CN112812057B - Metal nickel hydroxypyridine carboxylic acid complex, synthesis method thereof and application of complex in preparing formic acid by photocatalytic reduction of carbon dioxide - Google Patents
Metal nickel hydroxypyridine carboxylic acid complex, synthesis method thereof and application of complex in preparing formic acid by photocatalytic reduction of carbon dioxide Download PDFInfo
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- CN112812057B CN112812057B CN202110068614.3A CN202110068614A CN112812057B CN 112812057 B CN112812057 B CN 112812057B CN 202110068614 A CN202110068614 A CN 202110068614A CN 112812057 B CN112812057 B CN 112812057B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
- B01J2231/625—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2 of CO2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention relates to the technical field of metal organic complex photocatalytic materials, and discloses a metal nickel hydroxypyridine carboxylic acid complex, a synthesis method thereof and application of photocatalytic reduction of carbon dioxide to formic acid. The molecular formula of the metal nickel hydroxypyridine carboxylic acid complex is C 12 H 12 N 2 NiO 8 The synthesis method comprises the following steps: 2-chloropyridine-6-formic acid and nickel chloride hexahydrate are converted into two molecules of 2-hydroxypyridine-6-formic acid from two molecules of 2-chloropyridine-6-formic acid under the solvothermal condition, and then the two molecules of 2-chloropyridine-6-formic acid react with nickel ions in the nickel chloride hexahydrate to obtain the blue blocky crystal. The metal nickel hydroxypyridine carboxylic acid complex has novel structure, unique synthesis method and certain photocatalysis effect, and can be used as a cheap photocatalyst to catalyze and reduce carbon dioxide into formic acid. The method is simple in operation and has potential application value in the aspect of photocatalytic reduction of carbon dioxide.
Description
Technical Field
The invention relates to the technical field of metal organic complex photocatalytic materials, in particular to a metal nickel hydroxypyridine carboxylic acid complex, a synthesis method thereof and application of photocatalytic reduction of carbon dioxide to formic acid.
Background
With the development of industrial technology, fossil energy is burned, and green vegetation is reduced, resulting in CO in the atmosphere 2 The content is increased, which has a certain influence on our living environment. Thus, how to collect and utilize CO effectively 2 Reducing the CO2 content in the atmosphere has become an important topic of research in the scientific field. CO is processed by 2 Catalytic reduction to organic fuel, which can reduce CO to some extent 2 Is contained in the composition. Constructing a photocatalysis system, and utilizing visible light to catalyze and reduce CO 2 Can obtain, for example, CO and CH 3 OH、 CH 4 And the like. The core of the photocatalysis system is a photocatalysis material, the traditional photocatalysis material generally adopts rare noble metal complexes, and the research of the application of low-cost transition metal complexes to the photocatalysis reduction of carbon dioxide is relatively less, so that the preparation of the low-cost nickel coordination compound as a photocatalyst has a certain potential value. 2-chloropyridine-6-carboxylic acid is a good organic ligand, and a plurality of coordination sites are arranged in the molecule and can be coordinated with transition metal nickel to generate a metal organic compound with stable structure. Nickel dichloride hexahydrate and ligand 2-chloropyridine-6-formic acid are relatively low in cost, and the synthesized complex is applied to photocatalytic reduction of CO 2 It is economically viable.
Disclosure of Invention
In view of the above, the present invention provides an inexpensive metal nickel hydroxypyridine carboxylic acid complex that overcomes at least one of the deficiencies of the prior art described above.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first aspect of the present invention provides a metal nickel hydroxypyridine carboxylic acid complex of formula C 12 H 12 N 2 NiO 8 The structural formula is
The complex is solid crystal, belongs to triclinic system, and has a space group of P-1; the unit cell parameters are: α＝99.824(7)°，β＝94.277(6)°，γ＝113.325(7)°，/>
the complex takes 2-chloropyridine-6-formic acid as a ligand, and chlorine atoms in the ligand react with water to be converted into hydroxyl groups under the condition of high Wen Jian.
In a second aspect, the invention provides a method for synthesizing the metal nickel hydroxypyridine carboxylic acid complex of the first aspect: 2-chloropyridine-6-carboxylic acid and Nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) under the solvothermal condition, two molecules of 2-chloropyridine-6-formic acid are converted into two molecules of 2-hydroxypyridine-6-formic acid, and then the two molecules of 2-hydroxypyridine-6-formic acid react with nickel ions in nickel chloride hexahydrate to obtain the blue blocky crystals.
The synthesis method comprises the following steps:
s1, mixing nickel chloride hexahydrate and ligand 2-chloropyridine-6-formic acid, and dissolving the mixture by using a solvent to obtain a mixed solution;
s2, sealing the mixed solution prepared in the step S1, then carrying out solvothermal reaction, and slowly cooling to room temperature after the reaction is finished to obtain a blue block crystal;
s3, washing the crystal obtained in the step S2 by using a nonpolar solvent, and naturally airing to obtain a monocrystal sample of the complex.
The following is a preferred scheme of the above synthesis method:
in the step S1, the ratio of the amount of the nickel chloride hexahydrate to the amount of the ligand 2-chloropyridine-6-carboxylic acid is 1:2, the solvent is a mixed solvent of purified water and ethanol, and the nickel chloride hexahydrate and the 2-chloropyridine-6-carboxylic acid are dissolved in the purified water and the ethanol respectively and then mixed to obtain the mixed solution.
In the step S2, the solvothermal reaction is carried out at the temperature of 110-150 ℃, the reaction time is 48-96 hours, and the cooling rate is 15 ℃/h.
In step S3, the nonpolar solvent is petroleum ether.
In a third aspect, the present invention provides the use of a metal nickel hydroxypyridine carboxylic acid complex of the first aspect or synthesized by the method of the second aspect in the field of photocatalysis. The metal nickel hydroxypyridine carboxylic acid complex is used as a photocatalyst to catalyze and reduce carbon dioxide, and finally, formic acid is obtained through catalytic reduction.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the invention utilizes the characteristic of the multi-coordination site of the 2-chloropyridine-6-formic acid, and can form a metal coordination compound with stable structure with nickel ions.
And secondly, the invention adopts low-cost nickel salt as a raw material, thereby reducing the cost for preparing the catalyst.
Thirdly, the complex synthesized by the invention can be used as a catalyst to reduce carbon dioxide into formic acid, and the noble metal complex with high cost is avoided being used as a photocatalyst.
Finally, the invention adopts a solvothermal synthesis method, and the synthesized crystal has regular morphology and stable structure and can be used as a MoF material.
Drawings
FIG. 1 is a schematic representation of the crystal structural unit of a metal nickel hydroxypicolinate complex.
FIG. 2 is a liquid chromatogram of a metal nickel hydroxypyridine carboxylic acid complex as a catalyst for reducing carbon dioxide to produce formic acid.
FIG. 3 is a thermogravimetric analysis of a metal nickel hydroxypicolinate complex.
Detailed Description
First, the present invention uses inexpensive nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) is used as raw material, and a compound with novel structure, namely a metal nickel hydroxypyridine carboxylic acid complex, is provided by utilizing the characteristics that the multi-coordination site of 2-chloropyridine-6-formic acid and the central metal nickel ion can generate stable complex, and the molecular formula is C 12 H 12 N 2 NiO 8 The structural formula is as follows:
the complex is a solid crystal, belongs to a triclinic system, and has a space group of P-1; the unit cell parameters are: α＝99.824(7)°，β＝94.277(6)°，γ＝113.325(7)°，/>
next, the complex is prepared from nickel chloride hexahydrate (NiCl) 2 ·6H 2 O) and ligand 2-chloropyridine-6-formic acid are synthesized under solvothermal conditions. Under the solvothermal condition, the 2-chloropyridine-6-formic acid firstly generates 2-hydroxypyridine-6-formic acid, then two molecules of 2-hydroxypyridine-6-formic acid attack one molecule of nickel ions at the same time, and the blue blocky crystals are formed by coordination. The method comprises the following specific steps:
s1, nickel chloride hexahydrate (NiCl) with the mass ratio of 1:2 2 ·6H 2 O) and 2-chloropyridine-6-formic acid are dissolved by using an organic solvent (a mixed solvent of ethanol and purified water) to obtain a transparent green solution;
s2, sealing the mixed solution obtained in the step S1, and then carrying out solvothermal reaction at the reaction temperature of 110-150 ℃ for 48-96 hours at a constant temperature, and slowly cooling to room temperature after the reaction is finished at a cooling rate of 15 ℃/h to obtain a blue block crystal;
s3, washing the blue bulk crystal obtained in the step S2 with petroleum ether, and naturally airing to obtain the monocrystal sample of the metal nickel hydroxypyridine carboxylic acid complex.
Finally, the complex has potential application value in photocatalysis, and is especially used as a photocatalyst for reducing formic acid by carbon dioxide.
The present invention will be further described with reference to specific examples for the purpose of making a clear understanding of the technical aspects of the present invention to those skilled in the art.
Example 1
142.5mg (0.6 mmol) of NiCl was weighed out 2 .6H 2 O is dissolved in 15mL of polytetrafluoroethylene reaction kettle by adding 3mL of water, in addition, 187.4mg (1.2 mmol) of 2-chloropyridine-6-formic acid is weighed into a large test tube filled with magneton, 4mL of ethanol is added, stirring and dissolving are carried out on a magnetic stirrer, then the ethanol solution in the test tube is transferred into the polytetrafluoroethylene reaction kettle for reaction for 48h at 110 ℃, after the reaction is finished, the reaction kettle is cooled to room temperature, blue block crystals are separated out, and the blue block crystals are washed by petroleum ether and driedThus, a single crystal sample of the metal nickel hydroxypyridine carboxylic acid complex is obtained.
Example 2
142.5mg (0.6 mmol) of NiCl was weighed out 2 .6H 2 O is dissolved in 15mL of polytetrafluoroethylene reaction kettle by adding 3mL of water, in addition, 187.4mg (1.2 mmol) of 2-chloropyridine-6-formic acid is weighed into a large test tube filled with magneton, 4mL of ethanol is added, stirring and dissolving are carried out on the solution on a magnetic stirrer, then the ethanol solution in the test tube is transferred into the polytetrafluoroethylene reaction kettle to react for 48h at 130 ℃, after the reaction is finished, the solution is cooled to room temperature, blue block crystals are separated out, and the solution is washed by petroleum ether and dried, thus obtaining the monocrystal sample of the metal nickel hydroxypyridine carboxylic acid complex.
Example 3
142.5mg (0.6 mmol) of NiCl was weighed out 2 .6H 2 O is dissolved in 15mL of polytetrafluoroethylene reaction kettle by adding 3mL of water, in addition, 187.4mg (1.2 mmol) of 2-chloropyridine-6-formic acid is weighed into a large test tube filled with magneton, 4mL of ethanol is added, stirring and dissolving are carried out on the solution on a magnetic stirrer, then the ethanol solution in the test tube is transferred into the polytetrafluoroethylene reaction kettle to react for 48h at 150 ℃, after the reaction is finished, the solution is cooled to room temperature, blue block crystals are separated out, and the solution is washed by petroleum ether and dried, thus obtaining the monocrystal sample of the metal nickel hydroxypyridine carboxylic acid complex.
Example 4
142.5mg (0.6 mmol) of NiCl was weighed out 2 .6H 2 O is dissolved in 15mL of polytetrafluoroethylene reaction kettle by adding 3mL of water, in addition, 187.4mg (1.2 mmol) of 2-chloropyridine-6-formic acid is weighed into a large test tube filled with magneton, 4mL of ethanol is added, stirring and dissolving are carried out on the solution on a magnetic stirrer, then the ethanol solution in the test tube is transferred into the polytetrafluoroethylene reaction kettle to react for 72h at 150 ℃, after the reaction is finished, the solution is cooled to room temperature, blue block crystals are separated out, and the solution is washed by petroleum ether and dried, thus obtaining the monocrystal sample of the metal nickel hydroxypyridine carboxylic acid complex.
Example 5
142.5mg (0.6 mmol) of NiCl was weighed out 2 .6H 2 O is added into a 15mL polytetrafluoroethylene reaction kettle, 3mL of water is added into the reaction kettle to carry out the reactionDissolving, in addition, weighing 187.4mg (1.2 mmol) of 2-chloropyridine-6-formic acid in a large test tube with magnetons, adding 4mL of ethanol, stirring and dissolving on a magnetic stirrer, transferring the ethanol solution in the test tube into a polytetrafluoroethylene reaction kettle, reacting for 96 hours at 150 ℃, cooling to room temperature after the reaction is finished, precipitating blue blocky crystals, washing with petroleum ether, and airing to obtain the monocrystal sample of the metal nickel hydroxypicolinic acid complex.
The testing method comprises the following steps:
the synthesized metal nickel hydroxypicolinate complex was subjected to single crystal diffraction testing on a Rigaku R-AXIS SPIDER diffractometer, and the test results are shown in FIG. 1. The figure shows that the complex synthesized by the invention has novel structure.
The synthesized metal nickel hydroxypyridine carboxylic acid complex is used as a photocatalyst for reduction reaction of carbon dioxide, and the reaction product is subjected to liquid chromatography test in SHIMADZU LC-20A, and the result is shown in figure 2. FIG. 3 shows the results of thermogravimetric analysis of a metal nickel hydroxypicolinate complex, indicating that the complex is structurally stable.
Therefore, the metal nickel hydroxypyridine carboxylic acid complex synthesized by the method disclosed by the invention is novel in structure, has a certain photocatalytic effect, and can be used as a catalyst in a photocatalytic system to reduce carbon dioxide into formic acid. Moreover, the method is simple to operate and has potential application value in photocatalysis.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (9)
1. Metallic nickel hydroxypyridine carboxylic acid complex with a molecular formula of C 12 H 12 N 2 NiO 8 The structural formula is as follows:
。
2. the metal nickel hydroxypicolinate complex as set forth in claim 1, characterized in that the complex uses 2-chloropyridine-6-carboxylic acid as a ligand, and chlorine atoms in the ligand are converted into hydroxyl groups during the reaction.
3. The metal nickel hydroxypicolinate complex as set forth in claim 1, which is a solid crystal, belonging to a triclinic system, and the space group isP-1; the unit cell parameters are:a=6.0856 (4)Å、b=7.0672 (6) Å、c=8.7462 (7) Å、α=99.824 (7)°，β=94.277 (6)°，γ=113.325 (7)°，V =336.12 (5) Å 3 。
4. a method for synthesizing a metal nickel hydroxypyridine carboxylic acid complex according to any one of claims 1-3, wherein two molecules of 2-chloropyridine-6-carboxylic acid are converted into two molecules of 2-hydroxypyridine-6-carboxylic acid under the condition of mixed solvent heat of purified water and ethanol by 2-chloropyridine-6-carboxylic acid and then react with nickel ions in nickel chloride hexahydrate to obtain a blue blocky crystal.
5. The method for synthesizing a metal nickel hydroxypicolinate complex as set forth in claim 4, comprising the steps of:
s1, mixing nickel chloride hexahydrate and ligand 2-chloropyridine-6-formic acid, and dissolving the mixture by using a mixed solvent of purified water and ethanol to obtain a mixed solution;
s2, sealing the mixed solution prepared in the step S1, then carrying out solvothermal reaction, and slowly cooling to room temperature after the reaction is finished to obtain a blue block crystal;
s3, washing the crystal obtained in the step S2 by using petroleum ether, and naturally airing to obtain a monocrystal sample of the complex.
6. The method for synthesizing a metal nickel hydroxypyridine carboxylic acid complex according to claim 5, wherein in step S1, the ratio of the amount of the hexahydrated nickel chloride to the amount of the ligand 2-chloropyridine-6-carboxylic acid is 1:2.
7. The method for synthesizing a metal nickel hydroxypyridine carboxylic acid complex according to claim 5, wherein in the step S2, the solvothermal reaction is performed at 110-150 ℃ for 48-96 hours, and the cooling rate is 15 ℃/h.
8. The use of a metal nickel hydroxypyridine carboxylic acid complex according to any one of claims 1-3 or a metal nickel hydroxypyridine carboxylic acid complex synthesized by the method according to any one of claims 4-7 in the field of photocatalysis, wherein the metal nickel hydroxypyridine carboxylic acid complex is used as a photocatalyst for catalytic reduction of carbon dioxide.
9. Use of a metal nickel hydroxypicolinate complex as claimed in claim 8 in the field of photocatalysis, characterised in that carbon dioxide is catalytically reduced to formic acid.
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| 高鹏.基于5-羟基-2-吡啶羧酸的五个过渡金属配合物的合成、结构及荧光性质.无机化学学报.2015,第31卷(第11期),2236-2242. * |
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