CN115894494A - Ligand, complex and application in electrochemical reaction - Google Patents

Ligand, complex and application in electrochemical reaction Download PDF

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CN115894494A
CN115894494A CN202211704002.XA CN202211704002A CN115894494A CN 115894494 A CN115894494 A CN 115894494A CN 202211704002 A CN202211704002 A CN 202211704002A CN 115894494 A CN115894494 A CN 115894494A
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ligand
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CN115894494B (en
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顾均
彭建钊
程要提
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Southern University of Science and Technology
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Abstract

The application discloses ligands, complexes and applications in electrochemical reactions. In a first aspect of the present application, a ligand is provided, wherein the ligand has a structural formula shown in formula I. The N atom coordinated with metal in the existing phthalocyanine and porphyrin is pyrrole nitrogen, and two protons are removed after coordination to obtain a negative charge ligand, so that the whole complex is electrically neutral. Moreover, the ligand is a ligand of a closed-loop rigid structure formed by four pyridine groups, and a single bond between two adjacent pyridine groups is not rotatable and has a unique conformation. When the ligand and metal are utilized to form a complex, the aromatic ring structure of the complex is positioned on the same plane, so that the complex is endowed with stronger stability and catalytic activity.

Description

Ligand, complex and application in electrochemical reaction
Technical Field
The application relates to the technical field of complexes, in particular to a ligand, a complex and application in electrochemical reaction.
Background
Renewable energy conversion is an important method for developing clean energy and solving environmental problems, and a carbon dioxide electrolyzer and a fuel cell are two different types of devices in the current renewable energy conversion field, and are concerned about the characteristics of high efficiency and green. Among the strategies employed by carbon dioxide electrolyzers is the electrocatalytic carbon dioxide reduction (CO) 2 RR) technique for electrochemically converting atmospheric CO 2 Reduction to useful compounds (e.g. CO, CH) 4 、C 2 H 4 、C 2 H 5 OH and the like) which converts the electric energy into chemical energy, not only can reduce the content of carbon dioxide in the atmosphere, but also can realize the storage of the electric energy. The focus of the technology is how to develop a catalyst with excellent performance and low cost to realize high-efficiency conversion of electric energy. The fuel cell converts chemical energy of anode fuel into electric energy mainly through an electrochemical process, and an Oxygen Reduction Reaction (ORR) occurring at a cathode directly affects the conversion efficiency of the fuel cell. Currently, commercial catalysts are mainly platinum-based catalysts, but the use of noble metal platinum results in high cost of fuel cell catalysts. Therefore, development of an ORR catalyst with low cost and high catalytic efficiency is also a research hotspot of fuel cell technology.
Metal complexes in electrochemical reactions, especially carbon dioxide reduction (CO) 2 RR) and Oxygen Reduction Reaction (ORR), where M-N-C materials are considered to be among the most promising non-noble metal catalysts. The active center of such catalysts is generally considered to be MN formed by coordination of a metal M with 4 nitrogen atoms 4 The catalytic activity is affected by various factors such as transition metal source and nitrogen source. The nitrogen source is an important participant of the catalytic active center, the form of the nitrogen-containing ligand mainly comprises a pyrrole structure, phthalocyanine and porphyrin are mainly applied at present, and the bulk and various derivatives of the phthalocyanine and the porphyrin are commercialized. The N atom of the two structures which is coordinated with metal is pyrrole nitrogen, two protons are removed during four-coordination to form a negative charge ligand, and the negative charge ligand is coordinated with metal cations to form an electrically neutral complex. With respect to the neutral tetrapyridine ligandThe metal-nitrogen (M-N4) complex formed by the body and the metal in CO 2 Catalytic activity in electrochemical reactions such as RR and ORR has not been reported.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a ligand, a complex and application in electrochemical reaction, wherein the ligand is an electrically neutral ligand, a cationic complex can be obtained by utilizing the ligand and metal ions, and the ligand, the complex and the application in CO 2 RR and ORR have good catalytic activity.
In a first aspect of the present application, there is provided a ligand having the formula of formula i:
Figure BDA0004025639760000021
wherein R is 1 、R 2 、R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, carboxyl, aldehyde group, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl radical, C 1-30 Alkoxy radical, C 3-30 Cycloalkyloxy radical, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 Arylamino, and R 1 、R 2 、R 8 、R 9 、R 10 And R 11 Adjacent groups may be linked to each other to form a ring.
The ligand provided by the embodiment of the application has at least the following beneficial effects:
the N atom coordinated with metal in the existing phthalocyanine and porphyrin is pyrrole nitrogen, and two protons are removed after coordination to obtain a negative charge ligand, so that the whole complex is electrically neutral. Moreover, the ligand is a ligand of a closed-loop rigid structure formed by four pyridine groups, and a single bond between two adjacent pyridine groups is not rotatable and has a unique conformation. When the ligand and metal are utilized to form a complex, the aromatic ring structure of the complex is positioned on the same plane, so that the complex is endowed with stronger stability and catalytic activity.
Specifically, referring to fig. 1,a, b and c, an existing electronic structure in which a phthalocyanine, a porphyrin and a ligand in the embodiment of the present application are coordinated with a metal ion is respectively shown, wherein both N atoms of the phthalocyanine or the porphyrin and the metal are pyrrole nitrogen, so that two protons are removed after coordination, a negatively charged ligand is obtained, and the complex is electrically neutral as a whole; in contrast, the ligands claimed in this application, represented by c, have N for coordination that is pyridine nitrogen, which is not deprotonated after the pyrroside, and thus form electrically neutral ligands, giving cationic complexes.
Wherein R is 1 And R 2 Are the same substituents, or, R 1 And R 2 Are different substituents. When R is 1 And R 2 When they are the same substituents, R 1 And R 2 Selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, carboxyl, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl, C 1-30 Alkoxy radical, C 3-30 Cycloalkyl oxy, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 The same substituent in arylamino; when R is 1 And R 2 When they are different substituents, R 1 And R 2 Selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, carboxyl, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl radical, C 1-30 Alkoxy radical, C 3-30 Cycloalkyl oxy, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 Different substituents in arylamino.
Similarly, R 8 、R 9 、R 10 And R 11 Are the same radicals, or, R 8 、R 9 、R 10 And R 11 Are different groups. When R is 1 And R 2 When they are the same group, R 1 And R 2 Selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, carboxyl, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl radical, C 1-30 Alkoxy radical, C 3-30 Cycloalkyl oxy, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 The same substituent in arylamino; when R is 1 And R 2 When they are different substituents, R 1 And R 2 Selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, carboxyl, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl radical, C 1-30 Alkoxy radical, C 3-30 Cycloalkyloxy radical, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 Different substituents in arylamino.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, nitro, carboxyl, amino, pyrazinyl and C 1-20 Alkyl radical, C 1 -C 20 Alkylamino radical, C 1-20 Alkoxy radical, C 3-20 Cycloalkyl radical, C 3-20 Cycloalkyl oxy, C 6-30 Aryl radical, C 6-30 Aryloxy radical, C 6-30 An arylamino group.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, nitro, carboxyl, amino, pyrazinyl and C 1-10 Alkyl radical, C 1 -C 10 Alkylamino radical, C 1-10 Alkoxy radical, C 3-10 Cycloalkyl radical, C 3-10 Cycloalkyl oxy, C 6-20 Aryl radical, C 6-20 Aryloxy radical, C 6-20 An arylamino group.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-10 Alkyl radical, C 1 -C 10 Alkylamino radical, C 1-10 Alkoxy radical, C 3-10 Cycloalkyl radical, C 3-10 Cycloalkyl oxy, C 6-10 Aryl radical, C 6-10 Aryloxy radical, C 6-10 An arylamino group.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-8 Alkyl radical, C 1 -C 8 Alkylamino radical, C 1-8 Alkoxy radical, C 3-8 Cycloalkyl radical, C 3-8 Cycloalkyl oxy, C 6-8 Aryl radical, C 6-8 Aryloxy radical, C 6-8 An arylamino group.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-6 Alkyl radical, C 1 -C 6 Alkylamino radical, C 1-6 Alkoxy radical, C 3-6 Cycloalkyl radical, C 3-6 Cycloalkyloxy, phenyl, phenyloxy, phenylamino.
In some embodiments of the present application, R 1 、R 2 Are respectively and independently selected from hydrogen atom, halogen atom, methyl, ethyl, carbonyl, aldehyde group, carboxyl and amino.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, nitro, carboxyl, amino, pyrazinyl and C 1-20 Alkyl radical, C 1 -C 20 Alkylamino radical, C 1-20 Alkoxy radical, C 3-20 Cycloalkyl radical, C 3-20 Cycloalkyl oxy, C 6-30 Aryl radical, C 6-30 Aryloxy radical, C 6-30 An arylamino group.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, nitro, carboxyl, amino, pyrazinyl and C 1-10 Alkyl radical, C 1 -C 10 Alkylamino radical, C 1-10 Alkoxy radical, C 3-10 Cycloalkyl radical, C 3-10 Cycloalkyloxy radical, C 6-20 Aryl radical, C 6-20 Aryloxy radical, C 6-20 An arylamino group.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-10 Alkyl radical, C 1 -C 10 Alkylamino radical, C 1-10 Alkoxy radical, C 3-10 Cycloalkyl radical, C 3-10 Cycloalkyloxy radical, C 6-10 Aryl radical, C 6-10 Aryloxy radical, C 6-10 An arylamino group.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-8 Alkyl radical, C 1 -C 8 Alkylamino radical, C 1-8 Alkoxy radical, C 3-8 Cycloalkyl radical, C 3-8 Cycloalkyloxy radical, C 6-8 Aryl radical, C 6-8 Aryloxy radical, C 6-8 An arylamino group.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, nitro, carboxyl, amino, pyrazinyl and C 1-6 Alkyl radical, C 1 -C 6 Alkylamino radical, C 1-6 Alkoxy radical, C 3-6 Cycloalkyl, C 3-6 Cycloalkyloxy, phenyl, phenyloxy, phenylamino.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Are respectively and independently selected from hydrogen atom, halogen atom, methyl, ethyl, carbonyl, aldehyde group, carboxyl and amino.
In some embodiments of the present application, R 8 、R 9 、R 10 And R 11 Are all hydrogen atoms.
In some embodiments herein, the halogen atom is selected from at least one of fluorine, chlorine, bromine, iodine.
In some embodiments of the present application, R 1 、R 2 Can be linked to each other to form a ring, and/or, R 8 、R 9 May be linked to each other to form a ring, and/or, R 10 And R 11 Can be connected with each other to form a ring. In some of these embodiments, R 1 、R 2 Can be interconnected to form a five-or six-membered ring, and/or, R 8 、R 9 Can be interconnected to form a five-or six-membered ring, and/or, R 10 And R 11 Can be connected with each other to form a five-membered ring or a six-membered ring. In some of these embodiments, the five-or six-membered ring is independently selected from any of a carbocyclic ring, a heteroatom-containing carbocyclic ring. In some embodiments, the heteroatom-containing carbocycle is a carbocycle containing at least one heteroatom optionally selected from boron, nitrogen, oxygen, and sulfur. In some embodiments, the heteroatom-containing carbocycle is a carbocycle containing at least two heteroatoms optionally selected from boron, nitrogen, oxygen, and sulfur atoms. In some of these embodiments, R 1 、R 2 Can be linked to each other to form dioxolanes.
In some embodiments of the present application, R 1 、R 2 Each independently selected from hydrogen, halogen, methyl, ethyl, carbonyl, amino, or R 1 、R 2 Are linked to form dioxolanes.
In some embodiments of the present application, R 1 、R 2 While being a hydrogen atom, or a halogen atom, or a methyl group, or an ethyl group, or a carbonyl group, or an amino group, or R 1 、R 2 Are linked to form dioxolanes.
In some embodiments of the present application, R 1 、R 2 While being a hydrogen atom, or a halogen atom, or a methyl group, or an ethyl group, or a carbonyl group, or an amino group, or R 1 、R 2 Interconnected to form 1,3-dioxolane.
In some embodiments of the present application, R 1 、R 2 While being a hydrogen atom, or a halogen atom, or a methyl group, or an ethyl group, or a carbonyl group, or an amino group, or R 1 、R 2 Connected to form 2,2-dimethyl-1,3-dioxolane.
In a second aspect of the present application, there is provided a method for preparing a ligand, the method comprising the steps of:
Figure BDA0004025639760000051
s1: taking a compound III to react with a compound IV to obtain a compound V;
s2: reacting the compound V with a compound IX to obtain a compound VI;
s3: oxidizing the compound VI to obtain a compound VII;
s4: deprotecting the compound VII to obtain a compound VIII;
s5: reacting a compound VIII with a compound X to obtain a ligand shown in a formula I;
wherein R is 3 And R 4 Each independently selected from halogen atom, alkyl tin and boron group;
R 5 and R 6 Each independently selected from a boric acid group and a halogen atom;
R 7 is C 1-30 An alkyl group;
z is an amino protecting group.
In some embodiments of the present application, Z is any one of Boc, fmoc, cbz.
In some embodiments of the present application, R 3 And R 4 Each independently selected from any one of halogen atoms (including but not limited to chlorine atoms and bromine atoms), alkyl tin (including but not limited to butyl tin and methyl tin), boron groups (including but not limited to boric acid groups and boric acid pinacol esters).
In some embodiments of the present application, R 5 And R 6 Each independently selected from any one of a boric acid group, a chlorine atom and a bromine atom.
In some embodiments of the present application, compound iii in S1 is reacted with compound iv via Suzuki or Stille coupling to give compound v.
In some embodiments of the application, compound v in S2 is reacted with compound ix via Suzuki or Stille coupling to give compound vi.
In some embodiments herein, the catalyst in S1 and/or S2 is a palladium catalyst.
In some embodiments herein, the catalyst in S1 and/or S2 is selected from at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, and bis (tricyclohexylphosphine) palladium dichloride.
In some embodiments herein, the temperature of the coupling reaction in S1 and/or S2 is 60 to 150 ℃. The coupling reaction is facilitated at the reaction temperature.
In some embodiments of the present application, the oxidizing agent in S3 is selenium dioxide.
In some embodiments herein, the reaction temperature in S3 is 60 to 100 ℃.
In some embodiments of the present application, the reaction solvent in S3 is dioxane.
In some embodiments of the present application, the protecting group is Boc and the deprotection reaction in S4 is an acidic condition. In some of these embodiments, the acidic conditions in S4 are provided by at least one acid of hydrochloric acid, p-toluenesulfonic acid, trifluoroacetic acid, aluminum trichloride. In some of these embodiments, the acid in S4 is dissolved in any one of dichloromethane, ethyl acetate, and water to provide acidic conditions. In some embodiments, the volume ratio of acid to solvent in S4 is 1: (1-4). In some embodiments, the acid in S4 is trifluoroacetic acid, the solvent is dichloromethane, and the volume ratio of acid to solvent is 1: (1-4). In some embodiments, the ratio of trifluoroacetic acid to dichloromethane in S4 is about 1:2.
in some embodiments of the present application, the reaction of compound VIII in S5 with compound X at room temperature gives the ligand of formula I. In some of these embodiments, the reaction solvent is methanol.
In a third aspect of the present application, a complex is provided. The structural formula of the complex is shown as the formula II:
Figure BDA0004025639760000061
wherein M is a metal cation, X is an anion, and n is the ratio of the valence state of M to the valence state of X.
In some embodiments of the present application, M is a cation of a transition metal element.
In some embodiments of the present application, M is a cation of any one of the group consisting of metals from groups IB to VIIB and VIII of periods 4 through 6.
In some embodiments of the present application, M is a cation of any one of the metal elements scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury.
In some embodiments of the present application, M is selected from cations of any one of the metal elements of iron, cobalt, nickel, copper, manganese, ruthenium, platinum, chromium, and zinc.
In some embodiments of the present application, X is at least one of a halide, carboxylate, sulfate, sulfite, hydroxide, nitrate, phosphate, monohydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, chlorate, perchlorate, iodate, or periodate.
In some embodiments of the present application, X is at least one of fluoride, chloride, bromide, iodide, formate, acetate, phosphate, sulfate, perchlorate.
In some embodiments herein, n may be an integer or a decimal depending on the valence of M and X.
In a fourth aspect of the present application, there is provided a method for preparing the aforementioned complex, the method comprising the steps of:
taking the ligand or the ligand prepared by the preparation method of the complex;
reacting the ligand with MX n Complexing in solventAnd (3) synthesizing to form a complex shown in a formula II.
In some embodiments of the present application, the solvent is at least one of an organic solvent or water.
In some embodiments herein, the organic solvent is selected from at least one of methanol, ethanol, N-dimethylformamide, dimethylsulfoxide, dichloromethane.
In some embodiments of the present application, the ligand is conjugated to MX n The temperature of the complex reaction is 20-60 ℃.
In a fifth aspect of the present application, there is provided a catalyst comprising the aforementioned complex.
In some embodiments of the present application, the catalyst comprises a support and a complex immobilized on the support. In some of these embodiments, the support is a carbon support. In some of these embodiments, the support comprises at least one of carbon nanotubes, graphene, carbon black.
In some embodiments herein, the catalyst is a composite catalyst, which includes the aforementioned complexes and other metal or non-metal catalysts. In some of these embodiments, the metal catalyst comprises a metal element (e.g., a nanomaterial of Cu, co, sn, au, in, pb, ag, zn, etc.), a metal organic framework material (e.g., ni-MOF, niFe-MOF, etc.). In some of these embodiments, the non-metallic catalyst comprises a carbon material.
In a sixth aspect of the present application, there is provided an electrode or an electrolyte, which comprises the aforementioned complex, or the aforementioned catalyst.
In some embodiments of the present application, the electrode includes a conductive support and a catalyst layer formed on the conductive support, and a raw material of the catalyst layer includes the aforementioned catalyst or complex. In some of the embodiments, the conductive support is selected from at least one of carbon cloth, carbon paper, glassy carbon, carbon nanotubes, and graphite. In some embodiments, the raw material of the catalyst layer further includes at least one of a binder and an additive. In some of these embodiments, the binder and additives are selected from at least one of perfluorosulfonic acid type polymers (Nafion), polyvinylpyrrolidone, polyvinylpyridine. It will be appreciated that in some embodiments, the catalyst layer of the electrode may also contain no binder and additive, and/or the electrode may contain no conductive support and only the catalyst layer.
In some embodiments of the present application, the electrolyte is an acidic, neutral, or alkaline electrolyte. In some of these embodiments, the acid in the acid electrolyte that regulates the acidity of the electrolyte can be sulfuric acid, perchloric acid, or hydrochloric acid, at appropriate concentrations. The alkali for adjusting the alkalinity of the electrolyte in the alkaline electrolyte may be sodium hydroxide, potassium hydroxide or lithium hydroxide of an appropriate concentration.
In some embodiments of the present application, any one of other inorganic salts, organic salts, and catalysts may also be included in the electrolyte. In some embodiments, the solvent of the electrolyte is at least one of an inorganic solvent and an organic solvent, wherein the inorganic solvent may be water, and the organic solvent may be at least one of acetonitrile, N-dimethylformamide, tetrahydrofuran, and dimethylsulfoxide. In some embodiments, an organic salt or an inorganic salt can be added to the electrolyte to increase conductivity, including but not limited to at least one of bicarbonate, sulfate, perchlorate, tetrabutylammonium hexafluorophosphate.
In a seventh aspect of the present application, there is provided a device comprising the aforementioned complex, or the aforementioned catalyst, or the aforementioned electrode or electrolyte.
In some embodiments of the present application, the device is selected from any one of a fuel cell, a carbon dioxide electrolyzer.
In some embodiments of the present application, a device includes a cathode, an anode, and an electrolyte. The electrolyte or cathode includes the aforementioned complexes, catalysts, and the like.
In some embodiments of the present application, a fuel cell includes an anode, an oxygen-reducing cathode, and an electrolyte positioned between the anode and the oxygen-reducing cathode. In some of these embodiments, the electrolyte may be a solid electrolyte or a liquid electrolyte. In some of these embodiments, the oxygen reduction cathode includes the aforementioned catalyst or complex thereon; in other embodiments, the foregoing catalyst or complex is included in the electrolyte.
In some embodiments of the present application, a carbon dioxide electrolysis cell includes an anode, a cathode, and an electrolyte. In some of these embodiments, the electrolyte may be a solid electrolyte or a liquid electrolyte. In some of these embodiments, the cathode comprises the aforementioned catalyst or complex thereon; in other embodiments, the foregoing catalyst or complex is included in the electrolyte.
In an eighth aspect of the present application, there is provided a method for reducing a gas, which comprises mixing the foregoing complex or the foregoing catalyst with a gas, and electrocatalytically reducing the gas; the gas is selected from any one of carbon dioxide and oxygen.
In some embodiments of the present application, a method for reducing carbon dioxide is provided, the method comprising mixing the aforementioned complex or the aforementioned catalyst with carbon dioxide and water, and electrocatalytically reducing carbon dioxide.
In some embodiments of the present application, a method for reducing oxygen is provided, the method comprising mixing the aforementioned complex or catalyst with oxygen and hydrogen to electrocatalytically reduce oxygen.
In some embodiments of the present application, the electrochemical reaction is any one of a carbon dioxide reduction reaction and an oxygen reduction reaction.
In some embodiments of the present application, the carbon dioxide reduction reaction comprises a reaction in which carbon dioxide is reduced to form a product.
In some embodiments of the present application, the product of the reduction of carbon dioxide comprises at least one of a monocarbon compound, a dicarbon compound, and a tricarbon compound. In some embodiments, the one-carbon compound comprises at least one of carbon monoxide, formic acid, methanol, and methane. In some embodiments of the present application, the dicarbonic compound comprises at least one of ethylene, ethanol, ethylene glycol, acetic acid, oxalic acid. In some embodiments herein, the three-carbon compound comprises at least one of propylene, n-propanol, propionaldehyde, and acetone.
In some embodiments of the present application, the carbon dioxide reduction reaction comprises a reaction in which carbon dioxide is reduced to produce carbon monoxide.
In some embodiments of the present application, the oxygen reduction reaction comprises the reduction of oxygen to produce hydrogen peroxide.
In the embodiment of the application, a neutral tetrapyridine ligand is synthesized and prepared into metal-nitrogen (M-N) 4 ) Complexes of this type in electrocatalytic carbon dioxide reduction (CO) 2 RR) and Oxygen Reduction Reaction (ORR) exhibit excellent catalytic activity. The ligand is a closed-loop rigid structure, pyridine groups cannot rotate, and conformation is single; the N4 aromatic ring structure of the complex formed by the ligand and the metal ions is in the same plane, and the electrochemical catalytic reaction verifies that the complex has good catalytic activity and stability compared with the existing non-planar aromatic ring structure.
On the other hand, the complex formed by the electrically neutral ligand and the metal cation is a cationic complex, which is essentially different from the existing porphyrin and phthalocyanine complexes, and no cationic ligand is reported at present. The superiority of the catalytic performance of the neutral ligand and the anionic ligand is taken as a leading-edge scientific problem, and is one of the subjects explored in the field of electrocatalysis at present. The electric neutral ligand provided by the embodiment of the application is superior to the anionic ligand in performance, and shows that the electric neutral ligand has great prospect.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
Fig. 1 shows an electron structure of a ligand (c) provided in examples of the present application, which is different from that of a conventional phthalocyanine (a) or porphyrin (b) when coordinated to a metal ion.
FIG. 2 shows the results of an experiment on the catalytic activity of the electrocatalytic carbon dioxide reduction reaction in example 11 of the present application, wherein a is the partial current density j of the complexes 1 to 12 and Co (II) CPY as catalyst in the presence of CO as product co And b is the Faraday Efficiency (FE) distribution.
FIG. 3 is a diagram of the oxygen reduction reaction in example 12 of the present applicationIn response to the results of the catalytic activity test, a is the current density of Linear Sweep Voltammetry (LSV) of the test group and the control group, and b is the test group H 2 O 2 Yield and number of transferred electrons n.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and larger, smaller, larger, etc. are understood as excluding the present numbers, and larger, smaller, inner, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated. In the description that follows, although a logical order is shown in the flowcharts, in some cases, the steps shown or described may be performed in an order different than in the flowcharts.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing embodiments of the present application only and is not intended to be limiting of the application.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
The concentrations in the following examples are molar concentrations unless otherwise specified.
Materials, reagents, etc. used in the following examples are commercially available, and specific information is as follows:
2-aminophenylboronic acid: 97%, an Naiji chemistry;
di-tert-butyl dicarbonate: 98%, an Naiji chemistry;
triethylamine: AR, an Naiji chemistry;
4-dimethylaminopyridine: AR, bi-di-medicine;
dichloromethane: AR, great;
petroleum ether: AR, great;
ethyl acetate: AR, great;
anhydrous sodium sulfate: AR, great;
deuterated chloroform: 99.6% D, an Naiji chemistry;
8-bromo-2-methylquinoline: 97 percent, obtaining the medicine;
n-butyl lithium: 1.6M hexane solution, an Naiji chemistry;
trimethyl borate: 98%, an Naiji chemistry;
ultra-dry tetrahydrofuran: AR, an Naiji chemistry;
anhydrous ether: AR, great;
anhydrous methanol: AR, great;
2,9-dichloro-1,10-phenanthroline: AR, graduate medicine;
palladium tetratriphenylphosphine: AR, an Naiji chemistry;
ultra-dry 1,4-dioxane: AR, an Naiji chemistry;
selenium dioxide: AR, mcyrin biochemistry;
ultra-dry dichloromethane: AR, an Naiji chemistry;
trifluoroacetic acid: AR, an Naiji chemistry;
vinyl n-butyl ether: 98%, an Naiji chemistry;
anhydrous potassium carbonate: AR, mcelin biochemistry;
deuterated methanol: 99.8% D, an Naiji chemistry;
deuterated dimethyl sulfoxide: 99.9% D, an Naiji chemistry;
cobalt acetate tetrahydrate: AR, mcyrin biochemistry;
anhydrous ferric chloride: AR, mcelin biochemistry;
nickel acetate tetrahydrate: AR, mcelin biochemistry.
The compounds in the following examples were characterized using either nuclear magnetic resonance spectroscopy (Brucker ARX-400) or high resolution mass spectrometry (ESI).
The synthesis route of the complex in the following examples was carried out according to the following reaction equation:
Figure BDA0004025639760000121
example 1 preparation of Compounds 1-2
After 2-aminophenylboronic acid (2g, 14.6mmol, compound 1-1) was dissolved in 25mL of dichloromethane under an argon atmosphere, di-tert-butyl dicarbonate (3.5g, 16.1mmol), triethylamine (2.2g, 21.9 mmol) and 4-dimethylaminopyridine (178mg, 0.15mmol) were added at zero degrees centigrade, followed by warming to room temperature and overnight reaction, the reaction solution was concentrated to give a crude product, which was subjected to silica gel column purification (petroleum ether: ethyl acetate =10 (V/V)) to give a white hair substance (1.18 g), i.e., compound 1-2, in a yield of 34%.
Nuclear magnetic results for Compounds 1-2: 1 H NMR(400MHz,CDCl 3 )δ9.41(s,1H),7.81(d,J＝7.4Hz,1H),7.67(d,J＝8.3Hz,1H),7.31–7.21(m,1H),7.08–6.95(m,1H),1.39(s,9H). 13 C NMR(100MHz,CDCl 3 )δ154.75,142.63,134.96,133.72,131.13,123.05,116.61,82.97,28.48.
example 2 preparation of Compounds 1-4
8-bromo-2-methylquinoline (1g, 4.5mmol, compounds 1-3) was dissolved in 15mL of ultra-dry tetrahydrofuran under an argon atmosphere, then the system was placed in a dry ice acetone bath and 1.6M n-butyllithium (6.2 mL,9.9 mmol) was slowly added dropwise to the solution. After the addition of n-butyllithium was completed, the reaction mixture was allowed to react completely for 45 minutes. Trimethyl borate (1.2 g,11.3 mmol) was then added dropwise to the system, and the reaction was allowed to proceed for 1 hour after the addition was complete. Then, the reaction was allowed to warm to room temperature and continued for 2 hours, and then the reaction was quenched by adding 10mL of ultrapure water to the system. Then, 20mL of a 3M hydrochloric acid solution was added thereto, and the mixture was stirred at room temperature for 0.5 hour. Tetrahydrofuran in the reaction mixture was removed by rotary evaporator, the resulting reaction mixture was washed with 15mL of anhydrous ether, and the aqueous phase was basified with potassium carbonate to a pH of approximately 10. At this time, a precipitate was precipitated, filtered, and the resulting solid was washed with water, and finally washed with a very small amount of methanol to obtain a pale yellow solid (0.54 g), which was the compound 1-4, in a yield of 65%.
Nuclear magnetic results for compounds 1-4: 1 H NMR(400MHz,Chloroform-d)δ8.85(s,2H),8.44–8.34(m,1H),8.15(d,J＝8.4Hz,1H),7.95–7.87(m,1H),7.64–7.53(m,1H),7.41–7.26(m,1H),2.79(s,3H). 13 C NMR(100MHz,CDCl 3 )δ157.70,151.75,137.86,137.60,130.47,125.93,121.60,25.16.
example 3 preparation of Compounds 1-6
2,9-dichlorophenanthroline (0.5g, 2mmol, compound 1-5), compound 1-2 (521mg, 2.2mmol), potassium carbonate (415mg, 3mmol) were added to a high temperature internal pressure tube, then 8ml dioxane and 4ml ultra-purified water were added, argon gas was introduced for twenty minutes to remove air from the solution, tetratriphenylphosphine palladium (116mg, 0.05mol%) was added, after blocking, heating to 120 ℃ for reaction for 2 hours, then waiting to room temperature, 6ml water was added, after extraction three times with dichloromethane, the organic phase was collected, dried with anhydrous sodium sulfate, after filtration, the filtrate was concentrated, and then the crude product was subjected to silica gel column purification (petroleum ether: ethyl acetate =1:3 (V/V)) to give a pale yellow solid (382 mg), that is compound 1-6, with a yield of 47%.
Nuclear magnetic results for compounds 1-6: 1 H NMR(400MHz,CDCl 3 )δ11.92(s,1H),8.41–8.33(m,1H),8.17(d,J＝8.5Hz,1H),8.07(d,J＝8.4Hz,1H),7.88(d,J＝8.6Hz,1H),7.70–7.58(m,3H),7.52(d,J＝8.4Hz,1H),7.38–7.29(m,1H),7.04–6.95(m,1H),1.44(s,9H). 13 C NMR(101MHz,CDCl 3 )δ158.33,153.98,151.33,145.58,143.11,138.96,138.64,137.29,130.38,129.46,127.55,126.94,126.41,125.84,125.71,124.40,122.97,122.15,121.11,79.77,28.43.
example 4 preparation of Compounds 1-7
Compounds 1 to 6 (382mg, 0.94mmol), compounds 1 to 4 (193mg, 1.1mmol), potassium carbonate (195mg, 1.4mmol) were added to a high-temperature pressure resistant tube, then 8ml of dioxane and 4ml of ultra-pure water were added, argon gas was introduced for twenty minutes, then palladium tetratriphenylphosphine (54mg, 0.05mol%) was added, the reaction was heated to 120 ℃ for 2 hours after blocking, then the temperature was waited to room temperature, 6ml of water was added, after extraction with dichloromethane three times, the organic phase was collected, dried with anhydrous sodium sulfate, the filtrate was concentrated after filtration, and then the crude product was subjected to silica gel column purification (petroleum ether: ethyl acetate =1:1 (V/V)) to obtain yellow foamed solid (337 mg), i.e., compounds 1 to 7, with a yield of 70%.
Nuclear magnetic results for compounds 1-7: 1 H NMR(400MHz,CDCl 3 )δ12.16(s,1H),9.17–9.10(m,1H),9.03(d,J＝8.4Hz,1H),8.37(d,J＝8.3Hz,1H),8.34–8.24(m,2H),8.14(d,J＝8.4Hz,1H),7.98–7.91(m,2H),7.84–7.71(m,4H),7.51–7.43(m,1H),7.33(d,J＝8.4Hz,1H),7.21–7.12(m,1H),2.78(s,3H),1.23(s,9H). 13 C NMR(100MHz,CDCl 3 )δ158.68,157.63,157.24,154.17,145.69,145.43,144.60,138.48,137.33,136.65,134.53,133.27,129.85,129.48,129.21,127.86,127.67,127.57,126.83,126.59,126.57,126.13,125.49,122.57,122.30,122.19,121.64,79.58,28.12,25.69.
example 5 preparation of Compounds 1-8
Under an argon atmosphere, compounds 1 to 7 (300mg, 0.59mmol) were dissolved in 15m dioxane, selenium dioxide (130mg, 1.17mmol) was added, followed by raising to 80 ℃ for reaction for 3 hours, the reaction solution was concentrated to give a crude product, and the crude product was subjected to silica gel column purification (petroleum ether: ethyl acetate =1:3 (V/V)) to give a pale red foamy solid (264 mg) which was compounds 1 to 8, with a yield of 85%.
Nuclear magnetic data for compounds 1-8: 1 H NMR(400MHz,Chloroform-d)δ12.01(s,1H),10.14(s,1H),9.15(d,J＝7.1Hz,1H),8.87(d,J＝8.4Hz,1H),8.41–8.27(m,3H),8.25–8.18(m,1H),8.04–7.87(m,4H),7.84(d,J＝8.7Hz,1H),7.78(d,J＝8.7Hz,1H),7.71–7.64(m,1H),7.41–7.32(m,1H),7.13–7.06(m,1H),1.11(s,9H). 13 C NMR(100MHz,CDCl 3 )δ193.84,152.27,145.73,138.40,138.07,137.45,134.83,134.32,130.33,129.95,129.82,129.52,129.24,128.07,127.52,126.75,126.54,126.03,122.65,122.25,117.10,79.60,28.10.
example 6 preparation of Compounds 1-9
Compounds 1 to 8 (200mg, 0.38mmol) were dissolved in 8mL of dichloromethane, 4mL of trifluoroacetic acid was added, the reaction was allowed to react overnight at room temperature, the reaction solution was concentrated to give a tan crude product, which was then redissolved in 5mL of methanol and stirred for 2 hours, after removal of methanol by evaporation under reduced pressure, the crude product was washed with ethyl acetate and dichloromethane, respectively, to give red solids (110 mg), i.e., compounds 1 to 9, in 66% yield.
Nuclear magnetic data for compounds 1-9: 1 H NMR(500MHz,Methanol-d 4 )δ8.90(d,J＝7.2Hz,1H),8.82(d,J＝8.6Hz,1H),8.77(d,J＝8.7Hz,1H),8.54(d,J＝8.2Hz,1H),8.34(d,J＝7.6Hz,1H),8.19(s,2H),7.96–7.84(m,4H),7.69(d,J＝8.3Hz,1H),7.47–7.39(m,1H),7.11(d,J＝8.2Hz,1H),6.96(m,1H),5.98(s,1H),3.35(s,3H). 13 C NMR(125MHz,MeOH-d4)δ159.17,158.02,151.33,145.36,145.19,144.01,140.76,137.24,136.11,135.84,134.66,133.86,132.40,129.77,129.22,129.13,128.38,127.79,127.58,124.50,123.27,121.52,120.80,118.46,116.96,114.29,81.54.
example 7 preparation of Compounds 1-11
Compounds 1-9 (110mg, 0.25mmol) were dissolved in 6mL of methanol, 3mL of vinylbutyl ether was added, the reaction was allowed to react overnight at room temperature, after the reaction solution was concentrated, it was redissolved in 5mL of methanol and 2mL of 2M hydrochloric acid was added, stirred for 2 hours, and directly spin-dried to give a crude product, which was washed with ethyl acetate and dichloromethane, respectively, to give the ligand hydrochloride (91 mg) in 78% yield. Preparative chromatography gave a purer product, but with a reduced yield. Dissolving the obtained ligand hydrochloride by methanol, and alkalifying by potassium carbonate to obtain ligand compounds 1-11.
Nuclear magnetic data for compounds 1-11: 1 H NMR(500MHz,DMSO-d 6 )δ8.26(d,J＝8.4Hz,2H),8.21–8.14(m,4H),8.11–8.01(m,4H),7.83(d,J＝8.0Hz,2H),7.79(s,2H),7.63–7.54(m,2H). 13 CNMR(125MHz,DMSO-d 6 )δ155.25,154.67,144.89,144.34,139.01,136.71,132.35,132.24,130.91,127.90,127.07,126.43,126.16,122.69,119.37.
HRMS (ESI) theory C 30 H 17 N 4 + [M+H] + :433.1448; actually measuring: 433.1450.
example 8 preparation of complexes 1 to 12
The hydrochloride of the compound 1-11 (50mg, 0.11mmol) was dissolved in 5mL of methanol, followed by addition of cobalt acetate tetrahydrate (29mg, 0.12mmol), reaction overnight at room temperature with gradual precipitate formation, centrifugation and collection of the precipitate, addition of 5mL of methanol to wash the precipitate, collection and drying to give a dark green solid (15 mg), compound 1-12, in 22% yield. Iron, cobalt and nickel are paramagnetic and not suitable for nuclear magnetic characterization.
HRMS (ESI) theory C 30 H 16 CoN 4 2+ [M/Z] + :245.5348; actually measuring: 245.5349.
example 9 preparation of complexes 1 to 13
The hydrochloride of the compound 1-11 (50mg, 0.11mmol) was dissolved in 5mL of methanol, followed by addition of copper sulfate pentahydrate (30mg, 0.12mmol), reaction overnight at room temperature, gradual formation of precipitate, centrifugation and collection of precipitate, addition of 5mL of methanol to wash the precipitate, collection and drying to obtain a solid (28 mg) which is the compound 1-13 with a yield of 49%.
HRMS (ESI) theory C 30 H 16 N 4 Cu 2+ [M/Z] 2+ :247.5330; actually measuring: 247.5332.
example 10 preparation of complexes 1 to 14
The hydrochloride salt of compounds 1 to 11 (50mg, 0.11mmol) was dissolved in 5mL of methanol, followed by addition of anhydrous ferric chloride (20mg, 0.12mmol), reaction overnight at room temperature with gradual formation of precipitate, after centrifugation, the solid was collected, washed with 5mLX2 methanol, collected and dried to give a tan solid (25 mg) which was compounds 1 to 14 in 38% yield.
HRMS (ESI): theory C 30 H 16 N 4 FeCl 2 + [M/Z] + :558.0096; found that 558.0100.
Example 11 reduction of carbon dioxide (CO) 2 RR) determination and comparison of catalytic Activity
Preparing catalyst ink: 2mg of complex 1-12 (Co-N) 4 Complex) was dissolved in 1.95ml of n, n-dimethylformamide, followed by addition of 8mg of carbon nanotube (C-Nano, FT 9000) and 0.05mL of a perfluorosulfonic acid type polymer (Nafion) solution. And (3) carrying out ultrasonic treatment on the mixture for more than 3 hours to ensure that the complex and the carbon nano tube are thoroughly combined in a covalent bond mode.
Dropping a proper amount of catalyst ink into the solution of 1 × 1cm 2 The hydrophilic carbon cloth is properly heated and dried. The carbon cloth loaded with the catalyst is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl/saturated KCl solution is used as a reference electrode. The electrolyte concentration was 0.1M potassium bicarbonate solution. And (3) testing the performance of the complex for catalytic reduction of carbon dioxide by using an H-type electrolytic cell.
While using the cobalt complex Co (II) CPY as comparative example 1 (Angew Chem Int Ed Engl.2020Sep21;59 (39): 17104-17109.), its structural formula is shown below:
Figure BDA0004025639760000161
the catalyst ink was prepared by referring to the above method and tested for its performance in catalytic reduction of carbon dioxide compared to complexes 1-12.
The results are shown in FIG. 2. As can be seen from the figure, the cobalt complexes provided in the examples of the present application showed more excellent carbon dioxide reduction (CO) overall than the existing conjugated N4-macrocyclic cobalt complexes 2 RR) catalytic activity, in particular catalytic activity for the production of CO by reduction of carbon dioxide. Specifically, the CO partial current density of the complex 1-12 is maximum at about-1.09V and is higher than 45mA cm -2 And the selectivity of the reduction reaction is better, and the maximum Faraday efficiency of CO reaches 88 percent. Comparative example 1 also had only 30mA at the maximum current density of CO fraction . cm -2 Much lower than complexes 1-12. The catalytic activity of the cobalt complex Co (II) CPY in the carbon dioxide reduction reaction is higher than that of the existing phthalocyanine or porphyrin catalyst, and the electrocatalytic carbon dioxide reduction catalytic activity of the complex provided by the embodiment of the application is far higher than that of the existing porphyrin or phthalocyanine catalyst. The reason for this may be that the ligands provided in the examples of this application are electrically neutral ligands, whereas the existing porphyrins, phthalocyanines or Co (II) CPY are anionic ligands because of the need to remove two protons. Meanwhile, the catalyst has more excellent catalytic activity for reducing carbon dioxide due to various factors such as the influence of a mother nucleus structure and the like.
Example 12 determination of oxygen reduction (ORR) catalytic Activity
A catalyst ink was prepared according to the method of example 11 to thoroughly combine the complex with the carbon nanotubes.
10 μ L of catalyst ink was added dropwise to the disk electrode rotating the disk electrode as a working electrode, the ring electrode was a platinum ring, a platinum wire was used as a counter electrode, and Hg/HgO was used as a reference electrode. The electrolyte concentration was 0.1M potassium hydroxide solution. The rotating ring disk electrode was rotated at 1600rpm. With no addition of complexes 1-12 (Co-N) 4 Carbon nanotubes of Complex) as control group (CNTs), with addition of Complex 1-12 (Co-N) 4 Complexes) as experimental group (Coqpy + CNTs).
As shown in fig. 3, it can be seen that the current density of the experimental group rapidly increased around 0.8V (vs. rhe), while the increase in the current density of the control group was not significant. The selectivity of the oxygen reduction reaction product and the average electron transfer number were calculated by the loop current. The hydrogen peroxide selectivity of the experimental group is about 50%, and the average electron transfer number is about 3. Therefore, the complex has better catalytic activity as a catalyst for oxygen reduction reaction, particularly the catalytic activity for generating hydrogen peroxide by oxygen reduction catalysis.
Example 13
This example provides a ligand 1-11a and a complex 1-12a, which differs from the complex 1-12 provided in example 8 in that 2,9-dichlorophenanthroline (compound 1-5) is replaced by 2,9-dichloro-1,10-phenanthroline-5,6-dione (compound 1-5 a) during the synthesis, and the specific reaction for preparing compounds 1-51 from compounds 1-5 is as follows:
Figure BDA0004025639760000171
the structural formulas of ligands 1-11a and complexes 1-12a are as follows:
Figure BDA0004025639760000172
example 14
This example provides ligands 1-11b and complexes 1-13b, which are synthesized as ligands 1-11b by replacing compound 1-5 with 2,9-dichloro-4,7-diphenyl-1,10-phenanthroline. The structural formula is as follows:
Figure BDA0004025639760000173
example 15
This example provides ligands 1-11c and complexes 1-15c having the following structural formulae:
Figure BDA0004025639760000181
example 16
This example provides ligands 1-11d and complexes 1-16d of the formula:
Figure BDA0004025639760000182
the above examples 13-16 can be prepared by selecting appropriate materials according to the methods of the previous examples or other methods known in the art.
The complexes provided in examples 13 to 16 have good catalytic activities for electrocatalytic carbon dioxide reduction and oxygen reduction as measured by the methods of examples 11 to 12, and are not described herein again.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Claims (9)

1. A ligand, wherein the ligand has the structural formula shown in formula i:
Figure FDA0004025639750000011
wherein R is 1 、R 2 、R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, carboxyl, nitro, amino, pyrazinyl and C 1-30 Alkyl radical, C 1-30 Alkylamino radical, C 3-30 Cycloalkyl, C 1-30 Alkoxy radical, C 3-30 Cycloalkyloxy radical, C 6-40 Aryl radical, C 6-40 Aryloxy radical, C 6-40 Arylamino, and R 1 、R 2 、R 8 、R 9 、R 10 And R 11 Adjacent groups in the structure can be mutually connected to form a ring;
preferably, R 1 、R 2 、R 8 、R 9 、R 10 And R 11 Each independently selected from hydrogen atom, halogen atom, carbonyl, hydroxyl, aldehyde group, nitro, carboxyl, amino, pyrazinyl and C 1-20 Alkyl radical, C 1 -C 20 Alkylamino radical, C 1-20 Alkoxy radical, C 6-30 Aryl radical, C 6-30 Aryloxy radical, C 6-30 An arylamino group;
preferably, R 1 、R 2 、R 8 、R 9 、R 10 And R 11 Are respectively and independently selected from hydrogen atom, halogen atom, methyl, ethyl, carbonyl, aldehyde group, carboxyl and amino;
preferably, R 1 、R 2 May be linked to each other to form a ring, and/or, R 8 、R 9 May be linked to each other to form a ring, and/or, R 10 And R 11 Can be mutually connected to form a ring;
preferably, R 1 、R 2 Each independently selected from hydrogen, halogen, methyl, ethyl, carbonyl, amino, or R 1 、R 2 Are connected to each other to form dioxolane;
preferably, R 8 、R 9 、R 10 And R 11 Are all hydrogen atoms.
2. A process for the preparation of the ligand of claim 1, comprising the steps of:
Figure FDA0004025639750000021
s1: taking a compound III to react with a compound IV to obtain a compound V;
s2: reacting the compound V with a compound IX to obtain a compound VI;
s3: oxidizing the compound VI to obtain a compound VII;
s4: deprotecting the compound VII to obtain a compound VIII;
s5: reacting a compound VIII with a compound X to obtain a ligand shown in a formula I;
wherein R is 3 And R 4 Each independently selected from halogen atoms, alkanesTin and boron radicals;
R 5 and R 6 Each independently selected from a boric acid group and a halogen atom;
R 7 is C 1-30 An alkyl group;
z is an amino protecting group;
preferably, R 3 And R 4 Are respectively and independently selected from chlorine atom, bromine atom, butyl tin, methyl tin, boric acid group and boric acid pinacol ester;
preferably, the catalyst in S1 and/or S2 is a palladium catalyst;
preferably, the palladium catalyst is selected from at least one of tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium dichloride, 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (tricyclohexylphosphine) palladium dichloride;
preferably, the temperature of the coupling reaction in S1 and/or S2 is 60-150 ℃;
preferably, in S3: the oxidant is selenium dioxide; and/or; the reaction temperature is 60-100 ℃; and/or the reaction solvent is dioxane;
preferably, in S4: the deprotection reaction is an acidic condition; and/or; the acidic conditions are provided by trifluoroacetic acid; and/or, the solvent is dichloromethane; and/or the volume ratio of trifluoroacetic acid to dichloromethane is 1: (1-4).
3. The complex is characterized in that the structural formula of the complex is shown as a formula II:
Figure FDA0004025639750000031
wherein M is a metal cation, X is an anion, and n is the ratio of the valence state of M to the valence state of X;
preferably, M is a cation of a transition metal element, and/or X is at least one of a halide, carboxylate, sulfate, sulfite, hydroxide, nitrate, phosphate, monohydrogen phosphate, dihydrogen phosphate, carbonate, bicarbonate, chlorate, perchlorate, iodate, periodate.
4. A process for preparing the complex of claim 3, comprising the steps of:
taking the ligand of claim 1 or the ligand prepared by the preparation method of claim 2;
reacting said ligand with MX n Complexing in a solvent to form a complex shown as a formula II.
5. A catalyst comprising the complex of claim 3.
6. An electrode or an electrolyte comprising the complex of claim 3 or comprising the catalyst of claim 5.
7. A device comprising the complex of claim 3, or comprising the catalyst of claim 5, or comprising the electrode or electrolyte of claim 6;
preferably, the device is selected from any one of a fuel cell, a carbon dioxide electrolyser.
8. A method for reducing a gas, comprising mixing the complex according to claim 3 or the catalyst according to claim 5 with the gas to electrocatalytically reduce the gas; the gas is selected from any one of carbon dioxide and oxygen.
9. Use of a ligand according to claim 1, or a complex according to claim 3, or a catalyst according to claim 5, in an electrochemical reaction;
preferably, the electrochemical reaction is any one of a carbon dioxide reduction reaction and an oxygen reduction reaction.
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