CN115521291A - Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof - Google Patents
Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof Download PDFInfo
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- 239000003446 ligand Substances 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 12
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 4
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000003937 benzamidines Chemical class 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 21
- 238000003786 synthesis reaction Methods 0.000 abstract description 21
- 239000003504 photosensitizing agent Substances 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000013461 design Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000008313 sensitization Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 13
- 238000000967 suction filtration Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 239000012327 Ruthenium complex Substances 0.000 description 4
- NMVVJCLUYUWBSZ-UHFFFAOYSA-N aminomethylideneazanium;chloride Chemical compound Cl.NC=N NMVVJCLUYUWBSZ-UHFFFAOYSA-N 0.000 description 4
- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
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- 239000003502 gasoline Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Images
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/085—Organic compound
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a ligand and a preparation method thereof, a metal complex, a catalytic hydrogen production system and application thereof, wherein the ligand has a structural formulaWherein R is selected fromOrThrough the design of the ligand structure, the bimetal center can be selectively introduced, and the antenna is improvedThe energy transfer efficiency of the sensitization center can provide favorable support for the synthesis design of the photosensitizer and the catalyst.
Description
Technical Field
The invention relates to a catalytic hydrogen production technology, in particular to a ligand, a preparation method thereof, a metal complex, a catalytic hydrogen production system and application thereof.
Background
Hydrogen is one of the green clean energy sources that is currently considered to be better. As an energy carrier, hydrogen, because of its higher energy density (122 kJ/g) than gasoline (40 kJ/g), and its non-polluting reaction products, is expected to be the key to solving these growing world energy demand problems. The current main way to obtain hydrogen is to convert fossil fuel (such as petroleum, coal, natural gas, etc.) to obtain hydrogen, which is the current most important way to obtain hydrogen. However, this method still uses traditional fossil fuels, and these resources are calculated according to the consumption rate all over the world and can be used by human for up to 220 years.
In 1972, japanese academicians Fujishima and Honda used illumination of n-type semiconductor TiO 2 The electrodes cause the decomposition of water to produce hydrogen. The discovery of this phenomenon reveals that solar energy can be used to decompose water to produce hydrogen, i.e., solar energy can be converted to chemical energy by catalytic methods. In recent years, as researchers of various countries have studied the preparation, modification and photocatalytic theory of photocatalyst, tiO is removed 2 Besides, many new photocatalysts are discovered in succession, and the photocatalytic efficiency is correspondingly improved. Based on the research of the scholars, the reaction of photocatalytic hydrogen production is generally divided into homogeneous phase and heterogeneous phase, wherein the homogeneous photocatalytic hydrogen production system becomes a hotspot of the research of people due to the advantages of high catalytic activity, clear catalyst structure, convenient control of the reaction and the like. The classical photocatalytic hydrogen production system is divided into three parts: proton reduction catalyst, photosensitizer, electron donor sacrificial agent. The proton reduction type catalyst mainly acts to receive electrons brought by Photosensitizer (PS) photosensitized by the sun and reduce protons in a reduction system into hydrogen; metal complexes of a photosensitizer polypyridine or porphyrin ligand in a system which is sensitive to light andthe method has better separating capability of photoproduction electrons and holes; the electron donor sacrificial agent, which provides electrons to reduce the photosensitizer in an oxidized state to a ground state, is commonly used as Triethylamine (TEA), triethanolamine (TEOA), ethylenediaminetetraacetic acid (EDTA), ascorbic acid, and the like.
The ruthenium complex is used as a homogeneous catalyst system with the best effect at present, the oxidation-reduction capability of a ruthenium metal catalytic center of the ruthenium complex is strong, and the valence state change is more, so that the ruthenium complex plays a great role in photocatalytic reaction, and the ruthenium complex can serve as a photosensitizer and a catalyst in multiple reactions. Ruthenium is one of platinum group elements, easily forms a hexacoordinated complex, and easily coordinates with nitrogen, oxygen and other atoms, and a ligand containing bipyridine and a benzene ring is often used in the preparation process of the photosensitizer. The traditional ruthenium photosensitizer or catalyst for photocatalytic hydrogen production usually adopts a mononuclear structure, and coordination molecule water or methanol and the like firstly coordinate with metal ruthenium and then generate electron transfer through photocatalysis, so that the coordination molecules generate a photo-oxidation-reduction reaction.
The following formula shows the hydrogen production principle of the three-component system for photocatalytic hydrogen production:
the information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
The invention aims to provide a ligand and a preparation method thereof, a metal complex, a catalytic hydrogen production system and application thereof.
To achieve the above objects, the embodiments of the present invention provide a ligand having the structural formulaWherein R is selected fromOr
In one or more embodiments of the present invention, a method for preparing a ligand comprises the steps of: reacting S1, 2-aldehyde pyridine with 2-acetyl pyridine under strong alkali and low temperature conditions to obtain an intermediate 1, wherein the intermediate 1 has a structural formulaS2, weighing a proper amount of raw materials containing any one of 2-pyrimidine formamidine and derivatives thereof, benzamidine and derivatives thereof, processing to obtain an alcohol dispersion liquid I containing a proper amount of 2-pyrimidine formamidine or benzamidine, and dropwise adding a proper amount of intermediate 1 into the alcohol dispersion liquid I for full reaction to obtain the ligand. Preferably, the treatment process can be as follows: when the raw material is a hydrochloride derivative, an alcohol dispersion system (preferably an ethanol dispersion system) can be added with a proper amount of strong base such as NaOH and KOH (non-solution, such as solid particles) until the hydrochloric acid is completely reacted. Preferably, the intermediate 1 is added dropwise to an alcohol solution of the intermediate 1, preferably an ethanol solution. Preferably, the dropping rate is 2 to 8 drops/sec. Preferably, the stirring speed is 60-400rpm.
In one or more embodiments of the present invention, the strong base condition in S1 is under the condition that NaOH or KOH is added to the system.
In one or more embodiments of the invention, the low temperature condition in S1 is a reaction temperature of not higher than 10 ℃. Preferably, the conditions are ice salt water bath, ice-ice bath, etc.
In one or more embodiments of the invention, the 2-pyrimidine formamidine derivative and the benzamidine derivative in S2 are each a corresponding hydrochloride.
In one or more embodiments of the present invention, the intermediate 1 added dropwise to S2 is an alcoholic solution of the intermediate 1.
In one or more embodiments of the invention, the metal complex is a metal complex formed from a ligand as previously described and an active metal. The structural formula of a part of the metal complex is shown as the following formula:
in one or more embodiments of the present invention, the active metal is selected from transition metal elements. Further preferably, the active metal is selected from ruthenium, platinum, iridium. The screened complex is further optimized, and an effective photocatalysis effect can be obtained.
In one or more embodiments of the present invention, the catalytic hydrogen generation system includes at least a ligand as described above or a metal complex as described above. Preferably, the metal complex may act as a photosensitizer or catalyst.
In one or more embodiments of the invention, the use of a ligand as described above or a metal complex as described above or a catalytic hydrogen production system as described above for the electrolytic production of hydrogen.
Compared with the prior art, the ligand, the preparation method thereof, the metal complex, the catalytic hydrogen production system and the application thereof, which are disclosed by the embodiment of the invention, have lower synthesis yield compared with the traditional tpy, higher laboratory synthesis yield of the two ligands L-Pym and L-Ph, and can form better polypyridine coordination geometry with Ru and form a Ru polynuclear complex. Further according to molecular design, the ligand can be applied to the field of photocatalytic hydrogen production and used as a molecular framework of a photosensitizer or a catalyst.
Drawings
FIG. 1 shows a ligand L-Pym according to one embodiment of the present invention 1 H NMR spectrum;
FIG. 2 is a schematic representation of ligand L-Ph according to one embodiment of the present invention 1 H NMR spectrum;
FIG. 3 is a diagram of ligand intermediate 2 according to an embodiment of the present invention 1 H NMR spectrum;
FIG. 4 is a high resolution mass spectrum of an L-Ph-Ru-2 binuclear complex according to an embodiment of the present invention.
Detailed Description
The following detailed description of the present invention is provided in conjunction with the accompanying drawings, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The synthetic routes for the two ligands of the invention are shown in the above process schemes.
Example 1, shown below, demonstrates one possible preparation scheme for two ligands:
example 1
Synthesis of ligand intermediate 1:
0.72g (18 mmol) of NaOH was added to a 250mL Erlenmeyer flask containing 150mL of distilled water, and after dissolution with stirring, 5mL of 2-formylpyridine was added thereto, and the mixture was cooled in an ice bath so as not to exceed 10 ℃. 4mL of 2-acetylpyridine was added dropwise, and the reaction was stirred for 30min. When a large amount of light yellow precipitate appears in the system, the system is filtered by suction and washed by a large amount of water. Drying under reduced pressure at room temperature gave the pale yellow product, intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride is weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise over 20 min. And (3) carrying out reflux reaction for 6h, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%. Of the product shown in FIG. 1 1 H NMR(400MHz,Chloroform-d)δ9.52(s,1H),9.08(d,J=4.8Hz,2H),8.79(s,0H),8.71(s,1H),7.94–7.82(m,1H),7.52–7.38(m,2H)。
B: synthesis of ligand L-Ph:
benzamidine hydrochloride 1.7g (11 mmol) was weighed, added to 125mL of anhydrous ethanol, and stirred. 0.520g (13 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise over 1 h. And (3) carrying out reflux reaction for 24 hours, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%. m/z 310.1390. 1H NMR (400MHz, DMSO-d 6) delta 9.21 (s, 1H), 8.80 (d, J =4.1Hz, 3H), 8.75-8.64 (m, 5H), 8.07 (td, J =7.7,1.7Hz, 2H), 7.58 (d, J =2.0Hz, 3H) for the product as shown in FIG. 2.
Complex intermediate Ru-tpy-Cl 3 Synthesis of (2)
0.524g (2 mmol) of RuCl was weighed 3 ·3H 2 O, tpy 0.466g (2 mmol), dissolved in 250ml of absolute ethanol and refluxed for 8h with vigorous stirring. A large amount of precipitation occurred. Suction filtration and washing with ethanol gave a red-brown solid with a yield of 77%.
Synthesis of complex L-Ph-Ru-2
77mg (0.25 mmol) of the ligand L-Ph,330mg (0.75 mmol) of Ru-tpy-Cl are weighed out 3 In a 100mL round bottom flask, 50mg of ascorbic acid, 20mg of anhydrous LiCl, ethanol: h 2 20mL of O =4:1, and the reaction is refluxed for 24h under argon protection. After the reaction is finished, cooling to room temperature, carrying out suction filtration to remove insoluble substances, purifying the filtrate by a neutral alumina column, and collecting a mauve band, wherein the developing agent ratio is dichloromethane: methanol =5:1. The yield was 34%. As shown in FIG. 4, m/z:1012.1143, IR (using KBr pellet, cm-1): 517 (vw), 644 (w), 770 (vs), 1015 (m), 1385 (m), 1447 (m), 1568 (vs), 2855 (w), 2922 (vs), 3431 (vs).
One prior art ligand synthesis route is shown in the above process scheme.
Comparative example 1
Synthesis of ligand intermediate 2:
5g (41.5 mmol), 6g (50.3 mmol) of 2-acetylpyridine and N, N-dimethylamide dimethyl acetal are weighed out into a 100mL round-bottomed flask and dissolved in 30mL of toluene. Heating and refluxing, and connecting with a fractionating device to fractionate the produced methanol. After the reaction was carried out for 24 hours, a large amount of yellow-green precipitate was produced. Suction filtration and washing with a small amount of toluene gave the product intermediate 2 in 61% yield. m/z 177.0911. As shown in fig. 3 1 H NMR(400MHz,Chloroform-d)δ8.83–8.46(m,0H),8.15(d,J=7.9Hz,0H),7.91(d,J=12.7Hz,0H),7.86–7.72(m,0H),7.51–7.17(m,0H),6.45(d,J=12.6Hz,0H),3.08(d,J=71.4Hz,1H)。
Synthesis of ligand terpyridine tpy:
2.24g (20 mmol) of potassium tert-butoxide are dissolved in 50ml of THF and 1.21g (10 mmol) of 2-acetylpyridine are added and stirred at room temperature for 2h. After completion, 1.76g (10 mmol) of intermediate 2 was added and stirring continued at room temperature for 18h, the solution gradually turning dark red.
After the reaction was complete, 7.7g (0.1 mol) of NH were added 4 Ac and 25mL glacial acetic acid, and refluxing and reacting for 15min. After completion of the reaction, the solvent was removed by distillation under the reduced pressure to give a black oily residue, to which 50mL of hydrated Na was added 2 CO 3 Until no bubbles were produced, the solution was extracted with dichloromethane (100 mLx 3). Separating the aqueous phase, combining the organic phases and adding Na 2 SO 4 The solution was dried and spun to give a black oil, which was dissolved in 30mL of toluene.
The diatomaceous earth was used to aid filtration and the diatomaceous earth layer was washed with toluene, the solutions were combined, loaded onto a short neutral alumina column, and the chromatographic column was eluted with toluene as the eluent to give a near colorless solution. The solvent was spin dried and recrystallized from n-hexane to give pure product tpy in 30% yield.
Example 2
Synthesis of ligand intermediate 1:
to a 250mL conical flask containing 150mL of distilled water was added NaOH0.72g (18 mmol), and after dissolution with stirring, 5mL of 2-aldehyde pyridine was added, and the mixture was ice-cooled so as not to exceed 8 ℃. 4mL of 2-acetylpyridine is added dropwise at a dropping speed of 2 drops/second, and the reaction is stirred for 30min at a stirring speed of 400rpm. When a large amount of light yellow precipitate appears in the system, the system is filtered by suction and washed by a large amount of water. Drying under reduced pressure at room temperature gave the pale yellow product, intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride is weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A10 mL ethanol solution containing 1.05g (5 mmol) of intermediate 1 was slowly added dropwise at 2 drops/sec over 20 min. And (3) carrying out reflux reaction for 6h, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%.
B: synthesis of ligand L-Ph:
benzamidine hydrochloride 1.7g (11 mmol) was weighed, added to 125mL of anhydrous ethanol, and stirred. 0.520g (13 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise at 1 drop/sec over 1 h. And (3) carrying out reflux reaction for 24 hours, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%. m/z 310.1390.
Example 3
Synthesis of ligand intermediate 1:
0.72g (18 mmol) of NaOH was added to a 250mL Erlenmeyer flask containing 150mL of distilled water, and after dissolution by stirring, 5mL of 2-formylpyridine was added in an ice-water bath so as not to exceed 6 ℃. 4mL of 2-acetylpyridine is added dropwise at the dropping speed of 6 drops/second, the reaction is stirred for 30min, and the stirring speed is 200rpm. When a large amount of light yellow precipitate appears in the system, the system is filtered by suction and washed by a large amount of water. Drying under reduced pressure at room temperature gave the pale yellow product, intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride is weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise at 1 drop/sec, and the addition was completed in 20 min. And (3) carrying out reflux reaction for 6h, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%.
B: synthesis of ligand L-Ph:
benzamidine hydrochloride 1.7g (11 mmol) was weighed, added to 125mL of anhydrous ethanol, and stirred. 0.520g (13 mmol) of granular NaOH is weighed into the solution so that the hydrochloric acid is completely reacted and the solution becomes cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise over 1 h. And (3) carrying out reflux reaction for 24 hours, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%. m/z 310.1390.
Example 4
Synthesis of ligand intermediate 1:
a250 mL conical flask containing 150mL of distilled water was charged with 0.72g (18 mmol) of NaOH, and after dissolution with stirring, 5mL of 2-aldehyde pyridine was added in an ice salt water bath so as not to exceed 9 ℃. 4mL of 2-acetylpyridine is added dropwise at a dropping speed of 8 drops/second, and the reaction is stirred for 30min at a stirring speed of 60rpm. When a large amount of light yellow precipitate appears in the system, the system is filtered by suction and washed by a large amount of water. Drying under reduced pressure at room temperature gave the pale yellow product, intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride is weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, allowing the hydrochloric acid to react completely and the solution to become cloudy and opaque. A10 mL ethanol solution containing 1.05g (5 mmol) of intermediate 1 was slowly added dropwise at 3 drops/sec over 20 min. And (3) carrying out reflux reaction for 6 hours, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%.
B: synthesis of ligand L-Ph:
benzamidine hydrochloride 1.7g (11 mmol) was weighed, added to 125mL of anhydrous ethanol, and stirred. 0.520g (13 mmol) of granular NaOH is weighed into the solution so that the hydrochloric acid is completely reacted and the solution becomes cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 dissolved in 30mL of ethanol was slowly added dropwise at 2 drops/sec over 1 h. And (3) carrying out reflux reaction for 24 hours, cooling to room temperature to obtain a white solid precipitate, and carrying out suction filtration to obtain a product with the yield of 64%.
Including but not limited to the schemes shown in the above examples, naOH and solutions thereof can be replaced with KOH in equimolar amounts without affecting the synthesis of intermediates and ligands.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
2. A process for the preparation of a ligand according to claim 1, comprising the steps of:
reacting S1, 2-aldehyde pyridine with 2-acetyl pyridine under strong alkali and low temperature conditions to obtain an intermediate 1, wherein the structural formula of the intermediate 1 is shown in the specification
S2, weighing a proper amount of raw materials containing any one of 2-pyrimidine formamidine and derivatives thereof, benzamidine and derivatives thereof, processing to obtain an alcohol dispersion liquid I containing a proper amount of 2-pyrimidine formamidine or benzamidine, and dropwise adding a proper amount of the intermediate 1 into the alcohol dispersion liquid I for full reaction to obtain the ligand.
3. The method for preparing the ligand according to claim 2, wherein the strong base condition in S1 is the condition of adding NaOH or KOH in the system.
4. The method for preparing the ligand according to claim 2, wherein the low temperature condition in S1 is a reaction temperature of not higher than 10 ℃.
5. The method of claim 2, wherein the 2-pyrimidine formamidine derivative and the benzamidine derivative in S2 are hydrochloride salts corresponding to each other.
6. The method for preparing a ligand according to claim 2, wherein the intermediate 1 added dropwise to S2 is an alcoholic solution of intermediate 1.
7. A metal complex formed from the ligand of claim 1 and an active metal.
8. The metal complex of claim 7, wherein the active metal is selected from the group consisting of transition metals.
9. Catalytic hydrogen production system comprising at least a ligand according to claim 1 or a metal complex according to claim 7 or 8.
10. Use of a ligand according to claim 1 or a metal complex according to any one of claims 7 to 8 or a catalytic hydrogen production system according to claim 9 for the electrolytic production of hydrogen.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107445943A (en) * | 2017-09-01 | 2017-12-08 | 河南科技大学 | One kind uses the phenyl 4,6 2 of solid-state reaction under microwave 2(2 pyridines)The method of pyrimidine |
CN111848688A (en) * | 2020-08-11 | 2020-10-30 | 中国科学院长春应用化学研究所 | Cationic metal iridium complex, preparation method thereof and photocatalytic hydrolysis method |
CN114195827A (en) * | 2020-09-02 | 2022-03-18 | 广州大学 | Carboxyl substituted ruthenium complex and preparation method and application thereof |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107445943A (en) * | 2017-09-01 | 2017-12-08 | 河南科技大学 | One kind uses the phenyl 4,6 2 of solid-state reaction under microwave 2(2 pyridines)The method of pyrimidine |
CN111848688A (en) * | 2020-08-11 | 2020-10-30 | 中国科学院长春应用化学研究所 | Cationic metal iridium complex, preparation method thereof and photocatalytic hydrolysis method |
CN114195827A (en) * | 2020-09-02 | 2022-03-18 | 广州大学 | Carboxyl substituted ruthenium complex and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
PUSU ZHAO, ET AL.: "Hydrothermal Synthesis, Crystal Structures and Properties of Zinc(II) Di-nuclear Complex and Copper(I) Coordination Polymer Based on Building Block 2-Phenyl-4, 6-di(pyridin-2-yl)pyrimidine", BULL. KOREAN CHEM. SOC., pages 3743 - 3748 * |
ZHAO PU-SU, ET AL.: "Hydrothermal Syntheses, Crystal Structures and Fluorescence of a Copper(I) Polymer and a Salt with H2SO4 Based on a Pyrimidine Building Block", 结构化学, pages 551 - 561 * |
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CN116514879B (en) * | 2023-05-10 | 2024-08-16 | 四川轻化工大学 | Preparation and application of (4, 5-di (2-pyrimidine methylthio) -1, 3-dithiole-2-thione) nickel chloride |
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