CN113603648B - Cobalt complex and preparation method and application thereof - Google Patents
Cobalt complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN113603648B CN113603648B CN202110947567.XA CN202110947567A CN113603648B CN 113603648 B CN113603648 B CN 113603648B CN 202110947567 A CN202110947567 A CN 202110947567A CN 113603648 B CN113603648 B CN 113603648B
- Authority
- CN
- China
- Prior art keywords
- complex
- salicylaldehyde
- cobalt
- preparation
- crystals
- 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 13
- 150000004700 cobalt complex Chemical class 0.000 title abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000013078 crystal Substances 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 30
- SMQUZDBALVYZAC-UHFFFAOYSA-N ortho-hydroxybenzaldehyde Natural products OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 salicylaldehyde aminoguanidine Schiff base Chemical class 0.000 claims abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 239000002262 Schiff base Substances 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003504 photosensitizing agent Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- DOIVPHUVGVJOMX-UHFFFAOYSA-N 1,10-phenanthroline;ruthenium Chemical compound [Ru].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 DOIVPHUVGVJOMX-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004896 high resolution mass spectrometry Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HUHDNYSMBNOJGR-UHFFFAOYSA-N 2-[[4-(2-hydroxyphenyl)-2-[2-[(2-hydroxyphenyl)methylidene]hydrazinyl]-6-methyl-2H-pyrimidin-1-yl]methyl]phenol Chemical compound CC1=CC(C(C=CC=C2)=C2O)=NC(NN=CC(C=CC=C2)=C2O)N1CC(C=CC=C1)=C1O HUHDNYSMBNOJGR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical compound CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- HOBWAPHTEJGALG-JKCMADFCSA-N [(1r,5s)-8-methyl-8-azoniabicyclo[3.2.1]octan-3-yl] 3-hydroxy-2-phenylpropanoate;sulfate Chemical compound [O-]S([O-])(=O)=O.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1.C([C@H]1CC[C@@H](C2)[NH+]1C)C2OC(=O)C(CO)C1=CC=CC=C1 HOBWAPHTEJGALG-JKCMADFCSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/42—One nitrogen atom
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a cobalt complex and a preparation method and application thereof. The preparation method of the cobalt complex comprises the following steps: placing salicylaldehyde aminoguanidine Schiff base, salicylaldehyde and cobalt salt in a mixed solvent, adjusting the pH value of the system to be alkaline, reacting under a heating condition, cooling a reactant, separating out crystals, and collecting the crystals to obtain the salicylaldehyde aminoguanidine Schiff base; wherein the cobalt salt is CoCl 2 ·6H 2 O or Co (NO) 3 ) 2 ·6H 2 O; the mixed solvent is methanol and acetone according to the weight ratio of 1:1 in a volume ratio. The test result of the applicant shows that the complex as a homogeneous molecular photocatalyst shows excellent performances of high activity and high selectivity in carbon dioxide reduction, and has a remarkable catalytic effect.
Description
Technical Field
The invention relates to a copper metal complex, in particular to a cobalt complex and a preparation method and application thereof.
Background
Carbon dioxide (CO) in the atmosphere 2 ) Is one of the main components of greenhouse gases, which mainly result from the combustion of fossil fuels in human activities. In order to effectively treat and relieve CO 2 Environmental and climate problems caused by gas, and utilization of renewable energy solar energy to convert CO 2 The conversion into carbon-containing energy of useful value is of great significance.
CO 2 The carbon-oxygen double bond length between molecules is short (116 pm), the bond energy is high (803 KJ/mol), and the carbon-oxygen double bond is not easy to break, so the structure and the property of the carbon-oxygen double bond are stable and the carbon-oxygen double bond is not easy to activate. In the course of reduction, CO 2 The electric potential required for the single-electron reduction of molecules is high (-1.90V vs NHE), and in order to reduce the reduction electric potential, proton-coupled multi-electron transfer is generally accompanied, but the same as the proton-coupled multi-electron transferThe hydrogen evolution reaction brought by the introduction of protons reduces the selectivity of the target product, and in addition, CO 2 Low solubility in water also results in CO 2 The reduction efficiency is greatly reduced. The traditional photocatalyst for carbon dioxide reduction is generally a noble metal complex, such as Ru, ir, pt and other noble metal complexes, so that the price is high. In recent years, studies have been made to apply an inexpensive cobalt complex compound to photocatalytic reduction of carbon dioxide. For example, the invention patent with publication number CN110314700a discloses a cocatalyst for photocatalytic reduction of carbon dioxide, specifically a phthalocyanine metal complex shown in the following formula (1) or a poly-phthalocyanine metal complex shown in the following formula (2). The invention adopts the poly phthalocyanine metal complex as the cocatalyst, the system is a high-efficiency heterogeneous catalysis system, and the poly phthalocyanine metal complex can well inhibit the generation of byproduct hydrogen, and the selectivity to carbon monoxide is greatly improved.
It can be seen that the selection of a suitable catalytic system is critical to the overall catalytic reaction, and therefore, after the application problems in terms of catalytic activity, selectivity, stability and economy are comprehensively considered, it is desirable that the photocatalytic system used can be carried out under high-efficiency and low-cost conditions, and the range of practical application of the catalytic system can be expanded. At present, no relevant report that the cobalt complex taking 1- (2-hydroxybenzyl) -2- (2-hydroxybenzylidenehydrazino) -4- (2-hydroxyphenyl) -6-methylpyrimidine as a ligand is used as a catalyst in the photocatalytic carbon dioxide reduction is found.
Disclosure of Invention
The invention aims to provide a cobalt complex which can be used as a catalyst in photocatalytic carbon dioxide reduction and shows high activity and high selectivity in photocatalytic carbon dioxide reduction, and a preparation method and application thereof.
The cobalt complex is a compound shown as the following formula (I) or a pharmaceutically acceptable salt thereof:
the cobalt complex is a 1- (2-hydroxybenzyl) -2- (2-hydroxybenzylidenehydrazino) -4- (2-hydroxyphenyl) -6-methylpyrimidine cobalt complex, and the molecular formula is C 25 H 20 CoN 4 O 3 Belonging to the monoclinic system, P2 1 The/c space group is a mononuclear complex, and the unit cell parameters are as follows:
α＝90°，β＝103.016(5)°，γ＝90°；
the complex has a metal center cobalt ion as positive divalent, and the complex consists of a cobalt ion and a 1- (2-hydroxybenzyl) -2- (2-hydroxybenzylidenehydrazino) -4- (2-hydroxyphenyl) -6-methylpyrimidine ligand (HL) 2- ) The two nitrogen atoms and the two oxygen atoms are coordinated to form a mononuclear structure with a plane tetragonal configuration.
The preparation method of the cobalt complex comprises the following steps: placing salicylaldehyde aminoguanidine Schiff base, salicylaldehyde and cobalt salt in a mixed solvent, adjusting the pH value of the system to be alkaline, reacting under a heating condition, cooling a reactant, separating out crystals, and collecting the crystals to obtain a target product; wherein the content of the first and second substances,
the cobalt salt is CoCl 2 ·6H 2 O and/or Co (NO) 3 ) 2 ·6H 2 O；
The mixed solvent is methanol and acetone according to the weight ratio of 1:1 in a volume ratio.
In the preparation method, the molar ratio of the salicylaldehyde aminoguanidine Schiff base to the salicylaldehyde to the cobalt salt is a stoichiometric ratio, and the salicylaldehyde and the cobalt salt can be used in a relative excess amount in the actual operation process. The salicylaldehyde aminoguanidine schiff base can be prepared by referring to (A.Mondal, C.das, M.Corbella, A.Bauza, A.Frontera, M.saha, S.Mondal, K.das Saha, S.K.chattopadhyy, new J.chem.,2020,44,7319-7328), and can also be designed and synthesized by self. The amount of the mixed solvent to be used may be determined as required, and it is usually preferable that the raw materials to be reacted are dissolved. Specifically, the total amount of the mixed solvent used for all raw materials is generally 2-10 mL calculated by taking 1mmol of salicylaldehyde aminoguanidine Schiff base as a reference.
In the preparation method, the pH value of the system is adjusted to be alkaline by adopting an alkaline substance, wherein the alkaline substance can be a conventional choice in the prior art, and triethylamine is preferred. The pH of the system is preferably adjusted to 8 or more, more preferably adjusted to 8.5 or more, and still more preferably adjusted to 9 to 13.
In the above preparation method, the mixed solution obtained after adjusting the pH value is usually placed in a container, vacuumized, sealed and then placed under heating for reaction. The reaction is preferably carried out at not less than 50 ℃ and more preferably at 80 to 100 ℃. When the reaction is carried out at 80-100 ℃, the reaction time is usually controlled at 48-72 h. The reaction usually adopts a thick-wall hard glass tube with one closed end to contain the mixed solution obtained after the pH value is adjusted.
The invention also comprises the application of the cobalt complex in preparing a photocatalyst, in particular to the application of the cobalt complex as a catalyst in photocatalytic carbon dioxide reduction. In a specific application, the photocatalytic system comprises a photosensitizer, a photocatalyst, a sacrificial agent and a solvent, wherein the photocatalyst is the cobalt complex, and the photosensitizer, the sacrificial agent and the solvent are selected as in the prior art, and the photosensitizer is preferably [ Ru (phen) 3 ](PF 6 ) 2 、[Ru(phen) 3 ]Cl 2 Or [ Ru (bpy) 3 ]Cl 2 More preferably [ Ru (phen) 3 ](PF 6 ) 2 (ii) a The sacrificial agent is preferably Triethanolamine (TEOA) and/or Triethylamine (TEA), and the solvent is preferably a mixed solution containing water and acetonitrile. In the photocatalytic system, the concentration of the photosensitizer is preferably 400 to 500. Mu. Mol/L, the concentration of the photocatalyst is preferably 0.05 to 1. Mu. Mol/L, and the concentration of the sacrificial agent is preferably 0.30 to 0.35. Mu. Mol/L.
The present invention also provides a photocatalyst containing the above cobalt complex.
Compared with the prior art, the invention provides a cobalt complex obtained by in-situ cyclization of salicylaldehyde aminoguanidine with a novel structure and a preparation method thereof, and test results of an applicant show that the complex as a homogeneous molecular photocatalyst shows excellent performances of high activity and high selectivity in reduction of carbon dioxide and has a remarkable catalytic effect.
Drawings
FIG. 1 is an IR spectrum of the final product obtained in example 1 of the present invention.
FIG. 2 is a crystal structure diagram of the final product obtained in example 1 of the present invention.
Detailed Description
In order to better explain the technical solution of the present invention, the present invention is further described in detail with reference to the following examples, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, technical features used in the embodiments may be replaced with other technical features known in the art having equivalent or similar functions or effects without departing from the inventive concept.
The salicylaldehyde aminoguanidine Schiff base referred to in the following examples was prepared as follows:
salicylaldehyde (1.22g, 10mmol) was dissolved in methanol in a round-bottomed flask, and triethylamine (1.01g, 10mmol) was added dropwise. Aminoguanidine was dissolved in methanol and added to the above solution. The resulting mixture was refluxed for 3h, filtered, the filtrate was slowly evaporated at room temperature, an off-white solid precipitated, the solid was collected after washing with cold methanol and ether, dried and the product collected. The resulting product was characterized by reference to the characterization methods in the literature (a.mondal, c.das, m.corbella, a.bauza, a.frontera, m.saha, s.mondal, k.das Saha, s.k.chattopadhyay, new j.chem.,2020,44,7319-7328), and was identified as salicylaldehyde aminoguanidine schiff base.
Example 1
Taking salicylaldehyde (10 mu.L, 0.1 mmol), salicylaldehyde aminoguanidine Schiff base (0.0089g, 0.05mmol) and CoCl 2 ·6H 2 O (0.0118g, 0.05mmol) is placed in a glass tube with one closed end and the length of the glass tube is about 20cmAdding 1mL of mixed solvent consisting of methanol and acetone (the volume ratio of the methanol to the acetone is 1:1), fully dissolving by ultrasonic, adjusting the pH value of the system to 11 by triethylamine (40 mu L), vacuumizing, and sealing a glass tube by high-temperature fusion. And (3) placing the sealed glass tube in an oven at 80 ℃, reacting for 72 hours, slowly cooling to room temperature after the reaction is stopped, observing that black and red rhombus crystals are separated out at the bottom of the glass tube, collecting the crystals, and drying. The yield was 19% (0.0045 g based on Co) 2+ )。
The product obtained in this example was characterized:
(1) The infrared spectrum is shown in figure 1.
IR(KBr,cm -1 ):1600vs,1566s,1475m,1435m,1384w,1343w,1291w,1237m,1145m,1099w,1036w,845w,752s。
(2) And (3) analyzing a crystal structure:
selecting a black and red diamond crystal with moderate size, placing the black and red diamond crystal on a Supernova single crystal diffractometer of Agilent company, and adopting graphite to monochromate Mo-K α 
And (4) performing single crystal test by using rays. The initial crystal structures of the products obtained in the embodiment are solved by adopting a SHELXS-97 direct method, the geometric hydrogenation is carried out, and the non-hydrogen atom coordinates and the anisotropic thermal parameters are refined by adopting a SHELXL-97 full matrix least square method. The obtained crystallographic and structural refinement data are shown in table 1 below, part of the bond length and bond angle data are shown in tables 2 and 3 below, respectively, the chemical structure of the obtained black and red rhombohedral crystal is shown in fig. 2, and the obtained black and red rhombohedral crystal is determined to be the target product of the invention.
Table 1 crystallographic data for the cobalt complexes according to the invention:
table 2 bond length data for a portion of the cobalt complexes of the present invention
TABLE 3 partial bond angle data (. Degree.) of the cobalt complexes according to the invention
Comparative examples 1 to 1
Example 1 was repeated except that the mixed solvent was changed to a single solvent such as methanol, acetone, acetonitrile, dichloromethane, chloroform, DMF or DMSO. As a result, no crystals or precipitates of the objective product were formed.
Comparative examples 1 to 2
Example 1 was repeated except that methanol in the mixed solvent was replaced with ethanol, acetonitrile, dichloromethane, DMF or DMSO. As a result, no crystals or precipitates of the objective product were formed.
Comparative examples 1 to 3
Example 1 was repeated except that the volume ratio of methanol to acetone in the mixed solvent was changed to 1:2 or 1:4. as a result, no crystals or precipitates of the desired product were formed.
Comparative examples 1 to 4
Example 1 was repeated, except that the reaction was carried out at ordinary temperature instead. As a result, no crystals or precipitates of the desired product were formed.
Comparative examples 1 to 5
Example 1 was repeated except that the pH of the system was adjusted to =7. As a result, no crystals or precipitates of the desired product were formed.
Comparative examples 1 to 6
Example 1 was repeated except that Co (ClO) was used 4 ) 2 ·6H 2 O、CoSO 4 ·6H 2 O、CoBr 2 Or Co (OAc) 2 ·6H 2 O instead of CoCl 2 ·6H 2 O, the desired target product of the present invention is obtained, but none of the crystals of the cobalt complex of the present invention is obtained, illustrativeCo(ClO 4 ) 2 ·6H 2 O、CoSO 4 ·6H 2 O、CoBr 2 Or Co (OAc) 2 ·6H 2 O cannot reach the thermodynamic conditions for forming the cobalt complex crystals of the present invention.
Example 2
Example 1 was repeated except that the pH of the system was adjusted to =8.
As a result, black and red rhombohedral crystals were obtained. Yield 15% (based on Co) 2+ )。
The product obtained in the embodiment is subjected to high resolution mass spectrometry, infrared analysis and single crystal diffraction analysis, and the obtained black-red rhombohedral crystal is determined to be the target product of the invention.
Example 3
Example 1 was repeated except that the reaction was carried out at 100 ℃ for 48h and the pH of the system was adjusted with triethylamine =9, 10 or 13.
All results obtained black and red rhombohedral crystals.
The product obtained in the embodiment is subjected to high resolution mass spectrometry, infrared analysis and single crystal diffraction analysis, and the obtained black-red rhombohedral crystals are determined to be the target product of the invention.
Example 4
Example 1 was repeated except that Co (NO) was used 3 ) 2 ·6H 2 O instead of CoCl 2 ·6H 2 O。
As a result, black and red rhombohedral crystals were obtained.
The obtained black-red rhombohedral crystal is subjected to high-resolution mass spectrometry, infrared analysis and single crystal diffraction analysis, and the black-red rhombohedral crystal is determined to be the target product of the invention.
Experimental example 1: the cobalt complex of the invention is used as a homogeneous catalyst for photocatalysis of CO in a water-containing system 2 Reduction experiments were performed.
(1) The materials used were:
a photosensitizer: [ Ru (phen) 3 ](PF 6 ) 2 And (3) catalyst: the cobalt complex prepared according to inventive example 1 (hereinafter referred to as complex 1), sacrificial agent: TEA, LED lamp source (wavelength 450nm,light intensity of 100mW cm -2 The irradiation area is 0.8cm 2 ) 15-20 mL of a reactor made of quartz, CO 2 Gas, rubber tube, analytical balance, stirrer and gas chromatograph.
(2) Photocatalytic experiment steps:
the molecular formula of the cobalt-based catalyst complex 1 is C 25 H 20 CoN 4 O 3 2mg of photosensitizer [ Ru (phen) are weighed in turn 3 ](PF 6 ) 2 200. Mu.L of sacrificial agent TEA and 80. Mu.L of complex 1 were transferred into a quartz glass tube, 4mL of ultra-dry acetonitrile and 1mL of distilled water were added, the tube was sealed tightly with a rubber tube, and then CO was introduced 2 After the gas is used for 10-20 min, the fixed wavelength is 450nm, and the light intensity is 100mW cm -2 The irradiation area was 0.8cm 2 Irradiating for 10h while stirring, and injecting the gas sample into a gas chromatograph for CO 2 Detection of the reduction product CO shows that 0.05. Mu. Mol of the complex 1 produces 2.16. Mu. Mol of CO, the TON value is 8640, and the selectivity is as high as 97%.
Different parallel experiments were performed on the above method (as shown in table 4). As can be seen from Table 4, the cobalt complexes of the present invention catalyze CO photocatalytically under different catalytic system conditions 2 The catalytic effect of the reduction is obviously higher than that of other catalytic systems.
TABLE 4 photocatalytic CO with cobalt complexes according to the invention as catalysts 2 Reduction of experimental data
The reaction conditions are as follows: under the constant temperature condition of 25 ℃, an LED lamp (450nm, 100mW cm) -2 The illumination time is 10h, and the illumination area is 0.8cm 2 ) Irradiation was carried out with 5mL of a solution of catalyst (0.05. Mu.M), photosensitizer [ Ru (phen) 3 ](PF 6 ) 2 (0.4 mM), of the sacrificial agent TEA (0.3M)H 2 O/CH 3 CN (v/v 1:4). Number 1: complex 1 (0.05. Mu.M); sequence number 2: no illumination is needed; sequence No. 3: no catalyst is added; sequence number 4: no photosensitizer is added; number 5: no sacrificial agent is added; number 6: no CO 2 ，N 2 An atmosphere; number 7: complex 1 in 10% CO 2 Photocatalysis under atmosphere; number 8: coCl 2 ·6H 2 O(0.05μM)。
From the photocatalytic results, it can be seen that: the complex of the invention has better photocatalysis CO in a water-containing system as a homogeneous catalyst 2 And (4) reducing effect. In the photocatalytic system constructed by the invention, the photocatalytic system can catalyze CO 2 The reduction results are shown in Table 4, the TON value reaches 8640, and the selectivity is greater than 97%.
Claims (10)
1. A complex represented by the following formula (I) or a pharmaceutically acceptable salt thereof:
2. the preparation method of the complex as claimed in claim 1, which is characterized in that salicylaldehyde aminoguanidine Schiff base, salicylaldehyde and cobalt salt are put into a mixed solvent, the pH value of the system is adjusted to be alkaline, the reaction is carried out under the heating condition, the reactant is cooled, crystals are separated out, and the crystals are collected to obtain the target product; wherein the content of the first and second substances,
the cobalt salt is CoCl 2 ·6H 2 O or Co (NO) 3 ) 2 ·6H 2 O, or CoCl 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 A combination of O;
the mixed solvent is methanol and acetone according to the weight ratio of 1:1 in a volume ratio.
3. The process according to claim 2, wherein the pH of the system is adjusted to 8 or more.
4. The method according to claim 2, wherein the pH of the system is adjusted to be from 9 to 13.
5. The process according to claim 2, wherein the reaction is carried out at 50 ℃ or higher.
6. The process according to claim 2, wherein the reaction is carried out at 80 to 100 ℃.
7. The method of claim 2~6, wherein the pH of the system is adjusted to basic with a basic substance.
8. Use of the complex of claim 1 in the preparation of a photocatalyst.
9. Use according to claim 8 as a catalyst in photocatalytic carbon dioxide reduction.
10. A photocatalyst comprising the complex of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110947567.XA CN113603648B (en) | 2021-08-18 | 2021-08-18 | Cobalt complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110947567.XA CN113603648B (en) | 2021-08-18 | 2021-08-18 | Cobalt complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113603648A CN113603648A (en) | 2021-11-05 |
| CN113603648B true CN113603648B (en) | 2023-03-17 |
Family
ID=78341089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110947567.XA Active CN113603648B (en) | 2021-08-18 | 2021-08-18 | Cobalt complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113603648B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031647B (en) * | 2021-12-06 | 2023-07-25 | 广西师范大学 | Binuclear cobalt complex and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2700633A1 (en) * | 2012-08-23 | 2014-02-26 | Bayer MaterialScience AG | Method for producing linear and/or cyclic carbonate esters |
| US9266102B2 (en) * | 2013-03-29 | 2016-02-23 | The University Of Kentucky Research Foundation | Catalysts and methods of increasing mass transfer rate of acid gas scrubbing solvents |
| CN110314700B (en) * | 2018-03-28 | 2022-08-30 | 中国科学院理化技术研究所 | Cocatalyst for photocatalytic reduction of carbon dioxide, photocatalytic system and application of photocatalytic system |
-
2021
- 2021-08-18 CN CN202110947567.XA patent/CN113603648B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Antu Mondal et al..Biological promiscuity of a binuclear Cu(II) complex of aminoguanidine Schiff base:DNA binding, anticancer activity and histidine sensing ability of the complex.2020,第44卷第7319-7328页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113603648A (en) | 2021-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Reinforced photocatalytic reduction of CO 2 to CO by a ternary metal oxide NiCo 2 O 4 | |
| Sato et al. | Surface dynamics for creating highly active ru sites for ammonia synthesis: accumulation of a low-crystalline, oxygen-deficient nanofraction | |
| CN109174145B (en) | Dimolybdenum carbide/titanium dioxide composite photocatalyst and preparation method and application thereof | |
| CN108892783B (en) | Visible light driven hydrogen production metal-organic framework material based on eosin and preparation method thereof | |
| CN113769751A (en) | Preparation method and application of catalyst | |
| CN113603648B (en) | Cobalt complex and preparation method and application thereof | |
| CN114478648B (en) | Pyridine pyrrole ruthenium-like complex, preparation method thereof and application of pyridine pyrrole ruthenium-like complex as electrocatalytic ammoxidation catalyst | |
| CN111359644B (en) | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof | |
| CN113441160B (en) | Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof | |
| CN114425392B (en) | Carbon-nitrogen based composite material, preparation method and application thereof | |
| CN114308132B (en) | Protonated CdS-COF-366-M composite photocatalyst and preparation method thereof | |
| CN115872897B (en) | Schiff base cobalt complex, preparation method and application thereof | |
| CN107540660A (en) | It is a kind of using terpyridyl derivative as the iron complex and its synthetic method of part and application | |
| US10233077B2 (en) | Photocatalysis-induced partial oxidation of methanol reforming process for producing hydrogen | |
| JP6368719B2 (en) | Method for hydrogen production | |
| CN113083370A (en) | TiO connected by covalent bond2@ CTF-Py heterojunction material and preparation method and application thereof | |
| CN115872897A (en) | Schiff base cobalt complex, and preparation method and application thereof | |
| JP2764114B2 (en) | Method for producing methanol | |
| CN115197280B (en) | Metal cobalt complex with photocatalytic carbon dioxide reduction activity and preparation method and application thereof | |
| CN116874390A (en) | Mononuclear cobalt complex based on Salen ligand, preparation method and application thereof | |
| CN117447354A (en) | Schiff base ligand mononuclear cobalt complex, preparation method and application thereof | |
| CN113307831B (en) | Preparation method and application of cobalt (II) coumarin Schiff base complex | |
| CN111530500B (en) | Polycarbazole loaded cobalt hybrid material and preparation method and application thereof | |
| CN115893523A (en) | Preparation method and application of transition metal phosphide | |
| CN115806573A (en) | Mononuclear cobalt complex, and 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 |