CN115521291B - 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 PDF

Info

Publication number
CN115521291B
CN115521291B CN202211254754.0A CN202211254754A CN115521291B CN 115521291 B CN115521291 B CN 115521291B CN 202211254754 A CN202211254754 A CN 202211254754A CN 115521291 B CN115521291 B CN 115521291B
Authority
CN
China
Prior art keywords
ligand
hydrogen production
production system
catalytic hydrogen
mmol
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
Application number
CN202211254754.0A
Other languages
Chinese (zh)
Other versions
CN115521291A (en
Inventor
徐聪
陈琪
许瑶瑶
金向华
陈琦峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jinhong Gas Co ltd
Original Assignee
Jinhong Gas Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jinhong Gas Co ltd filed Critical Jinhong Gas Co ltd
Priority to CN202211254754.0A priority Critical patent/CN115521291B/en
Publication of CN115521291A publication Critical patent/CN115521291A/en
Application granted granted Critical
Publication of CN115521291B publication Critical patent/CN115521291B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • 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 the structural formula ofWhere R is selected fromOr (b)Through the design of the ligand structure, the bimetallic center can be selectively introduced, the energy transfer efficiency of the antenna-sensitization center is improved, and the method can provide favorable support for the synthesis design of photosensitizers and catalysts.

Description

Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof
Technical Field
The invention relates to a catalytic hydrogen production technology, in particular to a ligand and 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 currently considered to be better. Hydrogen, as an energy carrier, has become a key to solving these increasing world energy demand problems because of its energy density (122 kJ/g) higher than gasoline (40 kJ/g), and pollution-free reaction products. The current main way to obtain hydrogen is still to convert fossil fuels (such as petroleum, coal, natural gas, etc.) to obtain hydrogen, which is the most main method to obtain hydrogen at present. However, this approach is still used with conventional fossil fuels, and these resources are calculated from the worldwide consumption rate and are available for human use for up to 220 years.
In 1972, japanese scholars Fujishima and Honda used illuminating n-type semiconductor TiO 2 The electrodes cause decomposition of water to produce hydrogen. The discovery of this phenomenon reveals that one can use solar energy to effect the decomposition of water to produce hydrogen, that is, we can convert solar energy into chemical energy by catalytic means. In recent years, with research on photocatalyst preparation, modification, photocatalytic theory and the like by various nationists, besides TiO 2 In addition, a plurality of novel photocatalysts are discovered successively, and the photocatalytic efficiency is correspondingly improved. Based on the previous researches of scholars, the reactions of producing hydrogen by photocatalysis are generally divided into two types of homogeneous phase and heterogeneous phase, wherein the homogeneous phase photocatalysis hydrogen production system becomes a hot spot of the researches of people because of the advantages of high catalytic activity, clear catalyst structure, convenient control of the reactions and the like. Classical photocatalytic hydrogen production systems are divided into three parts: proton reduction catalysts, photosensitizers, electron donor sacrificial agents. Wherein, the proton reduction type catalyst has the main function of receiving electrons brought by a Photosensitizer (PS) sensitized by solar light and reducing protons in a reduction system into hydrogen; the photosensitizer polypyridine or porphyrin ligand metal complex in the system is sensitive to light and has better separation capability of photo-generated electrons and holes; the electron donor sacrificial agent provides electrons to reduce the photosensitizer in the oxidized state to the ground state, and common sacrificial agents are Triethylamine (TEA), triethanolamine (TEOA), ethylenediamine tetraacetic acid (EDTA), ascorbic acid, and the like.
The metal ruthenium complex is used as a homogeneous catalyst system with the best effect at present, and the ruthenium metal catalytic center has strong oxidation-reduction capability and a plurality of valence changes, so that the ruthenium complex plays a great role in photocatalytic reaction, and can be used as a photosensitizer and a catalyst in a plurality of reactions. Ruthenium is one of platinum group elements, is easy to form a hexacoordinated complex, and is easy to coordinate with atoms such as nitrogen and oxygen, and in the preparation process of a photosensitizer, a ligand containing bipyridine and a benzene ring is often used. The conventional ruthenium photosensitizer or catalyst for photocatalytic hydrogen production usually adopts a mononuclear structure, and after coordination molecules such as water or methanol are coordinated with metal ruthenium, electron transfer occurs through a photocatalytic effect, so that the coordination molecules generate photoinduced redox reaction.
The following demonstrates the hydrogen production principle of a 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 of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a ligand, a preparation method thereof, a metal complex, a catalytic hydrogen production system and application thereof, and by designing a ligand structure, a bimetallic center can be selectively introduced, so that the energy transfer efficiency of an antenna-sensitized center is improved, and a favorable support can be provided for the synthesis design of a photosensitizer and a catalyst.
To achieve the above object, embodiments of the present invention provide a ligand having the structural formulaWherein R is selected from->Or->
In one or more embodiments of the present invention, a method for preparing a ligand includes the steps of: s1, 2-aldehyde pyridine and 2-ethylAcyl pyridine reacts under the conditions of strong alkali and low temperature to obtain an intermediate 1, wherein the structural formula of the intermediate 1 isS2, 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 then 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 may be: when the raw material is a hydrochloride derivative, a proper amount of strong alkali such as NaOH, KOH (non-solution, such as solid particles and the like) and the like can be added into an alcohol dispersion system (preferably an ethanol dispersion system) of the raw material until the hydrochloric acid is completely reacted. Preferably, the addition of intermediate 1 is a drop of an alcoholic solution of intermediate 1, preferably an alcoholic solution. Preferably, the drop rate is 2-8 drops/second. Preferably, the stirring speed is 60-400rpm.
In one or more embodiments of the invention, the strong base condition in S1 is under the addition of NaOH or KOH to the system.
In one or more embodiments of the invention, the low temperature condition in S1 is a reaction temperature of no higher than 10 ℃. Preferably an ice salt water bath or an ice bath.
In one or more embodiments of the present invention, the 2-pyrimidine formamidine derivative and the benzamidine derivative in S2 are each the hydrochloride salts corresponding to each other.
In one or more embodiments of the present invention, intermediate 1 added dropwise in S2 is an alcoholic solution of intermediate 1.
In one or more embodiments of the invention, the metal complex is a metal complex formed from a ligand as described above and an active metal. The structural formula of part of the metal complex is shown as the following formula:
in one or more embodiments of the invention, the active metal is selected from transition metal elements. Further preferably, the active metal is selected from ruthenium, platinum, iridium. The complex after screening is further optimized, and an effective photocatalysis effect can be obtained.
In one or more embodiments of the invention, the catalytic hydrogen production system comprises 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.
The use of a ligand as described above or a metal complex as described above or a catalytic hydrogen production system as described above in one or more embodiments of the invention for the production of hydrogen by electrolysis.
Compared with the prior art, the ligand, the preparation method, the metal complex, the catalytic hydrogen production system and the application thereof according to the embodiment of the invention have lower synthesis yield compared with the traditional tpy, and the L-Pym and L-Ph ligand have higher laboratory synthesis yield, can form better polypyridine coordination geometry with Ru, and form 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 skeleton of a photosensitizer or a catalyst.
Drawings
FIG. 1 is a ligand L-Pym according to one embodiment of the invention 1 H NMR spectrum;
FIG. 2 is a ligand L-Ph according to one embodiment of the invention 1 H NMR spectrum;
FIG. 3 is a ligand intermediate 2 according to an embodiment of the invention 1 H NMR spectrum;
FIG. 4 is a high resolution mass spectrum of an L-Ph-Ru-2 dinuclear complex according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The synthetic route for the two ligands of the invention is shown in the process scheme described above.
Example 1, shown below, demonstrates one possible preparation scheme for two ligands:
example 1
Synthesis of ligand intermediate 1:
to a 250mL Erlenmeyer flask containing 150mL of distilled water, 0.72g (18 mmol) of NaOH was added, and after dissolution by stirring, 5mL of 2-aldehyde pyridine was added to make it not exceed 10 ℃. 4mL of 2-acetylpyridine was added dropwise, and the reaction was stirred for 30min. After a large amount of pale yellow precipitate appears in the system, the solution is filtered by suction and washed with a large amount of water. Drying under reduced pressure at room temperature to obtain pale yellow product intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride was weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise over 20 min. After 6h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation occurred, and the product was obtained by suction filtration in 64% yield. The product as 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:
1.7g (11 mmol) of benzamidine hydrochloride was weighed out and added to 125mL of absolute ethanol, followed by stirring. 0.520g (13 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise over 1 hour. After 24h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation was observed, and the product was obtained by suction filtration in 64% yield. m/z 310.1390. 1H NMR of the product shown in FIG. 2 (400 MHz, DMSO-d 6) δ9.21 (s, 1H), 8.80 (d, J=4.1 Hz, 3H), 8.75-8.64 (m, 5H), 8.07 (td, J=7.7, 1.7Hz, 2H), 7.58 (d, J=2.0 Hz, 3H).
Complex intermediate Ru-tpy-Cl 3 Is synthesized by (a)
0.524g (2 mmol) RuCl was weighed out 3 ·3H 2 O, tpy 0.466g (2 mmol) was dissolved in 250ml absolute ethanol and refluxed for 8h with vigorous stirring. A large amount of precipitation occurs. Suction filtration and washing with ethanol gave a reddish brown solid in 77% yield.
Synthesis of Complex L-Ph-Ru-2
77mg (0.25 mmol) of 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, and ethanol were added: h 2 Solution of o=4:1 in 20mL, reflux reaction under argon for 24h. After the reaction is completed, cooling to room temperature, removing insoluble substances by suction filtration, purifying filtrate by a neutral alumina column, and collecting mauve bands, wherein the developing agent proportion is methylene dichloride: methanol=5:1. The yield was 34%. M/z 1012.1143, IR (tabletting with KBr, cm-1) as shown in FIG. 4: 517 (vw), 644 (w), 770 (vs), 1015 (m), 1385 (m), 1447 (m), 1568 (vs), 2855 (w), 2922 (vs), 3431 (vs).
The synthetic route for one prior art ligand is shown in the process scheme described above.
Comparative example 1
Synthesis of ligand intermediate 2:
5g (41.5 mmol), 2-acetylpyridine and 6g (50.3 mmol) of N, N-dimethylformamide dimethyl acetal are weighed out in a 100mL round bottom flask and dissolved in 30mL toluene. Heating and refluxing, and connecting a fractionating device in parallel to fractionate the generated methanol. After 24 hours of reaction, a large amount of yellow-green precipitate was generated. Suction filtration and washing with a small amount of toluene gave 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 weighed out in 50ml of THF, 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 was continued at room temperature for 18h, the solution gradually turned to dark red.
After the reaction was completed, 7.7g (0.1 mol) of NH was added 4 Ac and 25mL glacial acetic acid, and reflux reacted for 15min. After completion of the reaction, the solvent was distilled off under reduced pressure to give a black oily residue to which 50mL of hydrated Na was added 2 CO 3 Until no bubbles were generated, the solution was extracted with dichloromethane (100 ml x 3). The aqueous phase was separated, the organic phases combined and taken up with Na 2 SO 4 The solution was dried and spun-dried to give a black oil, which was dissolved in 30mL toluene.
The layers were diafiltered against celite and the layers were washed with toluene, the solutions were combined, passed over a short neutral alumina column and the column was rinsed with toluene as eluent to give a near colorless solution. Spin-drying the solvent and recrystallisation from n-hexane gave the pure product tpy in 30% yield.
Example 2
Synthesis of ligand intermediate 1:
to a 250mL Erlenmeyer flask containing 150mL of distilled water was added NaOH0.72g (18 mmol), and after dissolution with stirring, 5mL of 2-aldehyde pyridine was added to make it not exceed 8 ℃. 4mL of 2-acetylpyridine was added dropwise at a dropping rate of 2 drops/sec, and the reaction was stirred for 30min at a stirring speed of 400rpm. After a large amount of pale yellow precipitate appears in the system, the solution is filtered by suction and washed with a large amount of water. Drying under reduced pressure at room temperature to obtain pale yellow product intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride was weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise at 2 drops/sec over 20 min. After 6h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation occurred, and the product was obtained by suction filtration in 64% yield.
B: synthesis of ligand L-Ph:
1.7g (11 mmol) of benzamidine hydrochloride was weighed out and added to 125mL of absolute ethanol, followed by stirring. 0.520g (13 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise at 1 drop/second over 1 hour. After 24h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation was observed, and the product was obtained by suction filtration in 64% yield. m/z 310.1390.
Example 3
Synthesis of ligand intermediate 1:
to a 250mL Erlenmeyer flask containing 150mL of distilled water, 0.72g (18 mmol) of NaOH was added, and after dissolution by stirring, 5mL of 2-aldehyde pyridine was added to make it not exceed 6℃in an ice-water bath system. 4mL of 2-acetylpyridine was added dropwise at a dropping rate of 6 drops/sec, and the reaction was stirred for 30min at a stirring speed of 200rpm. After a large amount of pale yellow precipitate appears in the system, the solution is filtered by suction and washed with a large amount of water. Drying under reduced pressure at room temperature to obtain pale yellow product intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride was weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise at 1 drop/second over 20 min. After 6h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation occurred, and the product was obtained by suction filtration in 64% yield.
B: synthesis of ligand L-Ph:
1.7g (11 mmol) of benzamidine hydrochloride was weighed out and added to 125mL of absolute ethanol, followed by stirring. 0.520g (13 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise at 3 g/sec over 1 hour. After 24h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation was observed, and the product was obtained by suction filtration in 64% yield. m/z 310.1390.
Example 4
Synthesis of ligand intermediate 1:
to a 250mL Erlenmeyer flask containing 150mL of distilled water was added 0.72g (18 mmol) of NaOH, and after stirring to dissolve, 5mL of 2-aldehyde pyridine was added to make it not exceed 9℃in an ice-salt water bath system. 4mL of 2-acetylpyridine was added dropwise at a dropping rate of 8 drops/second, and the reaction was stirred for 30min at a stirring speed of 60rpm. After a large amount of pale yellow precipitate appears in the system, the solution is filtered by suction and washed with a large amount of water. Drying under reduced pressure at room temperature to obtain pale yellow product intermediate 1.
A: synthesis of ligand L-Pym:
0.792g (5 mmol) of 2-pyrimidine formamidine hydrochloride was weighed into 100mL of absolute ethanol and stirred. 0.240g (6 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 1.05g (5 mmol) of intermediate 1 in 10mL of ethanol was slowly added dropwise at 3 drops/sec over 20 min. After 6h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation occurred, and the product was obtained by suction filtration in 64% yield.
B: synthesis of ligand L-Ph:
1.7g (11 mmol) of benzamidine hydrochloride was weighed out and added to 125mL of absolute ethanol, followed by stirring. 0.520g (13 mmol) of granular NaOH was weighed into the solution, so that the hydrochloric acid was completely reacted, and the solution became cloudy and opaque. A solution of 3.6g (17 mmol) of intermediate 1 in 30mL of ethanol was slowly added dropwise at 2 drops/sec over 1 hour. After 24h of reflux reaction, the mixture was cooled to room temperature, white solid precipitation was observed, and the product was obtained by suction filtration in 64% yield.
Including but not limited to the technical solutions presented in the examples above, naOH and its solutions can be replaced equimolar with KOH without affecting the preparation and synthesis of intermediates and ligands.
The foregoing descriptions of specific exemplary embodiments of the present invention are 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 the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various 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 (7)

1. Catalytic hydrogen production system at least comprises a metal complex L-Ph-Ru-2, wherein the metal complex isWherein M is Ru and R is Ph.
2. The catalytic hydrogen production system of claim 1 wherein the metal complex is a ligandWith Ru-tpy-Cl 3 Obtained by reaction of Ru-tpy-Cl 3 Is RuCl 3 ·3H 2 O is reacted with tpy, where tpy is +.>。
3. The catalytic hydrogen production system of claim 2 wherein the ligand preparation method comprises the steps of:
s1, 2-aldehyde pyridine reacts with 2-acetyl pyridine under the conditions of strong alkali and low temperature to obtain an intermediate 1, wherein the structural formula of the intermediate 1 is；
S2, weighing a proper amount of benzamidine, processing to obtain an alcohol dispersion liquid I containing a proper amount of benzamidine, and then dropwise adding a proper amount of intermediate 1 into the alcohol dispersion liquid I for full reaction to obtain the ligand.
4. A catalytic hydrogen production system as claimed in claim 3 wherein the strong base condition in S1 is under NaOH or KOH added to the system.
5. A catalytic hydrogen production system as claimed in claim 3 wherein the low temperature condition in S1 is a reaction temperature of no more than 10 ℃.
6. A catalytic hydrogen production system as claimed in claim 3 wherein said intermediate 1 added dropwise in S2 is an alcoholic solution of intermediate 1.
7. Use of a catalytic hydrogen production system as claimed in claim 1 in electrolytic hydrogen production.
CN202211254754.0A 2022-10-13 2022-10-13 Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof Active CN115521291B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211254754.0A CN115521291B (en) 2022-10-13 2022-10-13 Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211254754.0A CN115521291B (en) 2022-10-13 2022-10-13 Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof

Publications (2)

Publication Number Publication Date
CN115521291A CN115521291A (en) 2022-12-27
CN115521291B true CN115521291B (en) 2023-11-03

Family

ID=84700940

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211254754.0A Active CN115521291B (en) 2022-10-13 2022-10-13 Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof

Country Status (1)

Country Link
CN (1) CN115521291B (en)

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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..2013,3743-3748. *
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.2015,551-561. *

Also Published As

Publication number Publication date
CN115521291A (en) 2022-12-27

Similar Documents

Publication Publication Date Title
Queyriaux et al. Recent developments in hydrogen evolving molecular cobalt (II)–polypyridyl catalysts
Jiang et al. Chemical and photocatalytic water oxidation by mononuclear Ru catalysts
CN114195827B (en) Carboxyl substituted ruthenium complex and preparation method and application thereof
CN107899611B (en) Organic catalyst with visible light catalytic asymmetric photocatalytic hydroxylation performance, preparation method and application thereof
Lakadamyali et al. Colloidal metal oxide particles loaded with synthetic catalysts for solar H 2 production
Wang et al. A new structural motif for photoinitiated electron collection: Ru, Rh bimetallics providing insight into H 2 production via photocatalysis of water reduction by Ru, Rh, Ru supramolecules
CN115521291B (en) Ligand and preparation method thereof, metal complex, catalytic hydrogen production system and application thereof
CN111686821A (en) Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid
CN114247480A (en) Preparation method and application of dye-based metal organic framework photocatalyst for inert C-H activation
Miyazato et al. Redox Behavior and Catalytic Oxidation Reactions of Alcohols by a New Ruthenium (III)–Dioxolene–Amine Complex of Bis (2-pyridylmethyl)-2-aminoethylamine
CN107540660A (en) It is a kind of using terpyridyl derivative as the iron complex and its synthetic method of part and application
CN102199120B (en) Method for synthesizing 2,2'-bipyridine-4,4'-dicarboxylic acid
WO2024077554A1 (en) Ligand and preparation method therefor, metal complex, catalytic hydrogen production system, and use thereof
CN111686772A (en) Nickel-iron phosphonate nanobelt photocatalyst and preparation method thereof
CN114716459A (en) Carboxyl substituted ruthenium complex, preparation method and application thereof
JP2018516886A (en) Carboxylic ion cross-linked dinuclear iron sulfur cluster fluorescent probe, its production method and its use
CN104815699A (en) Full-color-photoresponsive titanium-dioxide-base photocatalytic material and preparation method thereof, and application of photocatalytic material in hydrogen production
Yang et al. Structural evolution of the Ru-bms complex to the real water oxidation catalyst of Ru-bda: the bite angle matters
CN115611952B (en) Catalyst, preparation method thereof, catalyst system and application
CN114685535B (en) Carboxyl substituted ruthenium complex and preparation method and application thereof
Li et al. A thiadiazolopyridine-functionalized Zr (iv)-based metal–organic framework for enhanced photocatalytic synthesis of tetrahydroquinolines under visible light
CN116651512B (en) Ru-Fe annular photocatalyst with strong visible light absorption and preparation method thereof
CN109970813B (en) Organic metal catalyst, preparation method and application thereof
CN111039993B (en) Ruthenium acetylacetonate complex and application thereof in hydrogen production by photolysis of water
CN113912652A (en) Photocatalytic hydrogen production catalyst and preparation method 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