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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Abstract
Description
技术领域technical field
本发明涉及金属有机配合物光催化材料技术领域，更具体地，涉及金属镍羟基吡啶羧酸配合物及其合成方法与光催化还原二氧化碳制甲酸应用。The invention relates to the technical field of metal-organic complex photocatalytic materials, and more specifically, relates to a metal nickel hydroxypyridine carboxylic acid complex and a synthesis method thereof and the application of photocatalytic reduction of carbon dioxide to formic acid.
背景技术Background technique
随着工业技术的发展，化石能源的燃烧，以及绿色植被的减少，导致大气中CO2含量增多，对我们的生活环境造成一定的影响。因此，如何有效收集并利用CO2，减少大气中CO2 含量已成为科研领域研究的重要课题。将CO2催化还原为有机燃料，某种程度上可以降低 CO2的含量。构建一个光催化体系，利用可见光催化还原CO2，可以获得如CO、CH3OH、 CH4等新的有机燃料。光催化体系的核心是光催化材料，传统的光催化材料通常选用稀有的贵金属配合物，而廉价的过渡金属配合物应用于光催化还原二氧化碳的研究相对较少，因此，制备廉价的镍配位化合物作为光催化剂具有一定的潜在价值。2-氯吡啶-6-甲酸是一个良好有机配体，该分子中有多个配位点，可以与过渡金属镍配位生成结构稳定的金属有机化合物。六水二氯化镍和配体2-氯吡啶-6-甲酸都比较廉价，合成的配合物应用于光催化还原CO2，在经济上是可行的。With the development of industrial technology, the combustion of fossil energy, and the reduction of green vegetation, the CO2 content in the atmosphere has increased, which has a certain impact on our living environment. Therefore, how to effectively collect and utilize CO 2 to reduce the content of CO 2 in the atmosphere has become an important topic in the field of scientific research. Catalytic reduction of CO2 to organic fuels can reduce CO2 content to some extent. By constructing a photocatalytic system and using visible light to reduce CO 2 , new organic fuels such as CO, CH 3 OH and CH 4 can be obtained. The core of the photocatalytic system is the photocatalytic material. Traditional photocatalytic materials usually use rare noble metal complexes, and there are relatively few studies on the application of cheap transition metal complexes in the photocatalytic reduction of carbon dioxide. Therefore, the preparation of cheap nickel-coordinated The compounds have certain potential value as photocatalysts. 2-Chloropyridine-6-carboxylic acid is a good organic ligand, and there are multiple coordination sites in the molecule, which can coordinate with the transition metal nickel to form a metal-organic compound with stable structure. Nickel dichloride hexahydrate and ligand 2-chloropyridine-6-carboxylic acid are relatively cheap, and the synthesized complex is economically feasible for photocatalytic reduction of CO 2 .
发明内容Contents of the invention
有鉴于此，本发明为克服上述现有技术所述的至少一种不足，提供一种廉价的金属镍羟基吡啶羧酸配合物。In view of this, the present invention provides a cheap metal nickel hydroxypyridine carboxylic acid complex in order to overcome at least one deficiency described in the above-mentioned prior art.
为了解决上述存在的技术问题，本发明采用下述技术方案：In order to solve the above-mentioned technical problems, the present invention adopts the following technical solutions:
本发明第一方面提供金属镍羟基吡啶羧酸配合物，分子式为C12H12N2NiO8，结构式为 The first aspect of the present invention provides a metal nickel hydroxypyridine carboxylic acid complex, the molecular formula is C 12 H 12 N 2 NiO 8 , and the structural formula is
上述配合物为固态晶体，属于三斜晶系，空间群为P-1；晶胞参数是： α＝99.824(7)°，β＝94.277(6)°，γ＝113.325(7)°，/> The above-mentioned complexes are solid crystals, belonging to the triclinic crystal system, and the space group is P-1; the unit cell parameters are: α=99.824(7)°, β=94.277(6)°, γ=113.325(7)°, />
上述配合物以2-氯吡啶-6-甲酸为配体，所述配体中的氯原子在高温件下与水反应转化为羟基。The above-mentioned complex uses 2-chloropyridine-6-carboxylic acid as a ligand, and the chlorine atom in the ligand reacts with water under a high temperature condition and converts into a hydroxyl group.
本发明第二方面提供第一方面所述金属镍羟基吡啶羧酸配合物的合成方法：将2-氯吡啶 -6-甲酸与六水合氯化镍(NiCl2·6H2O)在溶剂热条件下由两分子2-氯吡啶-6-甲酸转化成两分子 2-羟基吡啶-6-甲酸，再与六水合氯化镍中的镍离子反应得到蔚蓝色的块状晶体。The second aspect of the present invention provides a method for synthesizing the metal nickel hydroxypyridine carboxylic acid complex described in the first aspect: 2-chloropyridine-6-carboxylic acid and nickel chloride hexahydrate (NiCl 2 6H 2 O) under solvothermal conditions Next, two molecules of 2-chloropyridine-6-carboxylic acid are converted into two molecules of 2-hydroxypyridine-6-carboxylic acid, and then react with nickel ions in nickel chloride hexahydrate to obtain azure blue block crystals.
上述合成方法包括如下步骤：Above-mentioned synthetic method comprises the steps:
S1.将六水合氯化镍与配体2-氯吡啶-6-甲酸混合，并用溶剂溶解得到混合液；S1. Mix nickel chloride hexahydrate with ligand 2-chloropyridine-6-carboxylic acid, and dissolve with a solvent to obtain a mixed solution;
S2.将步骤S1制得的混合液进行密封，之后再进行溶剂热反应，反应结束后缓慢冷却至室温，得到蔚蓝色的块状晶体；S2. Seal the mixed solution prepared in step S1, and then carry out solvothermal reaction, and slowly cool to room temperature after the reaction, to obtain azure blue block crystals;
S3.用非极性溶剂洗涤步骤S2所得晶体，自然晾干，即制得该配合物的单晶样品。S3. The crystal obtained in step S2 is washed with a non-polar solvent, and dried naturally to obtain a single crystal sample of the complex.
以下是上述合成方法的优选方案：Below is the preferred scheme of above-mentioned synthetic method:
步骤S1中，所述六水合氯化镍与配体2-氯吡啶-6-甲酸的物质的量之比为1:2，所述溶剂为纯净水与乙醇的混合溶剂，所述六水合氯化镍、2-氯吡啶-6-甲酸分别于纯净水、乙醇中溶解后混合得到所述混合液。In step S1, the ratio of the amount of nickel chloride hexahydrate to the ligand 2-chloropyridine-6-carboxylic acid is 1:2, the solvent is a mixed solvent of pure water and ethanol, and the chlorine hexahydrate Nickel chloride and 2-chloropyridine-6-carboxylic acid were respectively dissolved in purified water and ethanol and then mixed to obtain the mixed solution.
步骤S2中，所述溶剂热反应在110～150℃下进行，反应时间为48～96小时，冷却速率为 15℃/h。In step S2, the solvothermal reaction is carried out at 110-150°C, the reaction time is 48-96 hours, and the cooling rate is 15°C/h.
步骤S3中，所述非极性溶剂为石油醚。In step S3, the non-polar solvent is petroleum ether.
本发明第三方面提供第一方明所述金属镍羟基吡啶羧酸配合物或第二方面所述方法合成的金属镍羟基吡啶羧酸配合物在光催化领域的应用。金属镍羟基吡啶羧酸配合物作为光催化剂将二氧化碳催化还原，最终催化还原为甲酸。The third aspect of the present invention provides the application of the metal nickel hydroxypyridine carboxylic acid complex described in the first statement or the metal nickel hydroxypyridine carboxylic acid complex synthesized by the method described in the second aspect in the field of photocatalysis. The metal nickel hydroxypyridine carboxylic acid complex was used as a photocatalyst to reduce carbon dioxide to formic acid.
本发明与现有技术相比较有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
首先，本发明利用了2-氯吡啶-6-甲酸多配位点的特点，可以与镍离子形成结构稳定的金属配位化合物。Firstly, the present invention utilizes the characteristic of multiple coordination sites of 2-chloropyridine-6-carboxylic acid, and can form a structurally stable metal coordination compound with nickel ions.
其次，本发明采用的是廉价的镍盐为原料，降低了制备催化剂的成本。Secondly, what the present invention uses is cheap nickel salt as a raw material, which reduces the cost of preparing the catalyst.
第三，本发明所合成的配合物可以作为催化剂将二氧化碳还原为甲酸，避免使用成本高的贵金属配合物作为光催化剂。Third, the complex synthesized by the present invention can be used as a catalyst to reduce carbon dioxide to formic acid, avoiding the use of expensive noble metal complexes as photocatalysts.
最后，本发明采用溶剂热合成法，合成的晶体形貌规则，结构稳定，还可以作为MoF材料。Finally, the present invention adopts a solvothermal synthesis method, and the synthesized crystals have regular morphology and stable structure, and can also be used as MoF materials.
附图说明Description of drawings
图1是金属镍羟基吡啶羧酸配合物的晶体结构单元示意图。Figure 1 is a schematic diagram of the crystal structure unit of the metal nickel hydroxypyridine carboxylic acid complex.
图2是金属镍羟基吡啶羧酸配合物作为催化剂还原二氧化碳制备甲酸的液相色谱图。Fig. 2 is the liquid chromatogram of formic acid prepared by reducing carbon dioxide with metal nickel hydroxypyridine carboxylic acid complex as a catalyst.
图3是金属镍羟基吡啶羧酸配合物的热重分析图。Fig. 3 is the thermal gravimetric analysis diagram of the metal nickel hydroxypyridine carboxylic acid complex.
具体实施方式Detailed ways
首先，本发明以廉价的六水合氯化镍(NiCl2·6H2O)为原料，利用2-氯吡啶-6-甲酸的多配位点、可以与中心金属镍离子生成稳定的配合物的特点，提出一种结构新颖的化合物——金属镍羟基吡啶羧酸配合物，其分子式为C12H12N2NiO8，结构式为：First, the present invention uses cheap nickel chloride hexahydrate (NiCl 2 6H 2 O) as a raw material, utilizes the multiple coordination points of 2-chloropyridine-6-carboxylic acid, and can form a stable complex with the central metal nickel ion Features, propose a compound with a novel structure - metal nickel hydroxypyridine carboxylic acid complex, its molecular formula is C 12 H 12 N 2 NiO 8 , and its structural formula is:
该配合物为固态晶体，属于三斜晶系，空间群为P-1；晶胞参数是： α＝99.824(7)°，β＝94.277(6)°，γ＝113.325(7)°，/> The complex is a solid crystal, belonging to the triclinic crystal system, and the space group is P-1; the unit cell parameters are: α=99.824(7)°, β=94.277(6)°, γ=113.325(7)°, />
其次，该配合物是由六水合氯化镍(NiCl2·6H2O)和配体2-氯吡啶-6-甲酸在溶剂热条件下合成。在溶剂热条件下，2-氯吡啶-6-甲酸先生成2-羟基吡啶-6-甲酸，然后，两分子的2-羟基吡啶-6-甲酸同时进攻一分子的镍离子，配位生成蔚蓝色的块状晶体。具体步骤如下：Secondly, the complex was synthesized from nickel chloride hexahydrate (NiCl 2 ·6H 2 O) and ligand 2-chloropyridine-6-carboxylic acid under solvothermal conditions. Under solvothermal conditions, 2-chloropyridine-6-carboxylic acid first generates 2-hydroxypyridine-6-carboxylic acid, and then two molecules of 2-hydroxypyridine-6-carboxylic acid simultaneously attack one molecule of nickel ion, and coordinate to form azure colored blocky crystals. Specific steps are as follows:
S1.将物质的量之比为1:2的六水合氯化镍(NiCl2·6H2O)与2-氯吡啶-6-甲酸用有机溶剂(乙醇和纯净水的混合溶剂)溶解得到透明绿色溶液；S1. Dissolve nickel chloride hexahydrate (NiCl 2 6H 2 O) and 2-chloropyridine-6-carboxylic acid in an organic solvent (a mixed solvent of ethanol and purified water) at a ratio of 1:2 to obtain a transparent green solution;
S2.将步骤S1得到的混合液密封后进行溶剂热反应，反应温度为110～150℃，恒温反应时间为48～96h，反应结束后缓慢冷却至室温，冷却速率为15℃/h，得到蔚蓝色的块状晶体；S2. Seal the mixed liquid obtained in step S1 and carry out solvothermal reaction. The reaction temperature is 110-150°C, and the constant temperature reaction time is 48-96h. After the reaction is completed, it is slowly cooled to room temperature at a cooling rate of 15°C/h to obtain azure colored massive crystals;
S3.用石油醚洗涤步骤S2所得蔚蓝色块状晶体，自然晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。S3. The azure blue blocky crystal obtained in step S2 was washed with petroleum ether, and dried naturally to obtain a single crystal sample of the metal nickel hydroxypyridine carboxylic acid complex.
最后，该配合物在光催化方面的应用上有潜在的应用价值，尤其作为二氧化碳还原甲酸的光催化剂。Finally, the complex has potential applications in photocatalysis, especially as a photocatalyst for carbon dioxide reduction of formic acid.
为了让本领域的技术人员更加清晰地理解本发明的技术方案，下面结合具体实施例对本发明做进一步阐述。In order to allow those skilled in the art to understand the technical solutions of the present invention more clearly, the present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
称取142.5mg(0.6mmol)NiCl2.6H2O于15mL的聚四氟乙烯反应釜中，加入3mL水将其溶解，另外，称取187.4mg(1.2mmol)2-氯吡啶-6-甲酸于装有磁子的大试管中，再加入4mL乙醇，在磁力搅拌器上搅拌溶解，之后将试管中的乙醇溶液转移至聚四氟乙烯反应釜中，于110℃下反应48h，反应结束后冷却至室温，析出蔚蓝色块状晶体，用石油醚洗涤并晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。Weigh 142.5mg (0.6mmol) NiCl 2 .6H 2 O in a 15mL polytetrafluoroethylene reactor, add 3mL water to dissolve it, and weigh 187.4mg (1.2mmol) 2-chloropyridine-6-carboxylic acid Add 4 mL of ethanol to a large test tube equipped with magnets, stir and dissolve on a magnetic stirrer, then transfer the ethanol solution in the test tube to a polytetrafluoroethylene reactor, and react at 110°C for 48 hours. After cooling to room temperature, blue blocky crystals were precipitated, washed with petroleum ether and dried to obtain a single crystal sample of metal nickel hydroxypyridine carboxylic acid complex.
实施例2Example 2
称取142.5mg(0.6mmol)NiCl2.6H2O于15mL的聚四氟乙烯反应釜中，加入3mL水将其溶解，另外，称取187.4mg(1.2mmol)2-氯吡啶-6-甲酸于装有磁子的大试管中，再加入4mL乙醇，在磁力搅拌器上搅拌溶解，之后将试管中的乙醇溶液转移至聚四氟乙烯反应釜中,于130℃下反应48h，反应结束后冷却至室温，析出蔚蓝色块状晶体，用石油醚洗涤并晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。Weigh 142.5mg (0.6mmol) NiCl 2 .6H 2 O in a 15mL polytetrafluoroethylene reactor, add 3mL water to dissolve it, and weigh 187.4mg (1.2mmol) 2-chloropyridine-6-carboxylic acid Add 4 mL of ethanol to a large test tube equipped with magnets, stir and dissolve on a magnetic stirrer, then transfer the ethanol solution in the test tube to a polytetrafluoroethylene reactor, and react at 130°C for 48 hours. After cooling to room temperature, blue blocky crystals were precipitated, washed with petroleum ether and dried to obtain a single crystal sample of metal nickel hydroxypyridine carboxylic acid complex.
实施例3Example 3
称取142.5mg(0.6mmol)NiCl2.6H2O于15mL的聚四氟乙烯反应釜中，加入3mL水将其溶解，另外，称取187.4mg(1.2mmol)2-氯吡啶-6-甲酸于装有磁子的大试管中，再加入4mL乙醇，在磁力搅拌器上搅拌溶解，之后将试管中的乙醇溶液转移至聚四氟乙烯反应釜中,于150℃下反应48h，反应结束后冷却至室温，析出蔚蓝色块状晶体，用石油醚洗涤并晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。Weigh 142.5mg (0.6mmol) NiCl 2 .6H 2 O in a 15mL polytetrafluoroethylene reactor, add 3mL water to dissolve it, and weigh 187.4mg (1.2mmol) 2-chloropyridine-6-carboxylic acid Add 4 mL of ethanol to a large test tube equipped with magnets, stir and dissolve on a magnetic stirrer, then transfer the ethanol solution in the test tube to a polytetrafluoroethylene reactor, and react at 150°C for 48 hours. After cooling to room temperature, blue blocky crystals were precipitated, washed with petroleum ether and dried to obtain a single crystal sample of metal nickel hydroxypyridine carboxylic acid complex.
实施例4Example 4
称取142.5mg(0.6mmol)NiCl2.6H2O于15mL的聚四氟乙烯反应釜中，加入3mL水将其溶解，另外，称取187.4mg(1.2mmol)2-氯吡啶-6-甲酸于装有磁子的大试管中，再加入4mL乙醇，在磁力搅拌器上搅拌溶解，之后将试管中的乙醇溶液转移至聚四氟乙烯反应釜中,于150℃下反应72h，反应结束后冷却至室温，析出蔚蓝色块状晶体，用石油醚洗涤并晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。Weigh 142.5mg (0.6mmol) NiCl 2 .6H 2 O in a 15mL polytetrafluoroethylene reactor, add 3mL water to dissolve it, and weigh 187.4mg (1.2mmol) 2-chloropyridine-6-carboxylic acid Add 4 mL of ethanol to a large test tube equipped with magnets, stir and dissolve on a magnetic stirrer, then transfer the ethanol solution in the test tube to a polytetrafluoroethylene reactor, and react at 150°C for 72 hours. After cooling to room temperature, blue blocky crystals were precipitated, washed with petroleum ether and dried to obtain a single crystal sample of metal nickel hydroxypyridine carboxylic acid complex.
实施例5Example 5
称取142.5mg(0.6mmol)NiCl2.6H2O于15mL的聚四氟乙烯反应釜中，加入3mL水将其溶解，另外，称取187.4mg(1.2mmol)2-氯吡啶-6-甲酸于装有磁子的大试管中，再加入4mL乙醇，在磁力搅拌器上搅拌溶解，之后将试管中的乙醇溶液转移至聚四氟乙烯反应釜中,于150℃下反应96h，反应结束后冷却至室温，析出蔚蓝色块状晶体，用石油醚洗涤并晾干，即制得金属镍羟基吡啶羧酸配合物的单晶样品。Weigh 142.5mg (0.6mmol) NiCl 2 .6H 2 O in a 15mL polytetrafluoroethylene reactor, add 3mL water to dissolve it, and weigh 187.4mg (1.2mmol) 2-chloropyridine-6-carboxylic acid Add 4 mL of ethanol to a large test tube equipped with magnets, stir and dissolve on a magnetic stirrer, then transfer the ethanol solution in the test tube to a polytetrafluoroethylene reactor, and react at 150°C for 96 hours. After cooling to room temperature, blue blocky crystals were precipitated, washed with petroleum ether and dried to obtain a single crystal sample of metal nickel hydroxypyridine carboxylic acid complex.
测试方法：Test Methods:
将合成的金属镍羟基吡啶羧酸配合物在Rigaku R-AXIS SPIDER衍射仪上完成单晶衍射测试，测试结果如图1所示。由图可知，本发明合成的配合物，结构新颖。The synthesized metal nickel hydroxypyridine carboxylic acid complex was subjected to a single crystal diffraction test on a Rigaku R-AXIS SPIDER diffractometer, and the test results are shown in Figure 1. It can be seen from the figure that the compound synthesized by the present invention has a novel structure.
将合成的金属镍羟基吡啶羧酸配合物作为光催化剂应用于二氧化碳的还原反应，反应产物在SHIMADZU LC-20A进行液相色谱测试，结果如图2所示。图3示出了金属镍羟基吡啶羧酸配合物的热重分析结果，表明此配合物结构稳定。The synthesized metal nickel hydroxypyridine carboxylic acid complex was used as a photocatalyst in the reduction reaction of carbon dioxide. The reaction product was tested by liquid chromatography on SHIMADZU LC-20A, and the results are shown in Figure 2. Figure 3 shows the thermogravimetric analysis results of the metal nickel hydroxypyridine carboxylic acid complex, which shows that the structure of the complex is stable.
可见，本发明合成的金属镍羟基吡啶羧酸配合物，不仅结构新颖，而且具有一定的光催化效果，可以在光催化系统中作为催化剂，将二氧化碳还原为甲酸。而且，本发明操作简单，在光催化方面有潜在的应用价值。It can be seen that the metal nickel hydroxypyridine carboxylic acid complex synthesized by the present invention not only has a novel structure, but also has a certain photocatalytic effect, and can be used as a catalyst in a photocatalytic system to reduce carbon dioxide to formic acid. Moreover, the invention is simple to operate and has potential application value in photocatalysis.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. For those of ordinary skill in the art, on the basis of the above description, other changes or changes in different forms can also be made. It is not necessary and impossible to exhaustively list all the implementation manners here. All modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the claims of the present invention.
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