CN115677787B - Cobalt pyrithione complex, preparation method and application thereof - Google Patents
Cobalt pyrithione complex, preparation method and application thereof Download PDFInfo
- Publication number
- CN115677787B CN115677787B CN202211073751.7A CN202211073751A CN115677787B CN 115677787 B CN115677787 B CN 115677787B CN 202211073751 A CN202211073751 A CN 202211073751A CN 115677787 B CN115677787 B CN 115677787B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- methanol
- hydrophobic
- preparing
- complex according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 title claims description 26
- 239000010941 cobalt Substances 0.000 title claims description 26
- 229960002026 pyrithione Drugs 0.000 title claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 25
- FGVVTMRZYROCTH-UHFFFAOYSA-N pyridine-2-thiol N-oxide Chemical compound [O-][N+]1=CC=CC=C1S FGVVTMRZYROCTH-UHFFFAOYSA-N 0.000 title claims description 25
- 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
- UOPTZAYKABCBRQ-UHFFFAOYSA-N cobalt pyridine Chemical compound [Co].c1ccncc1.c1ccncc1 UOPTZAYKABCBRQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 57
- 239000013078 crystal Substances 0.000 claims description 39
- 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 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 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
- 238000004729 solvothermal method Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000002904 solvent 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
- 238000001816 cooling Methods 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 7
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- -1 cobalt mercaptopyridine Chemical compound 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 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
- 238000012360 testing method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 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
- 229910000510 noble metal Inorganic materials 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- 235000000621 Bidens tripartita Nutrition 0.000 description 1
- 240000004082 Bidens tripartita Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution 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
- 208000006637 fused teeth Diseases 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- 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
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention relates to the technical field of metal coordination compound functional materials, and discloses a hydrophobic cobalt pyridine complex, a preparation method and application thereof. The hydrophobic cobalt pyridine complex has stable and novel structure, good thermal stability, certain photocatalytic effect, potential application value in photocatalysis, simple preparation method, high product purity, easy realization of preparation of cobalt pyridine complex, and contribution to application and popularization, and can be used as a catalyst in a photocatalytic system to convert methane into methanol.
Description
Technical Field
The invention relates to the technical field of metal coordination compound functional materials, in particular to a hydrophobic cobalt pyridine complex, a preparation method and application thereof.
Background
With the growing 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, has been found to be a considerable reserve in the world, exceeding petroleum. Methane has a higher hydrogen to carbon ratio than coal and petroleum and is considered a clean energy source. Besides being directly used as fuel, methane can be converted into methanol or other products with high added value through a catalytic technology, so that more efficient utilization is realized. The photocatalysis technology has the advantages of simple operation, low energy consumption, no secondary pollution, high efficiency and the like, so that the photocatalysis technology has important academic significance and industrial application value when being applied to the conversion of methane.
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 rise of free energy of Gibbs in the reaction is compensated. In addition, the photocatalytic reaction conditions are typically carried out under milder conditions, which provide a new route for the conversion of methane at low temperatures. In recent years, direct conversion of methane into oxygenated products such as methanol by the action of an oxidizing agent has been attracting attention. After development and utilization of light energy, research on photocatalytic methane conversion is also gradually in progress, and in a system for converting photocatalytic methane into methanol, a catalyst plays an important role, and a catalyst containing noble metals such as Rh, pt and the like has better photocatalytic performance, but has higher catalytic cost due to less noble metal reserves and high price, so that the catalyst is not beneficial to being applied to large-scale production. In view of the above, it is significant to develop inexpensive non-noble metal catalysts for the technical field of photocatalytic conversion of methane to methanol.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, provides a hydrophobic cobalt pyridine complex with novel structure and low price, and aims to solve the problem of higher production cost caused by the fact that a material containing noble metal is used as a catalyst in the reaction of converting methane into methanol in the prior art.
The technical scheme adopted by the invention is that the invention provides a cobalt-hydrophobic pyridine complex, in particular to a cobalt-hydrophobic pyridine complex, which has the following structural formula:
The invention also aims to provide a preparation method of the hydrophobic cobalt pyridine complex, which specifically comprises the following steps: in the presence of cobalt (II) perchlorate hexahydrate, 6-chloro-2, 2' -bipyridine is used as a ligand, thiocyanate is used as an auxiliary ligand, and the catalyst is synthesized by a solvothermal method.
It is a further object of the present invention to provide the use of the above cobalt pyrithione complex in the field of photocatalysis, in particular for the conversion of methane to methanol.
Compared with the prior art, the invention has the beneficial effects that: firstly, the invention utilizes the characteristic of double-tooth coordination of 6-chloro-2, 2 '-bipyridine to stably coordinate bivalent cobalt ions, and simultaneously, the chlorine atom of the 6-chloro-2, 2' -bipyridine is substituted by a solvogroup to obtain a solvosyl cobalt pyridine complex with novel structure. And secondly, the invention adopts cheap cobalt salt as a raw material, thereby reducing the preparation cost of the catalyst. And the preparation method provided by the invention is simple, the product purity is high, and the preparation of the cobalt pyrithione complex is easy to realize. Finally, the hydrophobic cobalt pyridine complex has good thermal stability, has a photocatalysis effect, can be used in the reaction of converting methane into methanol, and has a better application prospect in the field of converting methane into methanol by photocatalysis.
Drawings
FIG. 1 is a schematic representation of the crystal structure unit of the cobalt pyrithione complex of the present invention.
FIG. 2 is a 1H NMR chart of a cobalt pyrithione complex of the present invention.
FIG. 3 is a graph of a gas chromatograph showing the reduction of methane to methanol using the cobalt pyrithione complex of the present invention as a photocatalyst.
FIG. 4 is a thermogram of cobalt pyrithione complexes of the present invention.
Detailed Description
The invention provides a cobalt-hydrophobic pyridine complex, which has the following structural formula:
The molecular formula of the cobalt pyrithione complex is C 22H16CoN6S4.
The crystal of the above-mentioned hydrophobic cobalt pyridine complex is triclinic system, and its space group isThe unit cell parameters are: α＝80.333(12)°,β＝75.638(11)°,γ＝88.581(11)°,/>
The decomposition temperature of the above-mentioned cobalt-hydrophobic pyridine complex is 173.4 ℃.
The invention also provides a preparation method of the hydrophobic cobalt pyridine complex, which comprises the following steps: under the condition of the existence of cobalt (II) perchlorate hexahydrate, 6-chloro-2, 2' -bipyridine is used as a ligand, thiocyanate is used as an auxiliary ligand, and the cobalt pyrithione complex is synthesized by a solvothermal method.
Wherein the chemical formula of the cobalt (II) perchlorate hexahydrate is [ Co (ClO 4)2·6H2 O ], and the chlorine atom of the 6-chlorine-2, 2' -bipyridine is converted into sulfhydryl in the solvothermal synthesis process.
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, performing solvothermal reaction, cooling to room temperature after the reaction is finished, and collecting precipitated red blocky crystals;
S3, washing the red blocky crystals obtained in the step S2, and drying to obtain the monocrystal sample of the cobalt pyrithione complex.
In step S1, the thiocyanate is preferably potassium thiocyanate. The molar ratio of 6-chloro-2, 2 '-bipyridine, potassium thiocyanate and cobalt (II) perchlorate hexahydrate is preferably 1:1:1, and the dosage ratio of 6-chloro-2, 2' -bipyridine and the good solvent is preferably (0.1-0.2) mmol/20 mL. 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 added, 1 part of acetonitrile is added, and finally 0.5 part of methanol is added.
During 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 with a good solvent for dissolution; specifically, when the good solvent is measured, firstly 0.5 part of methanol is measured according to the volume ratio and mixed with the solute, then 1 part of acetonitrile is added for uniform mixing, and finally 0.5 part of methanol is added for uniform mixing; finally, the dosage ratio of the three solutes to the good solvent is (0.1-0.2) mmol/20 mL. 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 room temperature is 10 ℃/h; the time of the solvothermal reaction is preferably 24 to 48 hours for obtaining a better reaction effect. After the solvothermal reaction is finished, two crystals, namely a colorless transparent bulk crystal and a red bulk crystal, are obtained, the two crystals are separated, and a single crystal test result shows that the colorless transparent bulk crystal is cobalt perchlorate, and the red bulk crystal is the target product-cobalt pyrithione complex.
In step S3, the brown bulk crystals are preferably washed with methanol and/or acetonitrile. After washing, a vacuum drying oven may be used to dry, thereby obtaining a single crystal sample of the cobalt pyrithione complex.
The preparation method has simple steps and is easy to prepare the hydrophobic cobalt pyridine complex.
The invention also provides application of the hydrophobic cobalt pyridine complex as a photocatalyst, and particularly relates to the photocatalyst used in a reaction of converting methane into methanol.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. 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 exemplary embodiments according to the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The invention will now be further illustrated with reference to specific examples, which are given solely for the purpose of illustration and are not to be construed as limiting the invention. The test specimens and test procedures used in the following examples include those (if the specific conditions of the experiment are not specified in the examples, generally according to conventional conditions or according to the recommended conditions of the reagent company; the reagents, consumables, etc. used in the examples described below are commercially available unless otherwise specified).
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. Sealing the mixed solution, performing solvothermal reaction at 120 ℃ for 72 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 the 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. Sealing the finally obtained mixed liquid, performing solvothermal reaction at 120 ℃, cooling to room temperature at the speed of 10 ℃ per hour after the reaction for 72 hours to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product-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. Sealing the finally obtained mixed liquid, performing solvothermal reaction at 130 ℃, cooling to room temperature at the speed of 10 ℃ per hour after reacting for 48 hours to obtain red and colorless transparent blocky crystals, separating the two crystals to obtain a target product-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. Sealing the finally obtained mixed liquid, performing solvothermal reaction at 135 ℃ 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-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. Sealing the finally obtained mixed liquid, performing solvothermal reaction at 140 ℃ for 24 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-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 single crystal samples obtained in examples 1 to 7 were diffraction tested on a Rigaku R-AXIS SPIDER diffractometer, and the results are shown in FIG. 1. The test result shows that the synthesized product is the cobalt pyrithione complex with novel structure.
2. 1H NMR test
The cobalt pyrithione complex prepared in the examples was subjected to structural determination using 1H NMR techniques. The test results are shown in FIG. 2 ,1H NMR(600MHz,DMSO-d6)δ8.67(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 PC (propylene carbonate) is used as a solvent in the photocatalytic system, and relevant parameters are detected in a gas phase: the split ratio is 50:1, the FID column, and the carrier gas is N2. The test results show that the liquid product obtained after reduction can detect the chromatographic peak of methanol, which shows that methane can be reduced to methanol when the cobalt pyrithione complex is used as a photocatalyst.
4. Thermogravimetric test
The prepared cobalt pyrithione complex is subjected to thermogravimetric testing in an SDT-650 thermogravimetric analyzer in the United states, and the testing 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 cobalt pyrithione complex synthesized by the method has the advantages of novel structure, better thermal stability, certain photocatalytic effect, potential application value in photocatalysis by converting methane into methanol in a photocatalytic system, simple preparation method, high product purity, easy realization of preparation of the cobalt pyrithione complex and contribution to application and popularization.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The structural formula of the cobalt mercaptopyridine complex is as follows:
。
2. the cobalt-hydrophobic pyridine complex according to claim 1, wherein the crystal of the cobalt-hydrophobic pyridine complex is triclinic, and the space group is P The unit cell parameter is ：a = 8.6861(9) Å, b = 9.4314(14) Å, c = 14.823(2) Å, α = 80.333(12)°, β = 75.638(11)°, γ = 88.581(11)°, V = 1159.5(3) Å3; and/or the decomposition temperature of the cobalt-hydrophobic pyridine complex is 173.4 ℃.
3. A method for preparing the hydrophobic cobalt pyridine complex according to claim 1 or 2, which is 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 (II) perchlorate hexahydrate, and the hydrophobic cobalt pyridine complex is synthesized by a solvothermal method.
4. A process for the preparation of a cobalt mercaptopyridine complex according to claim 3 comprising the steps of:
s1, respectively dissolving 6-chloro-2, 2' -bipyridine, cobalt (II) perchlorate hexahydrate and thiocyanate in a good solvent consisting of methanol and acetonitrile, and mixing to obtain a mixed solution;
s2, placing the mixed solution obtained in the step S1 in a closed environment, performing solvothermal reaction, cooling to room temperature after the reaction is finished, and collecting precipitated red blocky crystals;
S3, washing the red blocky crystals obtained in the step S2, and drying to obtain the monocrystal sample of the cobalt-pyrithione complex.
5. The method for preparing a cobalt mercaptopyridine complex according to claim 4, wherein in the step S1, the thiocyanate is potassium thiocyanate.
6. The method for preparing a cobalt (ll) pyrithione complex according to claim 5, wherein in step S1, the molar ratio of 6-chloro-2, 2 '-bipyridine, potassium thiocyanate to cobalt (II) perchlorate hexahydrate is 1:1:1, and/or the ratio of 6-chloro-2, 2' -bipyridine to the good solvent is (0.1 to 0.2) mmol/20 mL.
7. The method for preparing a cobalt pyrithione complex according to claim 5, wherein in step S1, the volume ratio of methanol to acetonitrile is 1:1, and the method for preparing the good solvent comprises the following steps: according to the volume ratio, 0.5 part of methanol is added, 1 part of acetonitrile is added, and finally 0.5 part of methanol is added.
8. The method for preparing a cobalt pyrithione complex according to any one of claims 4 to 7, wherein in step S2, the solvothermal reaction is performed at a temperature of 120 to 140 ℃ for 24 to 72 hours at a cooling rate of 10 ℃/h.
9. The method for preparing a cobalt pyrithione complex according to any one of claims 4 to 7, wherein in step S3, methanol and/or acetonitrile is used to wash the red bulk crystals.
10. Use of a cobalt-hydrophobic pyridine complex according to any one of claims 1 to 2 or prepared by a method according to any one of claims 3 to 9 as a photocatalyst in a reaction for converting methane to methanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073751.7A CN115677787B (en) | 2022-09-02 | 2022-09-02 | Cobalt pyrithione complex, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073751.7A CN115677787B (en) | 2022-09-02 | 2022-09-02 | Cobalt pyrithione complex, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115677787A CN115677787A (en) | 2023-02-03 |
| CN115677787B true CN115677787B (en) | 2024-04-26 |
Family
ID=85060832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211073751.7A Active CN115677787B (en) | 2022-09-02 | 2022-09-02 | Cobalt pyrithione complex, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115677787B (en) |
Citations (3)
| 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 |
-
2022
- 2022-09-02 CN CN202211073751.7A patent/CN115677787B/en active Active
Patent Citations (3)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115677787A (en) | 2023-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105233872B (en) | A kind of Pd@MIL-101 composite materials and its preparation method and application | |
| Wang et al. | Hydrogen-bond activation of N2 molecules and photocatalytic nitrogen fixation | |
| CN111303445A (en) | Cobalt-based metal organic framework material and application | |
| CN108394950B (en) | Method for adsorbing noble metal gold ions | |
| CN107175133B (en) | A kind of silicon dioxide carried copper-dipyridyl catalyst and preparation method thereof | |
| CN111450894B (en) | Ce-based organometallic complex catalytic material and preparation and application thereof | |
| CN109705168A (en) | A kind of double-core nickel coordination compound and the preparation method and application thereof | |
| CN103467367B (en) | Cobalt complex having electrocatalytic activity on hydrogen peroxide | |
| CN115677787B (en) | Cobalt pyrithione complex, preparation method and application thereof | |
| Yang et al. | Photocatalytic C–N coupling towards urea synthesis with a palladium-supported CeO 2 catalyst | |
| Sun et al. | Sulfur atom-directed metal–ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation | |
| CN111286035B (en) | Zn (II) complex based on 4, 4' -dicarboxylic acid dimethyl azobenzene and adenine and synthetic method and application thereof | |
| CN104607251A (en) | Frame compound catalyst material containing mixed valence Cu and preparation method thereof | |
| CN112500580A (en) | Preparation method and application of cobalt-based metal organic framework catalyst for activating oxygen molecules | |
| Ji et al. | A new boat-like tungstoarsenate functionalized by carboxyethyltin and its catalytic properties | |
| Qu et al. | Insights into the Pd nanocatalysts directed by morphology effect for CO and methyl nitrite coupling to dimethyl oxalate | |
| CN115477661A (en) | Trinuclear pyridine copper complex and preparation method and application thereof | |
| CN113717391B (en) | Boron-containing zirconium-based metal organic framework material and preparation method and application thereof | |
| CN112898349B (en) | Manganese metal complex with 4,4 '-diamino-2, 2' -bipyridine as ligand, and synthetic method and photocatalytic application thereof | |
| CN115448959A (en) | Polynuclear cobalt formate complex and preparation method and application thereof | |
| CN108623493B (en) | Under mild condition with CO2N-formylation synthesis method for carbon source | |
| CN107698777B (en) | Copper-coordinated porous polymer, preparation method and application | |
| CN108610281B (en) | Zinc complex with three-dimensional porous structure and synthesis method and application thereof | |
| CN111635365A (en) | Mixed-valence copper (I, II) complex and in-situ synthesis method thereof | |
| CN110317233A (en) | Metallic nickel and Metallic Manganese Complex and the preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |