CN115677787A - Mercapto pyridine cobalt complex and preparation method and application thereof - Google Patents
Mercapto pyridine cobalt complex and preparation method and application thereof Download PDFInfo
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- -1 Mercapto pyridine cobalt Chemical compound 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010668 complexation reaction Methods 0.000 title description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 126
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 45
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000013078 crystal Substances 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- XRCUTZKABNKOEY-UHFFFAOYSA-N 2-chloro-6-pyridin-2-ylpyridine Chemical compound ClC1=CC=CC(C=2N=CC=CC=2)=N1 XRCUTZKABNKOEY-UHFFFAOYSA-N 0.000 claims description 15
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 11
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical group [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 10
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 150000004687 hexahydrates Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 description 14
- 229960002026 pyrithione Drugs 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KPOBHNYTWJSVKF-UHFFFAOYSA-L cobalt(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KPOBHNYTWJSVKF-UHFFFAOYSA-L 0.000 description 1
- PLTOVEJYEUZSKT-UHFFFAOYSA-N cobalt;pyridine Chemical compound [Co].C1=CC=NC=C1 PLTOVEJYEUZSKT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the technical field of metal coordination compound functional materials, and discloses a mercapto-pyridine cobalt complex and a preparation method and application thereof. The mercapto cobalt pyridine complex has the advantages of stable and novel structure, better thermal stability, certain photocatalysis effect, simple preparation method, high product purity, easy realization of preparation of the mercapto cobalt pyridine complex and contribution to application and popularization, and can be used as a catalyst in a photocatalysis system to convert methane into methanol.
Description
Technical Field
The invention relates to the technical field of metal coordination compound functional materials, and particularly relates to a mercapto-pyridine cobalt complex and a preparation method and application thereof.
Background
With the increasing shortage of petroleum resources, people pay more and more attention to the development and utilization of natural gas. Methane, the major component of natural gas, is in considerable quantities throughout the world and has been detected to exceed petroleum. Methane has a higher hydrogen-carbon ratio than coal and petroleum, and is considered as a clean energy source. Besides being directly used as fuel, the methane can be converted into methanol or other high value-added products through a catalytic technology, so that more efficient utilization is realized. The photocatalytic technology has the advantages of simple operation, low energy consumption, no secondary pollution, high efficiency and the like, so the application of the photocatalytic technology to the conversion of methane has important academic significance and industrial application value.
The photocatalytic reaction is excited by light energy to generate high-energy electrons and holes, and the high-energy electrons and the holes participate in the activation of a methane C-H bond and the formation of free radicals, so that the Gibbs free energy rise of the reaction is compensated. In addition, the photocatalytic reaction conditions are generally carried out under milder conditions, which provides a new approach for converting methane at low temperatures. In recent years, attention has been paid to direct conversion of methane to an oxygen-containing product such as methanol by the action of an oxidizing agent. After the development and utilization of light energy, research on the conversion of photocatalytic methane is also deepened step by step, in a system for converting the photocatalytic methane into methanol, a catalyst plays an important role, and although the catalyst containing Rh, pt and other precious metals has better photocatalytic performance, the catalyst cost is higher due to the fact that the precious metals are low in storage amount and expensive, and the application of the catalyst in large-scale production is not facilitated. In view of this, it is significant to develop a low-cost non-noble metal catalyst in the technical field of converting methane into methanol by photocatalysis.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides a cobalt sparsely-based pyridine complex with a novel structure and low price, which is used for solving the problem of high production cost caused by applying a material containing noble metal as a catalyst in the reaction of converting methane into methanol in the prior art.
The invention adopts the technical scheme that a mercapto-pyridine cobalt complex, in particular to a mercapto-pyridine cobalt complex, which has the following structural formula:
the invention also aims to provide a preparation method of the mercapto cobalt pyridine complex, which comprises the following steps: in the presence of cobalt (II) perchlorate hexahydrate, 6-chlorine-2,2' -bipyridine is used as a ligand, thiocyanate is used as an auxiliary ligand, and the synthesis is carried out by a solvothermal method.
The invention further aims to provide the application of the cobalt mercapto pyridine complex in the field of photocatalysis, wherein the photocatalyst is particularly used in the reaction of converting methane into methanol.
Compared with the prior art, the invention has the following beneficial effects: firstly, the invention utilizes the characteristic of bidentate coordination of 6-chloro-2,2 '-bipyridine to stably coordinate divalent cobalt ions, and simultaneously, chlorine atoms of 6-chloro-2,2' -bipyridine are substituted by hydrophobe to obtain the hydrophobe pyridine cobalt complex with a novel structure. Secondly, the invention adopts cheap cobalt salt as raw material, thus reducing the preparation cost of the catalyst. Thirdly, the preparation method provided by the invention is simple, the product purity is high, and the preparation of the mercapto cobalt pyridine complex is easy to realize. Finally, the mercapto cobalt pyridine complex has good thermal stability and photocatalysis, can be used for the reaction of converting methane into methanol, and has good application prospect in the field of converting methane into methanol by photocatalysis.
Drawings
FIG. 1 is a schematic diagram of a crystal structure unit of a cobalt pyrithione complex of the present invention.
FIG. 2 is a 1H NMR chart of a cobalt pyrithione complex according to the present invention.
FIG. 3 is a gas chromatographic test chart of the cobalt pyrithione complex of the present invention as a photocatalyst for reducing methane to methanol.
FIG. 4 is a thermogram of a cobalt pyrithione complex according to the present invention.
Detailed Description
The invention provides a mercapto-pyridine cobalt complex, which has the following structural formula:
the molecular formula of the mercapto cobalt pyridine complex is C 22 H 16 CoN 6 S 4 。
The crystal of the mercapto cobalt pyridine complex is a triclinic system, and the space group is
The unit cell parameters are:
α＝80.333(12)°,β＝75.638(11)°,γ＝88.581(11)°,
the decomposition temperature of the mercapto cobalt pyridine complex is 173.4 ℃.
The invention also provides a preparation method of the mercapto-pyridine cobalt complex, which comprises the following steps: under the condition of the existence of cobalt perchlorate hexahydrate (II), 6-chlorine-2,2' -bipyridine is used as a ligand, thiocyanate is used as an auxiliary ligand, and the mercapto pyridine cobalt complex is synthesized by a solvothermal method.
Wherein the chemical formula of cobalt (II) perchlorate hexahydrate is [ Co (ClO) 4 ) 2 ·6H 2 O]In the solvothermal synthesis process, the chlorine atom of 6-chloro-2,2' -bipyridine is converted into mercapto.
The preparation method specifically comprises the following steps:
s1, respectively dissolving 6-chloro-2,2' -bipyridine, cobalt (II) perchlorate hexahydrate and thiocyanate in a good solvent, and mixing to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a closed environment, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, and collecting separated red blocky crystals;
and S3, washing the red blocky crystal obtained in the step S2, and drying to obtain a single crystal sample of the mercapto-pyridine cobalt complex.
In step S1, the thiocyanate is preferably potassium thiocyanate. The molar ratio of the 6-chloro-2,2 '-bipyridine to the potassium thiocyanate to the cobalt (II) perchlorate hexahydrate is preferably 1, and the dosage ratio of the 6-chloro-2,2' -bipyridine to the good solvent is preferably (0.1-0.2) mmol:20mL. The good solvent is preferably composed of methanol and acetonitrile, the volume ratio of the methanol to the acetonitrile is preferably 1:1, and the preparation method of the good solvent is as follows: according to the volume ratio, 0.5 part of methanol is firstly added, then 1 part of acetonitrile is added, and finally 0.5 part of methanol is added.
In the specific operation, three solutes of 6-chloro-2,2' -bipyridine, potassium thiocyanate and cobalt (II) perchlorate hexahydrate are respectively weighed, and then the solutes are respectively mixed and dissolved with a good solvent; specifically, when a good solvent is measured, according to the volume ratio, 0.5 part of methanol is firstly measured and mixed with a solute, the mixture is dissolved, then 1 part of acetonitrile is added and mixed uniformly, and finally 0.5 part of methanol is added and mixed uniformly; finally, the dosage ratio of the three solutes to the good solvent is (0.1-0.2) mmol:20mL. And finally, mixing the solutions which are respectively dissolved to obtain a mixed solution.
In the step S2, the temperature of the solvothermal reaction is 120-140 ℃, the time is 24-72 hours, and the cooling speed to the room temperature is 10 ℃/h; the solvothermal reaction time is preferably 24 to 48 hours for better reaction effect. After the solvothermal reaction is finished, two crystals, namely colorless transparent blocky crystals and red blocky crystals are obtained, the two crystals are separated, and a single crystal test result shows that the colorless transparent blocky crystals are cobalt perchlorate, and the red blocky crystals are the target product, namely the cobalt pyrithione complex.
In step S3, the brown bulk crystals are preferably washed with methanol and/or acetonitrile. After washing, drying can be carried out by adopting a vacuum drying oven, so as to obtain a single crystal sample of the cobalt pyrithione complex.
The preparation method has simple steps and is easy to prepare and obtain the mercapto-pyridine cobalt complex.
The invention also provides application of the mercapto-pyridine cobalt complex as a photocatalyst, and particularly the photocatalyst is used for a reaction of converting methane into methanol.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention will now be further described with reference to specific examples, which are provided for the purpose of illustration only and are not to be construed as limiting the invention. The test samples and test procedures used in the following examples include the following (generally, according to the conventional conditions or according to the conditions recommended by a reagent company if the specific conditions of the experiment not specified in the examples; reagents, consumables and the like used in the following examples are commercially available without specific description).
Example 1
36.7mg (0.1 mmol) of cobalt (II) perchlorate hexahydrate, 19.1mg (0.1 mmol) of 6-chloro-2,2' -bipyridine and 9.7mg (0.1 mmol) of potassium thiocyanate were dissolved in methanol (5 mL), acetonitrile (10 mL), methanol (5 mL), respectively, and the three solutions were mixed to obtain a mixed solution. And sealing the mixed solution, carrying out solvent thermal reaction at 120 ℃, reacting for 72h, cooling to room temperature at the speed of 10 ℃ per hour to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product, namely red blocky crystals, washing with methanol/acetonitrile, and drying in a vacuum drying oven to obtain the single crystal sample of the target product.
Example 2
73.3mg (0.2 mmol) of cobalt (II) perchlorate hexahydrate, 38.1mg (0.2 mmol) of 6-chloro-2,2' -bipyridine and 19.4mg (0.2 mmol) of potassium thiocyanate were dissolved in methanol (5 mL), acetonitrile (10 mL), methanol (5 mL), respectively, and the three solutions were mixed to obtain a mixed solution. And sealing the finally obtained mixed liquid, carrying out solvent thermal reaction at 120 ℃, after 72 hours of reaction, cooling to room temperature at the speed of 10 ℃ per hour to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product, namely, red blocky crystals, washing with methanol/acetonitrile, and drying in a vacuum drying oven to obtain the single crystal sample of the target product.
Example 3
73.3mg (0.2 mmol) of cobalt (II) perchlorate hexahydrate, 38.1mg (0.2 mmol) of 6-chloro-2,2' -bipyridine and 19.4mg (0.2 mmol) of potassium thiocyanate were dissolved in methanol (5 mL), acetonitrile (10 mL), methanol (5 mL), respectively, and the three solutions were mixed to obtain a mixed solution. And sealing the finally obtained mixed liquid, carrying out solvent thermal reaction at 130 ℃, after 48h of reaction, cooling to room temperature at the speed of 10 ℃ per hour to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product, namely, red blocky crystals, washing with methanol/acetonitrile, and drying in a vacuum drying oven to obtain the single crystal sample of the target product.
Example 4
73.3mg (0.2 mmol) of cobalt (II) perchlorate hexahydrate, 38.1mg (0.2 mmol) of 6-chloro-2,2' -bipyridine and 19.4mg (0.2 mmol) of potassium thiocyanate were dissolved in methanol (5 mL), acetonitrile (10 mL), methanol (5 mL), respectively, and the three solutions were mixed to obtain a mixed solution. And sealing the finally obtained mixed liquid, carrying out solvent thermal reaction at 135 ℃, reacting for 48 hours, cooling to room temperature at the speed of 10 ℃ per hour to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product, namely, red blocky crystals, washing with methanol/acetonitrile, and drying in a vacuum drying oven to obtain the single crystal sample of the target product.
Example 5
73.3mg (0.2 mmol) of cobalt (II) perchlorate hexahydrate, 38.1mg (0.2 mmol) of 6-chloro-2,2' -bipyridine and 19.4mg (0.2 mmol) of potassium thiocyanate were dissolved in methanol (5 mL), acetonitrile (10 mL), methanol (5 mL), respectively, and the three solutions were mixed to obtain a mixed solution. And sealing the finally obtained mixed liquid, carrying out solvent thermal reaction at 140 ℃, cooling to room temperature at the speed of 10 ℃ per hour after reacting for 24 hours to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product, namely, red blocky crystals, washing with methanol/acetonitrile, and drying in a vacuum drying oven to obtain the single crystal sample of the target product.
Test method
1. Single crystal diffraction test
The results of diffraction tests on the single crystal samples obtained in examples 1 to 7 on a Rigaku R-AXIS SPIDER diffractometer are shown in FIG. 1. Test results show that the synthesized product is a cobalt pyrithione complex with a novel structure.
2. 1H NMR measurement
The cobalt pyrithione complexes obtained in the examples were structurally determined by 1H NMR technique. The test results are shown in fig. 2, 1H NMR (600mhz, dmso-d 6) δ 8.67 (s, 1H), 8.30 (d, J =48.0hz, 2h), 8.00 (d, J =24.0hz, 2h), 7.98 (s, 1H), 7.50 (d, J =54.0hz, 2h).
3. Gas chromatography detection
When the prepared cobalt pyrithione complex is used as a photocatalyst to reduce methane, the gas phase test result of the liquid product in GC-2014C is shown in figure 3. Wherein the solvent used in the photocatalysis system is PC (propylene carbonate), and the gas phase detection related parameters are as follows: the split ratio is 50, 1, FID column, and the carrier gas is N2. The test result shows that the liquid product obtained after reduction can measure the chromatographic peak of the methanol, and the result shows that the methane can be reduced into the methanol when the cobalt pyrithione complex is used as the photocatalyst.
4. Thermogravimetric testing
The prepared cobalt pyrithione complex is subjected to thermogravimetric test in an SDT-650 thermogravimetric analyzer in the United states, and the test result is shown in figure 4. The test result shows that the decomposition temperature of the cobalt pyrithione complex is 173.4 ℃, and the cobalt pyrithione complex has good thermal stability.
5. Conclusion of the test
In conclusion, the synthesized cobalt pyrithione complex has a novel structure, good thermal stability and a certain photocatalytic effect, can be used as a catalyst in a photocatalytic system to convert methane into methanol, has potential application value in the aspect of photocatalysis, has a simple preparation method and high product purity, is easy to prepare the cobalt pyrithione complex, and is beneficial to application and popularization.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The mercapto cobalt pyridine mercapto cobalt complex has the following structural formula:
2. the cobalt mercapto-pyridine complex according to claim 1, wherein the crystal of the cobalt mercapto-pyridine complex is triclinic and the space group is
The unit cell parameters are:
α＝80.333(12)°,β＝75.638(11)°,γ＝88.581(11)°,
and/or the decomposition temperature of the mercapto cobalt pyridine complex is 173.4 ℃.
3. The preparation method of the mercapto cobalt pyridine complex as claimed in claim 1 or 2, characterized in that 6-chloro-2,2' -bipyridine is used as a ligand and thiocyanate is used as an auxiliary ligand in the presence of cobalt perchlorate (II) hexahydrate, and the synthesis is carried out by a solvothermal method.
4. The preparation method of the mercapto-pyridine cobalt complex as claimed in claim 3, characterized by comprising the following steps:
s1, respectively dissolving 6-chloro-2,2' -bipyridine, cobalt (II) perchlorate hexahydrate and thiocyanate in a good solvent, and mixing to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a closed environment, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, and collecting separated red blocky crystals;
and S3, washing the red blocky crystal obtained in the step S2, and drying to obtain a single crystal sample of the mercapto-pyridine cobalt complex.
5. The method for preparing a cobalt mercapto-pyridine complex according to claim 4, wherein in step S1, the thiocyanate is potassium thiocyanate.
6. The preparation method of the cobalt sparsylpyridine complex according to claim 5, wherein in step S1, the molar ratio of the 6-chloro-2,2' -bipyridine, the potassium thiocyanate and the cobalt (II) perchlorate hexahydrate is 1.
7. The preparation method of the mercapto-pyridine cobalt complex according to claim 5, wherein in step S1, the good solvent is composed of methanol and acetonitrile, the volume ratio of the methanol to the acetonitrile is 1:1, and the preparation method of the good solvent is as follows: according to the volume ratio, 0.5 part of methanol is firstly added, then 1 part of acetonitrile is added, and finally 0.5 part of methanol is added.
8. The method for preparing a cobalt sparsylpyridine complex according to any one of claims 4 to 7, wherein in step S2, the temperature of the solvothermal reaction is 120 to 140 ℃, the time is 24 to 72 hours, and the cooling rate is 10 ℃/h.
9. The method for preparing a cobalt mercaptopyridine complex according to any one of claims 4 to 7, wherein in step S3, the brown bulk crystals are washed with methanol and/or acetonitrile.
10. Use of a cobalt mercapto pyridine complex according to any one of claims 1 to 2 or prepared by a process according to any one of claims 3 to 9 as a photocatalyst for the conversion of methane to methanol.
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| WO2019205309A1 (en) * | 2018-04-28 | 2019-10-31 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine iron or cobalt metal complex catalyst, preparation method therefor, and application thereof |
| CN112194687A (en) * | 2020-11-12 | 2021-01-08 | 云南师范大学 | Metal nickel complex with ether bond bridging type bipyridyl carboxylic acid as ligand, and synthesis method and photocatalytic application thereof |
| CN112898349A (en) * | 2021-01-19 | 2021-06-04 | 云南师范大学 | Metal manganese complex with 4,4 '-diamino-2, 2' -bipyridine as ligand, synthetic method and photocatalytic application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019205309A1 (en) * | 2018-04-28 | 2019-10-31 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine iron or cobalt metal complex catalyst, preparation method therefor, and application thereof |
| CN112194687A (en) * | 2020-11-12 | 2021-01-08 | 云南师范大学 | Metal nickel complex with ether bond bridging type bipyridyl carboxylic acid as ligand, and synthesis method and photocatalytic application thereof |
| CN112898349A (en) * | 2021-01-19 | 2021-06-04 | 云南师范大学 | Metal manganese complex with 4,4 '-diamino-2, 2' -bipyridine as ligand, synthetic method and photocatalytic application thereof |
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