method is simple, and the purification is convenient; the viologen compound is adopted as a nitrogen-containing ligand, and the viologen ligand has good water solubility, is beneficial to crystallization of crystalline materials, and improves the synthesis yield; the synthesized crystalline material is sensitive to temperature, can generate a thermochromic phenomenon, and can be used as a temperature-sensitive material.
Description
Technical Field
The invention relates to a crystalline catalytic material and a synthetic method thereof, in particular to a viologen nickel complex modified octamolybdate crystalline material, a synthetic method and application thereof.
Background
The multi-metal hydrochloride compound modified by the viologen organic ligand is an inorganic-organic hybrid crystalline functional material and has the optical properties of abundant structure, photochromism or thermochromic and the like. However, the design and synthesis of such crystalline materials face the main problem that the design and synthesis of the first suitable viologen ligand has low organic molecule usage rate, but it is difficult to obtain crystalline materials with novel structure and excellent performance. Secondly, preparing a compound with specific properties by adopting a molecular clipping method. The synthesis method of the heteropoly compound modified by the viologen metal complex is mainly a hydrothermal method, a solvothermal method and the like, and the method has the advantages of convenience and rapidness. The disadvantage is that it is difficult to control.
Disclosure of Invention
The invention aims to solve the technical problem of providing a viologen nickel complex modified polymolybdate-based crystalline material which is convenient and quick in synthesis method and has good response to ultraviolet rays, and a synthesis method and application thereof.
In order to solve the problems existing in the background technology, the technical solution of the invention is as follows:
a crystalline material based on viologen nickel complexes and octamolybdates, the molecular formula of the compound is:
Ni II (3cbbp)(β-Mo 8 O 26 ) (ii) a Wherein 3cbbp is 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-onium.
The synthesis method of the octamolybdate crystalline material based on the modification of the viologen nickel complex comprises the following specific steps:
(1) Mixing Ni (NO) 3 ) 2 Adding sodium molybdate and viologen organic ligand into deionized water, and stirring at room temperature for 40min to form a suspension mixture, wherein the viologen organic ligand is 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-onium;
(2) Adjusting the pH to be 4.0-5.0 by using 1.0mol/L ammonia water solution, pouring the solution into a high-pressure reaction kettle, heating the solution to 130 ℃, preserving the temperature for 9 days, and performing gradient cooling to room temperature to obtain massive yellow crystals;
(3) And (3) cleaning the block yellow crystal obtained in the step (2) with deionized water, naturally airing at room temperature, and modifying the viologen nickel complex with the isopolymolybdate crystal state material.
In the step (2), the temperature rising rate of the reaction kettle is 70-85 ℃/h when the temperature is raised, and the temperature reducing rate is 8 ℃/h when the temperature is reduced.
The adding amount of the deionized water in the step (3) is 60% of the volume of the high-pressure reaction kettle.
The viologen nickel complex modified octamolybdate crystalline material is applied as a photochromic material.
Due to the adoption of the technical scheme, the invention has the following beneficial effects: the present invention uses octamolybdate as inorganic building block, and connects it with viologen nickel complex to form one-dimensional crystalline material. Wherein: ni II (3cbbp)(β-Mo 8 O 26 ) The structure is a two-dimensional layer structure, the synthetic method is simple, and the purification is convenient; the viologen compound is adopted as a nitrogen-containing ligand, and the viologen ligand has good water solubility, is beneficial to crystallization of crystalline materials, and improves the synthesis yield; the synthesized crystalline material is sensitive to temperature, can generate a thermochromic phenomenon, and can be used as a temperature-sensitive material.
Drawings
In order to more clearly illustrate the present invention, embodiments will be briefly described below with reference to the accompanying drawings.
FIG. 1 is a diagram of the coordination environment of an octamolybdate crystalline material based on modification of viologen nickel complexes synthesized by the present invention;
FIG. 2 shows Ni synthesized by the present invention II (3cbbp)(β-Mo 8 O 26 ) A one-dimensional supramolecular chain diagram of (a);
FIG. 3 shows the addition of Ni synthesized according to the present invention II (3cbbp)(β-Mo 8 O 26 ) The thermochromic pattern of (a);
FIG. 4 shows the addition of Ni synthesized according to the present invention II (3cbbp)(β-Mo 8 O 26 ) Ammonia discoloration map of (a).
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the technical scheme in the embodiment of the invention will be clearly and completely described below with reference to the attached drawings in the embodiment of the invention.
Example 1
The synthesis method of the octamolybdate crystalline material based on the modification of the viologen nickel complex comprises the following specific steps:
(1) Mixing Ni (NO) 3 ) 2 Adding sodium molybdate and viologen organic ligand into deionized water, and stirring at room temperature for 40min to form a suspension mixture, wherein the viologen organic ligand is 1- (3-cyanobenzyl) -4,4' -dipyridyl-1-onium;
(2) Adjusting the pH to be 4.0-5.0 by using 1.0mol/L ammonia water solution, pouring the solution into a high-pressure reaction kettle, heating the solution to 130 ℃, preserving the temperature for 9 days, and performing gradient cooling to room temperature to obtain massive yellow crystals;
(3) And (3) cleaning the block yellow crystal obtained in the step (2) with deionized water, naturally airing at room temperature, and modifying the viologen nickel complex with the isopolymolybdate crystal state material.
In the step (2), the temperature rising rate of the reaction kettle is 70-85 ℃/h when the temperature is raised, and the temperature reducing rate is 8 ℃/h when the temperature is reduced.
The adding amount of the deionized water in the step (3) is 60% of the volume of the high-pressure reaction kettle.
Example 2
Synthesis of Ni II (3cbbp)(β-Mo 8 O 26 ) Wherein 3cbbp is 3-1- (3-cyanobenzyl) -4,4' -bipyridyl-1-ium.
0.1mmol of 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-ium, 0.13mmol of sodium molybdate, and 0.5mmol of Ni (NO) 3 ) 2 And 10mL H 2 Sequentially adding O into a 50mL beaker, stirring at room temperature for 30min, adjusting the pH to 4.5 with 1.0mol/L NaOH solution, and pouringHeating to 160 ℃ at a heating rate of 80 ℃/h in a 25mL high-pressure reaction kettle, preserving heat for 5 days under a hydrothermal condition, cooling to room temperature at a cooling rate of 10 ℃/h to obtain green blocky crystals, washing with deionized water for 2 times, and naturally drying at room temperature to obtain Ni II (3cbbp)(β-Mo 8 O 26 ) The yield is 40%, the coordination environment diagram is shown in figure 2, and the two-dimensional layered diagram is shown in figure 3.
Characterization of octamolybdate crystalline material based on viologen nickel complex modification
Determination of Crystal Structure
Single crystals of appropriate size were selected with a microscope and analyzed at room temperature using a Bruker SMART 1000CCD diffractometer (graphite monochromator, mo-Ka,
) Diffraction data was collected. Scan mode w- φ, the diffraction data was corrected for absorption using the SADABS program. Data reduction and structure resolution were done using SAINT and SHELXTL programs, respectively. And determining all non-hydrogen atom coordinates by a least square method, and obtaining the hydrogen atom position by a theoretical hydrogenation method. And (3) refining the crystal structure by adopting a least square method. FIGS. 1 and 2 show the basic coordination and stacking of the viologen nickel complex modified octamolybdate crystalline material synthesized in example 1. Some parameters of the collection of the crystallographic diffraction point data and the structure refinement are shown in the following table:
thermochromic test
Ni synthesized in example 1 II (3cbbp)(β-Mo 8 O 26 ) (Compound 1);
and performing a thermochromic experiment, and determining the temperature sensitivity of the compound 1 by taking the color change of the crystal material as a basis for judging thermochromic.
The specific experimental steps are as follows:
placing a plurality of granules of the compound 1 on a glass sheet, placing the glass sheet under an optical microscope with an electronic eyepiece, adjusting the visual field focal length to be clear, photographing and storing, then moving the glass sheet into an oven at 60 ℃, heating for 5 minutes at the temperature, taking out the glass sheet, placing under the microscope, photographing and storing. The above steps are repeated at 70, 80, 823060 and 180 deg.C. It can be observed that the color of compound 1 gradually changed from light green to dark green. After heating, compound 1 was photographed every 10 minutes, and it was found that the compound gradually returned to its original color, that is, compound 1 gradually changed from dark green to light green, taking 3 hours.
Ammonia induced discoloration test
Ni synthesized in example 1 II (3cbbp)(β-Mo 8 O 26 ) 0.5 (Compound 1);
and performing an ammonia discoloration experiment, wherein the color change of the crystal material is used as a basis for judging ammonia discoloration, and the ammonia discoloration experiment is used for determining the temperature sensitivity of the compound 1.
The specific experimental steps are as follows:
and (3) picking out the compound 1 with a regular and complete structure under an optical microscope, placing the compound under the optical microscope provided with the SAGA electron eyepiece, adjusting the focal length of the visual field to be clear, and taking a picture for storage. Then preparing ammonia water solution with the concentration of 1, 2, 823070, 8230and 12mol/L respectively, placing the compound 1 in 1mol/L ammonia water, taking a picture of the compound 1 again in an ammonia gas atmosphere with the concentration for 3min, repeating the steps, and taking a picture for storage when the compound 1 is respectively in ammonia gas atmospheres with other concentrations.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. The viologen nickel complex modified octamolybdate-based crystalline material is characterized in that the molecular formula of a compound of the viologen nickel complex modified octamolybdate-based crystalline material is as follows: ni II (3cbbp)(β-Mo 8 O 26 ) (ii) a Wherein 3cbbp is 1- (3-cyanobenzyl) -4,4' -bipyridyl-1-onium.
2. The synthesis method of the octamolybdate crystalline material modified based on the viologen nickel complex is characterized by comprising the following specific steps:
(1) Mixing Ni (NO) 3 ) 2 Adding sodium molybdate and viologen organic ligand into deionized water, and stirring at room temperature for 40min to form a suspension mixture, wherein the viologen organic ligand is 1- (3-cyanobenzyl) -4,4' -dipyridyl-1-onium;
(2) Adjusting the pH to be 4.0-5.0 by using 1.0mol/L ammonia water solution, pouring the solution into a high-pressure reaction kettle, heating the solution to 130 ℃, preserving the temperature for 9 days, and performing gradient cooling to room temperature to obtain massive yellow crystals;
(3) And (3) cleaning the massive yellow crystal obtained in the step (2) by using deionized water, naturally airing at room temperature, and modifying the material in the isopolymolybdate crystal state by using the viologen nickel complex.
3. The method for synthesizing the octamolybdate crystalline material based on the modification of the viologen nickel complex as claimed in claim 2, wherein in the step (2), the temperature rising rate of the reaction kettle is 70-85 ℃/h when the temperature is raised, and the temperature falling rate of the reaction kettle is 8 ℃/h when the temperature is lowered.
4. The method for synthesizing the octamolybdate crystalline material based on the modification of the viologen nickel complex as claimed in claim 2, wherein the addition amount of the deionized water in the step (3) is 60% of the volume of the high-pressure reaction kettle.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086606A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of nickel-bridged flexible ligand and polymolybdate hybridized material |
| CN109942831A (en) * | 2019-04-10 | 2019-06-28 | 山西师范大学 | Two kinds of photochromic purpurine Subjective and Objective MOFs materials and its preparation and application |
| CN112281218A (en) * | 2020-09-21 | 2021-01-29 | 山西师范大学 | Electron transfer type photochromic crystal material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086606A (en) * | 2014-07-08 | 2014-10-08 | 吉林化工学院 | Structure and preparation method of nickel-bridged flexible ligand and polymolybdate hybridized material |
| CN109942831A (en) * | 2019-04-10 | 2019-06-28 | 山西师范大学 | Two kinds of photochromic purpurine Subjective and Objective MOFs materials and its preparation and application |
| CN112281218A (en) * | 2020-09-21 | 2021-01-29 | 山西师范大学 | Electron transfer type photochromic crystal material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孙小娟: "紫精-多金属氧酸盐杂化新材料的制备及其光催化热性的探究" * |
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