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 PDF

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CN115521291A
CN115521291A CN202211254754.0A CN202211254754A CN115521291A CN 115521291 A CN115521291 A CN 115521291A CN 202211254754 A CN202211254754 A CN 202211254754A CN 115521291 A CN115521291 A CN 115521291A
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ligand
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徐聪
陈琪
许瑶瑶
金向华
陈琦峰
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Jinhong Gas Co ltd
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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 formula
Figure DDA0003889335730000011
Wherein R is selected from
Figure DDA0003889335730000012
Or
Figure DDA0003889335730000013
Through 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

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, 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:
Figure BDA0003889335710000021
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 formula
Figure BDA0003889335710000031
Wherein R is selected from
Figure BDA0003889335710000032
Or
Figure BDA0003889335710000033
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 formula
Figure BDA0003889335710000034
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 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:
Figure BDA0003889335710000041
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.
Figure BDA0003889335710000051
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).
Figure BDA0003889335710000071
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)

1. A ligand has a structural formula
Figure FDA0003889335700000011
Wherein R is selected from
Figure FDA0003889335700000012
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
Figure FDA0003889335700000013
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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