CN114892196B - Hierarchical porous material and preparation method and application thereof - Google Patents

Hierarchical porous material and preparation method and application thereof Download PDF

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CN114892196B
CN114892196B CN202210668347.8A CN202210668347A CN114892196B CN 114892196 B CN114892196 B CN 114892196B CN 202210668347 A CN202210668347 A CN 202210668347A CN 114892196 B CN114892196 B CN 114892196B
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陈轶群
张俊茹
吴强
王喜章
杨立军
胡征
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Abstract

本发明属于二氧化碳还原技术领域,具体涉及一种多级孔材料及其制备方法和应用。本发明提供了一种多级孔材料的制备方法,包括以下步骤:将模板剂、表面修饰剂和极性溶剂混合,得到基体材料;在所述基体材料表面原位生长金属有机化合物,得到前驱体材料;将所述前驱体材料依次进行焙烧和酸浸处理,得到所述多级孔材料;所述模板剂具有疏松多孔结构;所述模板剂包括金属氧化物、金属盐和硅的氧化物中的一种或几种。利用本发明提供的制备方法得到的多级孔材料,在作为二氧化碳电化学还原制备一氧化碳的催化剂时,能够进一步提升二氧化碳转化过程中的反应动力学,提高一氧化碳的法拉第效率和分电流密度。

The invention belongs to the technical field of carbon dioxide reduction, and specifically relates to a hierarchical porous material and its preparation method and application. The invention provides a method for preparing hierarchical porous materials, which includes the following steps: mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material; growing a metal organic compound in situ on the surface of the matrix material to obtain a precursor The precursor material is roasted and acid leached in sequence to obtain the hierarchical porous material; the template agent has a loose porous structure; the template agent includes metal oxides, metal salts and silicon oxides one or more of them. When used as a catalyst for the electrochemical reduction of carbon dioxide to produce carbon monoxide, the hierarchical porous material obtained by the preparation method provided by the invention can further improve the reaction kinetics in the carbon dioxide conversion process and improve the Faradaic efficiency and partial current density of carbon monoxide.

Description

一种多级孔材料及其制备方法和应用A kind of multi-level porous material and its preparation method and application

技术领域Technical field

本发明属于二氧化碳还原技术领域,具体涉及一种多级孔材料及其制备方法和应用。The invention belongs to the technical field of carbon dioxide reduction, and specifically relates to a hierarchical porous material and its preparation method and application.

背景技术Background technique

化石燃料的燃烧造成了二氧化碳的过量排放,加速了全球气候变暖,从而导致了海平面上升和一系列极端天气的发生。因此,将二氧化碳转化为有价值的碳产品势在必行。The burning of fossil fuels has caused excessive emissions of carbon dioxide and accelerated global warming, leading to rising sea levels and a series of extreme weather events. Therefore, converting carbon dioxide into valuable carbon products is imperative.

现有的二氧化碳转化技术中,二氧化碳电化学还原技术具有反应条件温和、反应易于控制和易于模块化的优点。二氧化碳电化学还原的产物主要包括一氧化碳、甲烷、乙烯、甲酸盐、乙酸盐、甲醇或乙醇,其中,一氧化碳具有选择性高,易与电解液分离的优点,同时也可作为化学原料直接参与工业合成。Among the existing carbon dioxide conversion technologies, carbon dioxide electrochemical reduction technology has the advantages of mild reaction conditions, easy reaction control, and easy modularization. The products of electrochemical reduction of carbon dioxide mainly include carbon monoxide, methane, ethylene, formate, acetate, methanol or ethanol. Among them, carbon monoxide has the advantages of high selectivity and easy separation from the electrolyte. It can also be directly used as a chemical raw material. Industrial synthesis.

二氧化碳电化学还原制备一氧化碳的催化剂主要包括银合金催化剂、碳纳米管负载金属复合催化剂等,但是目前的催化剂的活性较低,造成二氧化碳电化学还原过程中一氧化碳法的拉第效率和分电流密度低的缺陷。Catalysts for the electrochemical reduction of carbon dioxide to produce carbon monoxide mainly include silver alloy catalysts, carbon nanotube-supported metal composite catalysts, etc. However, the current catalysts have low activity, resulting in low Radian efficiency and partial current density of the carbon monoxide method during the electrochemical reduction of carbon dioxide. Defects.

发明内容Contents of the invention

本发明的目的在于提供一种多级孔材料及其制备方法和应用,利用本发明提供的方法制备得到的多级孔材料作为二氧化碳电化学还原制备一氧化碳的催化剂,能够提高一氧化碳的法拉第效率和分电流密度。The object of the present invention is to provide a hierarchical porous material and its preparation method and application. The hierarchical porous material prepared by the method provided by the invention can be used as a catalyst for the electrochemical reduction of carbon dioxide to prepare carbon monoxide, which can improve the Faradaic efficiency and separation of carbon monoxide. current density.

为了实现上述目的,本发明提供如下技术方案:In order to achieve the above objects, the present invention provides the following technical solutions:

本发明提供了一种多级孔材料的制备方法,包括以下步骤:The invention provides a method for preparing multi-level porous materials, which includes the following steps:

将模板剂、表面修饰剂和极性溶剂混合,得到基体材料;Mix template agent, surface modification agent and polar solvent to obtain matrix material;

在所述基体材料表面原位生长金属有机化合物,得到前驱体材料;Grow metal organic compounds in situ on the surface of the base material to obtain a precursor material;

将所述前驱体材料依次进行焙烧和酸浸处理,得到所述多级孔材料;The precursor material is roasted and acid leached in sequence to obtain the hierarchical porous material;

所述模板剂具有疏松多孔结构;The template agent has a loose porous structure;

所述模板剂包括金属氧化物、金属盐和硅的氧化物中的一种或几种。The template agent includes one or more of metal oxides, metal salts and silicon oxides.

优选的,所述金属氧化物包括氧化镁和/或氧化锌;所述金属盐包括碱式碳酸镁;所述硅的氧化物包括二氧化硅。Preferably, the metal oxide includes magnesium oxide and/or zinc oxide; the metal salt includes basic magnesium carbonate; and the silicon oxide includes silicon dioxide.

优选的,所述金属有机化合物包括沸石咪唑骨架或金属有机配合物。Preferably, the metal organic compound includes a zeolite imidazole framework or a metal organic complex.

优选的,当所述金属有机化合物为沸石咪唑骨架时,所述原位生长包括以下步骤:将所述基体材料、第一可溶性金属盐、第二可溶性金属盐、2-甲基咪唑和极性溶剂混合,经络合反应,得到所述前驱体材料;Preferably, when the metal organic compound is a zeolite imidazole framework, the in-situ growth includes the following steps: combining the matrix material, the first soluble metal salt, the second soluble metal salt, 2-methylimidazole and polar The solvents are mixed and the precursor material is obtained through a complexation reaction;

所述第一可溶性金属盐为可溶性锌盐;The first soluble metal salt is a soluble zinc salt;

所述第二可溶性金属盐包括可溶性镍盐、可溶性铁盐、可溶性钴盐、可溶性铜盐、可溶性锰盐、可溶性钌盐和可溶性银盐中的一种或几种。The second soluble metal salt includes one or more of soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt.

优选的,当所述金属有机化合物为金属有机配合物时,所述原位生长包括以下步骤:Preferably, when the metal-organic compound is a metal-organic complex, the in-situ growth includes the following steps:

将基体材料、可溶性金属盐、有机物配体和极性溶剂混合,经络合反应,得到所述前驱体材料;Mix the matrix material, soluble metal salt, organic ligand and polar solvent, and undergo a complexation reaction to obtain the precursor material;

所述可溶性金属盐包括可溶性镍盐、可溶性铁盐、可溶性钴盐、可溶性铜盐、可溶性锰盐、可溶性钌盐和可溶性银盐中的一种或几种;The soluble metal salt includes one or more of soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;

所述有机物配体包括邻菲啰啉、甲酰胺、三聚氰胺和聚苯胺中的一种或几种。The organic ligand includes one or more of phenanthroline, formamide, melamine and polyaniline.

优选的,所述焙烧的温度为600~1200℃,保温时间为0.5~10h。Preferably, the roasting temperature is 600-1200°C, and the holding time is 0.5-10h.

优选的,所述模板剂替换为聚苯乙烯;Preferably, the template is replaced with polystyrene;

当所述模板剂为聚苯乙烯时,所述多级孔材料的制备方法不包括酸浸处理。When the template agent is polystyrene, the preparation method of the hierarchical porous material does not include acid leaching treatment.

本发明还提供了上述技术方案所述制备方法制备得到的多级孔材料,所述多级孔材料为金属掺杂的多级孔碳材料。The present invention also provides a hierarchical porous material prepared by the preparation method described in the above technical solution, where the hierarchical porous material is a metal-doped hierarchical porous carbon material.

优选的,所述金属包括镍、铁、钴、铜、锰、钌和银中的一种或几种;Preferably, the metal includes one or more of nickel, iron, cobalt, copper, manganese, ruthenium and silver;

所述金属的质量百分含量为0.5~15.0%。The mass percentage of the metal is 0.5-15.0%.

本发明还提供了上述技术方案所述的多级孔材料在催化二氧化碳还原反应中的应用。The present invention also provides the application of the hierarchical porous material described in the above technical solution in catalyzing carbon dioxide reduction reaction.

本发明提供了一种多级孔材料的制备方法,包括以下步骤:将模板剂、表面修饰剂和极性溶剂混合,得到基体材料;在所述基体材料表面原位生长金属有机化合物,得到前驱体材料;将所述前驱体材料依次进行焙烧和酸浸处理,得到所述多级孔材料;所述模板剂具有疏松多孔结构;所述模板剂包括金属氧化物、金属盐和硅的氧化物中的一种或几种。本发明通过在具有疏松多孔结构的模板剂表面原位生长金属有机化合物,在经过焙烧和酸浸处理后,金属有机化合物会形成与模板剂形貌类似的的多级孔结构,同时在经过焙烧和酸浸处理后,模板剂的疏松多孔结构会传递到碳材料上,最终形成具有多级孔结构的金属掺杂的碳材料;得到的多级孔材料在作为二氧化碳电化学还原制备一氧化碳的催化剂时,能够改善物料在孔道中的运输和活性位点的暴露,从而能够提升二氧化碳转化过程中的反应动力学,提高一氧化碳的法拉第效率和分电流密度。The invention provides a method for preparing hierarchical porous materials, which includes the following steps: mixing a template agent, a surface modification agent and a polar solvent to obtain a matrix material; growing a metal organic compound in situ on the surface of the matrix material to obtain a precursor The precursor material is roasted and acid leached in sequence to obtain the hierarchical porous material; the template agent has a loose porous structure; the template agent includes metal oxides, metal salts and silicon oxides one or more of them. In the present invention, metal organic compounds are grown in situ on the surface of a template with a loose porous structure. After roasting and acid leaching, the metal organic compounds will form a hierarchical porous structure similar in morphology to the template. At the same time, after roasting After acid leaching treatment, the loose porous structure of the template agent will be transferred to the carbon material, eventually forming a metal-doped carbon material with a hierarchical porous structure; the obtained hierarchical porous material is used as a catalyst for the electrochemical reduction of carbon dioxide to produce carbon monoxide. When used, it can improve the transportation of materials in the pores and the exposure of active sites, thereby improving the reaction kinetics during the conversion of carbon dioxide and improving the Faradaic efficiency and partial current density of carbon monoxide.

附图说明Description of drawings

图1为实施例1得到的多级孔材料的STEM图;Figure 1 is a STEM image of the hierarchical porous material obtained in Example 1;

图2为实施例1得到的多级孔材料的SEM图;Figure 2 is an SEM image of the hierarchical porous material obtained in Example 1;

图3为实施例1的合成路线示意图;Figure 3 is a schematic diagram of the synthetic route of Example 1;

图4为以实施例1得到的多级孔材料为催化剂催化二氧化碳还原制备一氧化碳时的一氧化碳的法拉第效率图;Figure 4 is a Faraday efficiency diagram of carbon monoxide when the hierarchical porous material obtained in Example 1 is used as a catalyst to catalyze the reduction of carbon dioxide to produce carbon monoxide;

图5为以实施例1得到的多级孔材料为催化剂催化二氧化碳还原制备一氧化碳时的分电流密度图。Figure 5 is a partial current density diagram when the hierarchical porous material obtained in Example 1 is used as a catalyst to catalyze the reduction of carbon dioxide to produce carbon monoxide.

具体实施方式Detailed ways

本发明提供了一种多级孔材料的制备方法,包括以下步骤:The invention provides a method for preparing multi-level porous materials, which includes the following steps:

将模板剂、表面修饰剂和极性溶剂混合,得到基体材料;Mix template agent, surface modification agent and polar solvent to obtain matrix material;

在所述基体材料表面原位生长金属有机化合物,得到前驱体材料;Grow metal organic compounds in situ on the surface of the base material to obtain a precursor material;

将所述前驱体材料依次进行焙烧和酸浸处理,得到所述多级孔材料;The precursor material is roasted and acid leached in sequence to obtain the hierarchical porous material;

所述模板剂具有疏松多孔结构;The template agent has a loose porous structure;

所述模板剂包括金属氧化物、金属盐和硅的氧化物中的一种或几种。The template agent includes one or more of metal oxides, metal salts and silicon oxides.

在本发明中,若无特殊说明,所有制备原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well known to those skilled in the art.

本发明将模板剂、表面修饰剂和极性溶剂混合,得到基体材料。In the present invention, a template agent, a surface modification agent and a polar solvent are mixed to obtain a matrix material.

在本发明中,所述模板剂具有疏松多孔结构。在本发明中,所述模板剂包括金属氧化物、金属盐和硅的氧化物中的一种或几种。在本发明中,所述金属氧化物优选包括氧化镁和/或氧化锌。在本发明中,所述金属盐优选包括碱式碳酸镁。在本发明中,所述硅的氧化物优选包括二氧化硅。当所述模板剂为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the template agent has a loose porous structure. In the present invention, the template agent includes one or more of metal oxides, metal salts and silicon oxides. In the present invention, the metal oxide preferably includes magnesium oxide and/or zinc oxide. In the present invention, the metal salt preferably includes basic magnesium carbonate. In the present invention, the silicon oxide preferably includes silicon dioxide. When the template agent is two or more of the above selections, the present invention has no special limit on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述表面修饰剂优选包括聚乙烯吡咯烷酮、十二烷基三甲基溴化铵、双十六烷基三甲基溴化铵和十二烷基磺酸钠中一种或几种;当所述表面修饰剂为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the surface modification agent preferably includes one of polyvinylpyrrolidone, dodecyltrimethylammonium bromide, dishexadecyltrimethylammonium bromide and sodium dodecyl sulfonate, or Several types; when the surface modification agent is two or more of the above-mentioned choices, the present invention has no special limit on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述极性溶剂优选包括甲醇、乙醇、二甲基亚砜、N,N-二甲基甲酰胺和水中的一种或几种;当所述极性溶剂为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide and water; when the polar solvent is selected from the above When there are two or more kinds of substances, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述表面修饰剂和模板剂的质量比优选为1:10~10:1,进一步优选为1:9~9:1,更优选为1:8~8:1。In the present invention, the mass ratio of the surface modification agent and the template agent is preferably 1:10 to 10:1, more preferably 1:9 to 9:1, and more preferably 1:8 to 8:1.

在本发明中,所述模板剂和极性溶剂的用量比优选为0.5~50mg:1mL,进一步优选为5~45mg:1mL,更优选为10~40mg:1mL。In the present invention, the usage ratio of the template agent and the polar solvent is preferably 0.5 to 50 mg: 1 mL, more preferably 5 to 45 mg: 1 mL, and more preferably 10 to 40 mg: 1 mL.

在本发明中,所述混合优选在室温的条件下进行。在本发明中,所述混合优选包括依次进行超声和搅拌。在本发明中,所述超声的功率优选为200~3000W,进一步优选为500~2500W,更优选为1000~2000W;时间优选为30min。在本发明中,所述搅拌的转速优选为100~10000rpm,进一步优选为500~9000rpm,更优选为1000~8000rpm;时间优选为6h。所述混合完成后,本发明还优选包括对得到的混合物进行离心分离。本发明对所述分离离心的过程没有特殊的要求,采用本领域技术人员熟知的过程进行即可。In the present invention, the mixing is preferably performed at room temperature. In the present invention, the mixing preferably includes sonication and stirring in sequence. In the present invention, the power of the ultrasound is preferably 200-3000W, more preferably 500-2500W, and more preferably 1000-2000W; the time is preferably 30 minutes. In the present invention, the stirring speed is preferably 100 to 10,000 rpm, more preferably 500 to 9,000 rpm, and more preferably 1,000 to 8,000 rpm; the stirring time is preferably 6 hours. After the mixing is completed, the present invention preferably also includes centrifuging the resulting mixture. The present invention has no special requirements for the separation and centrifugation process, and it can be carried out using processes well known to those skilled in the art.

得到所述基体材料后,本发明在所述基体材料表面原位生长金属有机化合物,得到前驱体材料。After obtaining the matrix material, the present invention grows a metal organic compound in situ on the surface of the matrix material to obtain a precursor material.

在本发明中,所述金属有机化合物优选具有疏松多孔结构。In the present invention, the metal organic compound preferably has a loose porous structure.

在本发明中,所述金属有机化合物优选包括沸石咪唑骨架或金属有机配合物。In the present invention, the metal organic compound preferably includes a zeolite imidazole framework or a metal organic complex.

在本发明中,当所述金属有机化合物为沸石咪唑骨架时,所述原位生长优选包括以下步骤:将所述基体材料、第一可溶性金属盐、第二可溶性金属盐、2-甲基咪唑和极性溶剂混合,经络合反应,得到前驱体材料。In the present invention, when the metal organic compound is a zeolite imidazole framework, the in-situ growth preferably includes the following steps: combining the matrix material, the first soluble metal salt, the second soluble metal salt, and 2-methylimidazole. Mix it with a polar solvent and undergo a complexation reaction to obtain the precursor material.

在本发明中,所述第一可溶性金属盐优选为可溶性锌盐;所述可溶性锌盐优选包括硝酸锌、氯化锌、硫酸锌、丙酮锌和醋酸锌中的一种或几种;当所述可溶性锌盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸锌优选以六水合硝酸锌的形式进行添加。In the present invention, the first soluble metal salt is preferably a soluble zinc salt; the soluble zinc salt preferably includes one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc acetonate and zinc acetate; when the When the soluble zinc salts are two or more of the above selections, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In specific embodiments of the present invention, the zinc nitrate is preferably added in the form of zinc nitrate hexahydrate.

在本发明中,所述第二可溶性金属盐优选包括可溶性镍盐、可溶性铁盐、可溶性钴盐、可溶性铜盐、可溶性锰盐、可溶性钌盐和可溶性银盐中的一种或几种;当所述第二可溶性金属盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the second soluble metal salt preferably includes one or more of soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt; when When the second soluble metal salt is two or more of the above-mentioned choices, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述可溶性镍盐优选包括硝酸镍、柠檬酸镍、醋酸镍、硫酸镍和氯化镍中的一种或几种;当所述可溶性镍盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸镍优选以六水合硝酸镍的形式进行添加。In the present invention, the soluble nickel salt preferably includes one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more of the above selections, When , the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In specific embodiments of the present invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.

在本发明中,所述可溶性铁盐优选包括硝酸铁、柠檬酸铁铵、柠檬酸铁、醋酸铁、乙酰丙酮铁、硫酸铁、二茂铁、氯化铁、醋酸亚铁、硝酸亚铁、硫酸亚铁、乳酸亚铁、氯化亚铁和柠檬酸亚铁中的一种或几种;当所述可溶性铁盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸铁优选以九水合硝酸铁的形式进行添加。In the present invention, the soluble iron salt preferably includes ferric nitrate, ferric ammonium citrate, ferric citrate, ferric acetate, ferric acetylacetonate, ferric sulfate, ferrocene, ferric chloride, ferrous acetate, ferrous nitrate, One or more of ferrous sulfate, ferrous lactate, ferrous chloride and ferrous citrate; when the soluble iron salt is two or more of the above selections, the ratio of the specific substance in the present invention There are no special restrictions and can be mixed in any proportion. In specific embodiments of the present invention, the iron nitrate is preferably added in the form of iron nitrate nonahydrate.

在本发明中,所述可溶性钴盐优选包括硝酸钴、柠檬酸钴、醋酸钴、硫酸钴和氯化钴中的一种或几种;当所述可溶性钴盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸钴优选以六水合硝酸钴的形式进行添加。In the present invention, the soluble cobalt salt preferably includes one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two of the above specific selections In the above, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In specific embodiments of the present invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.

在本发明中,所述可溶性铜盐优选包括硝酸铜、醋酸铜、硫酸铜、氯化铜、醋酸亚铜、硝酸亚铜、硫酸亚铜和氯化亚铜中的一种或几种;当所述可溶性铜盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述硝酸铜优选以六水合硝酸铜的进行添加。In the present invention, the soluble copper salt preferably includes one or more of copper nitrate, copper acetate, copper sulfate, copper chloride, cuprous acetate, cuprous nitrate, cuprous sulfate and cuprous chloride; when When the soluble copper salts are two or more of the above-mentioned specific selections, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In the present invention, the copper nitrate is preferably added as copper nitrate hexahydrate.

在本发明中,所述可溶性锰盐优选包括硝酸锰、柠檬酸锰、醋酸锰、硫酸锰和氯化锰中的一种或几种;当所述可溶性锰盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述硝酸锰优选以六水合硝酸锰的形式进行添加。In the present invention, the soluble manganese salt preferably includes one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two of the above specific choices In the above, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.

在本发明中,所述可溶性钌盐优选包括氯化钌、醋酸钌和二茂钌中一种或几种;当所述可溶性钌盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述可溶性银盐优选包括硝酸银。In the present invention, the soluble ruthenium salt preferably includes one or more of ruthenium chloride, ruthenium acetate and ruthenium dicene; when the soluble ruthenium salt is two or more of the above specific selections, the present invention is suitable for all The proportions of the specific substances mentioned above are not particularly limited, and they can be mixed in any proportion. In the present invention, the soluble silver salt preferably includes silver nitrate.

在本发明中,所述极性溶剂优选包括甲醇、乙醇、二甲基亚砜、N,N-二甲基甲酰胺和水中的一种或几种;当所述极性溶剂为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide and water; when the polar solvent is the specific selection above When there are two or more of them, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述第二可溶性金属盐和第一可溶性金属盐的质量比优选为1:20~20:1,进一步优选为1:17~17:1,更优选为1:15~15:1。在本发明中,所述第一可溶性金属盐和极性溶剂的用量比优选为0.5~50mg:1mL,进一步优选为5~45mg:1mL,更优选为10~40mg:1mL。In the present invention, the mass ratio of the second soluble metal salt and the first soluble metal salt is preferably 1:20-20:1, more preferably 1:17-17:1, and more preferably 1:15-15 :1. In the present invention, the usage ratio of the first soluble metal salt and the polar solvent is preferably 0.5 to 50 mg: 1 mL, more preferably 5 to 45 mg: 1 mL, and more preferably 10 to 40 mg: 1 mL.

本发明对所述混合的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。The present invention has no special limitations on the mixing process, and it can be carried out by using processes well known to those skilled in the art.

在本发明的具体实施例中,所述混合的过程优选包括:将基体材料和第一极性溶剂第一混合,得到第一混合液;将第一可溶性金属盐、第二可溶性金属盐和第二极性溶剂第二混合,得到第二混合液;将2-甲基咪唑和第三极性溶剂第三混合,得到第三混合液;将所述第二混合液和第三混合液滴入第一混合液中。In a specific embodiment of the present invention, the mixing process preferably includes: first mixing the base material and the first polar solvent to obtain a first mixed liquid; mixing the first soluble metal salt, the second soluble metal salt and the third Mix the bipolar solvent for a second time to obtain a second mixed liquid; mix 2-methylimidazole and a third polar solvent for a third time to obtain a third mixed liquid; drop the second mixed liquid and the third mixed liquid into in the first mixture.

在本发明中,所述第一极性溶剂、所述第二极性溶剂和所述第三极性溶剂的种类均和上述限定的极性溶剂的种类相同,在此不再赘述。In the present invention, the types of the first polar solvent, the second polar solvent and the third polar solvent are all the same as the types of polar solvents defined above, and will not be described again here.

在本发明中,所述第一极性溶剂、所述第二极性溶剂和所述第三极性溶剂的总体积和上述技术方案限定的极性溶剂的体积相同。In the present invention, the total volume of the first polar solvent, the second polar solvent and the third polar solvent is the same as the volume of the polar solvent defined in the above technical solution.

在本发明中,所述基体材料和第一极性溶剂的用量比优选为0.5~100mg:1mL,进一步优选为20~80mg:1mL。在本发明中,所述第一可溶性金属盐和第二极性溶剂的用量比优选为0.5~100mg:1mL,进一步优选为20~50mg:1mL。在本发明中,所述2-甲基咪唑和第三极性溶剂的用量比为优选为0.5~100mg:1mL,进一步优选为20~50mg:1mL。In the present invention, the usage ratio of the matrix material and the first polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 20 to 80 mg: 1 mL. In the present invention, the usage ratio of the first soluble metal salt and the second polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 20 to 50 mg: 1 mL. In the present invention, the usage ratio of the 2-methylimidazole and the third polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 20 to 50 mg: 1 mL.

本发明对所述第一混合、第二混合和第三混合的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。The present invention has no special limitations on the processes of the first mixing, the second mixing and the third mixing, and can be carried out using processes well known to those skilled in the art.

在本发明中,所述第二混合液和所说第三混合液的滴入速度独立的优选为2~10mL/min,进一步优选为5mL/min。In the present invention, the dripping speeds of the second mixed liquid and the third mixed liquid are independently preferably 2 to 10 mL/min, and more preferably 5 mL/min.

在本发明中,所述络合反应的温度优选为20~200℃,进一步优选为40~180℃,更优选为60~160℃;时间优选为6~48h,进一步优选为10~40h,更优选为15~35h。在本发明中,所述络合反应优选在搅拌的条件下进行;所述搅拌的转速优选为100~10000rpm,进一步优选为300~9000rpm,更优选为800~8000rpm。在本发明中,所述络合反应优选在回流的条件下进行。In the present invention, the temperature of the complexation reaction is preferably 20 to 200°C, more preferably 40 to 180°C, more preferably 60 to 160°C; the time is preferably 6 to 48h, further preferably 10 to 40h, and more Preferably it is 15 to 35 hours. In the present invention, the complexing reaction is preferably carried out under stirring conditions; the rotating speed of the stirring is preferably 100 to 10000 rpm, more preferably 300 to 9000 rpm, and more preferably 800 to 8000 rpm. In the present invention, the complexation reaction is preferably carried out under reflux conditions.

所述络合反应完成后,本发明还优选包括将得到的产物进行离心分离、干燥和研磨。本发明对所述离心分离和研磨的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。在本发明中,所述干燥的温度优选为70℃;时间优选为12h。在本发明中,所述干燥优选在真空烘箱中进行。After the complexation reaction is completed, the present invention also preferably includes centrifuging, drying and grinding the obtained product. The present invention has no special limitations on the processes of centrifugal separation and grinding, and can be carried out using processes well known to those skilled in the art. In the present invention, the drying temperature is preferably 70°C; the drying time is preferably 12 hours. In the present invention, the drying is preferably performed in a vacuum oven.

在本发明中,当所述金属有机化合物为金属有机配合物时,所述原位生长优选包括以下步骤:In the present invention, when the metal organic compound is a metal organic complex, the in situ growth preferably includes the following steps:

将基体材料、可溶性金属盐、有机物配体和极性溶剂混合,经络合反应,得到所述前驱体材料。The matrix material, soluble metal salt, organic ligand and polar solvent are mixed, and the precursor material is obtained through a complexation reaction.

在本发明中,所述可溶性金属盐优选包括可溶性镍盐、可溶性铁盐、可溶性钴盐、可溶性铜盐、可溶性锰盐、可溶性钌盐和可溶性银盐中的一种或几种。In the present invention, the soluble metal salt preferably includes one or more of soluble nickel salt, soluble iron salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt.

在本发明中,所述可溶性镍盐优选包括硝酸镍、柠檬酸镍、醋酸镍、硫酸镍和氯化镍中的一种或几种;当所述可溶性镍盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸镍优选以六水合硝酸镍的形式进行添加。In the present invention, the soluble nickel salt preferably includes one or more of nickel nitrate, nickel citrate, nickel acetate, nickel sulfate and nickel chloride; when the soluble nickel salt is two or more of the above selections, When , the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In specific embodiments of the present invention, the nickel nitrate is preferably added in the form of nickel nitrate hexahydrate.

在本发明中,所述可溶性铁盐优选包括硝酸铁、柠檬酸铁铵、柠檬酸铁、醋酸铁、乙酰丙酮铁、硫酸铁、二茂铁、氯化铁、醋酸亚铁、硝酸亚铁、硫酸亚铁、乳酸亚铁、氯化亚铁和柠檬酸亚铁中的一种或几种;当所述可溶性铁盐为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸铁优选以九水合硝酸铁的形式进行添加。In the present invention, the soluble iron salt preferably includes ferric nitrate, ferric ammonium citrate, ferric citrate, ferric acetate, ferric acetylacetonate, ferric sulfate, ferrocene, ferric chloride, ferrous acetate, ferrous nitrate, One or more of ferrous sulfate, ferrous lactate, ferrous chloride and ferrous citrate; when the soluble iron salt is two or more of the above selections, the ratio of the specific substance in the present invention There are no special restrictions and can be mixed in any proportion. In specific embodiments of the present invention, the iron nitrate is preferably added in the form of iron nitrate nonahydrate.

在本发明中,所述可溶性钴盐优选包括硝酸钴、柠檬酸钴、醋酸钴、硫酸钴和氯化钴中的一种或几种;当所述可溶性钴盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明的具体实施例中,所述硝酸钴优选以六水合硝酸钴的形式进行添加。In the present invention, the soluble cobalt salt preferably includes one or more of cobalt nitrate, cobalt citrate, cobalt acetate, cobalt sulfate and cobalt chloride; when the soluble cobalt salt is two of the above specific selections In the above, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In specific embodiments of the present invention, the cobalt nitrate is preferably added in the form of cobalt nitrate hexahydrate.

在本发明中,所述可溶性铜盐优选包括硝酸铜、醋酸铜、硫酸铜、氯化铜、醋酸亚铜、硝酸亚铜、硫酸亚铜和氯化亚铜中的一种或几种;当所述可溶性铜盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述硝酸铜优选以六水合硝酸铜的进行添加。In the present invention, the soluble copper salt preferably includes one or more of copper nitrate, copper acetate, copper sulfate, copper chloride, cuprous acetate, cuprous nitrate, cuprous sulfate and cuprous chloride; when When the soluble copper salts are two or more of the above-mentioned specific selections, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In the present invention, the copper nitrate is preferably added as copper nitrate hexahydrate.

在本发明中,所述可溶性锰盐优选包括硝酸锰、柠檬酸锰、醋酸锰、硫酸锰和氯化锰中的一种或几种;当所述可溶性锰盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述硝酸锰优选以六水合硝酸锰的形式进行添加。In the present invention, the soluble manganese salt preferably includes one or more of manganese nitrate, manganese citrate, manganese acetate, manganese sulfate and manganese chloride; when the soluble manganese salt is two of the above specific choices In the above, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion. In the present invention, the manganese nitrate is preferably added in the form of manganese nitrate hexahydrate.

在本发明中,所述可溶性钌盐优选包括氯化钌、醋酸钌和二茂钌中一种或几种;当所述可溶性钌盐为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述可溶性银盐优选包括硝酸银。In the present invention, the soluble ruthenium salt preferably includes one or more of ruthenium chloride, ruthenium acetate and ruthenium dicene; when the soluble ruthenium salt is two or more of the above specific selections, the present invention is suitable for all The proportions of the specific substances mentioned above are not particularly limited, and they can be mixed in any proportion. In the present invention, the soluble silver salt preferably includes silver nitrate.

在本发明中,所述有机物配体优选包括邻菲啰啉、甲酰胺、三聚氰胺和聚苯胺中的一种或几种;当所述有机物配体为上述选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the organic ligand preferably includes one or more of phenanthroline, formamide, melamine and polyaniline; when the organic ligand is two or more of the above selections, the present invention There is no particular limit to the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述极性溶剂优选包括甲醇、乙醇、二甲基亚砜、N,N-二甲基甲酰胺和水中的一种或几种;当所述极性溶剂为上述具体选择中的两种以上时,本发明对所述具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the polar solvent preferably includes one or more of methanol, ethanol, dimethyl sulfoxide, N,N-dimethylformamide and water; when the polar solvent is the specific selection above When there are two or more of them, the present invention has no special limitation on the proportion of the specific substances, and they can be mixed in any proportion.

在本发明中,所述可溶性金属盐和有机物配体的质量比优选为1:50~50:1,进一步优选为1:30~30:1,更优选为1:20~20:1。在本发明中,所述可溶性金属盐和极性溶剂的用量比优选为0.5~500mg:1mL,进一步优选为10~450mg:1mL,更优选为50~400mg:1mL。In the present invention, the mass ratio of the soluble metal salt and the organic ligand is preferably 1:50-50:1, more preferably 1:30-30:1, and more preferably 1:20-20:1. In the present invention, the usage ratio of the soluble metal salt and the polar solvent is preferably 0.5 to 500 mg: 1 mL, more preferably 10 to 450 mg: 1 mL, and more preferably 50 to 400 mg: 1 mL.

本发明对所述混合的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。The present invention has no special limitations on the mixing process, and it can be carried out by using processes well known to those skilled in the art.

在本发明的具体实施例中,所述混合的过程优选包括:将基体材料和第四极性溶剂第四混合,得到第四混合液;将可溶性金属盐和第五极性溶剂第五混合,得到第五混合液;将有机物配体和第六极性溶剂第六混合,得到第六混合液;将所述第五混合液和第六混合液滴入第四混合液中。In a specific embodiment of the present invention, the mixing process preferably includes: mixing the base material and the fourth polar solvent for the fourth time to obtain a fourth mixed liquid; mixing the soluble metal salt and the fifth polar solvent for the fifth time, A fifth mixed liquid is obtained; the organic ligand and the sixth polar solvent are mixed for a sixth time to obtain a sixth mixed liquid; the fifth mixed liquid and the sixth mixed liquid are dropped into the fourth mixed liquid.

在本发明中,所述第四极性溶剂、所述第五极性溶剂和所述第六极性溶剂的种类均和上述限定的极性溶剂的种类相同,在此不再赘述。In the present invention, the fourth polar solvent, the fifth polar solvent and the sixth polar solvent are all the same as the polar solvents defined above, and will not be described again.

在本发明中,所述第四极性溶剂、所述第五极性溶剂和所述第六极性溶剂的总体积和上述技术方案限定的极性溶剂的体积相同。In the present invention, the total volume of the fourth polar solvent, the fifth polar solvent and the sixth polar solvent is the same as the volume of the polar solvent defined in the above technical solution.

在本发明中,所述基体材料和第四极性溶剂的用量比优选为0.5~100mg:1mL,进一步优选为10~80mg:1mL。在本发明中,所述可溶性金属盐和第五极性溶剂的用量比优选为0.5~100mg:1mL,进一步优选为10~80mg:1mL。在本发明中,所述有机物配体和第六极性溶剂的用量比为优选为0.5~100mg:1mL,进一步优选为10~80mg:1mL。In the present invention, the usage ratio of the matrix material and the fourth polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 10 to 80 mg: 1 mL. In the present invention, the usage ratio of the soluble metal salt and the fifth polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 10 to 80 mg: 1 mL. In the present invention, the usage ratio of the organic ligand and the sixth polar solvent is preferably 0.5 to 100 mg: 1 mL, and more preferably 10 to 80 mg: 1 mL.

本发明对所述第四混合、第五混合和第六混合的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。The present invention has no special limitations on the processes of the fourth mixing, the fifth mixing and the sixth mixing, and can be carried out using processes well known to those skilled in the art.

在本发明中,所述第五混合液和所说第六混合液的滴入速度独立的优选为2~10mL/min,进一步优选为5mL/min。In the present invention, the dripping speeds of the fifth mixed liquid and the sixth mixed liquid are independently preferably 2 to 10 mL/min, and more preferably 5 mL/min.

在本发明中,所述络合反应的温度优选为20~200℃,进一步优选为40~180℃,更优选为60~160℃;时间优选为6~48h,进一步优选为10~40h,更优选为15~35h。在本发明中,所述络合反应优选在搅拌的条件下进行;所述搅拌的转速优选为100~10000rpm,进一步优选为300~9000rpm,更优选为800~8000rpm。在本发明中,所述络合反应优选在回流的条件下进行。In the present invention, the temperature of the complexation reaction is preferably 20 to 200°C, more preferably 40 to 180°C, more preferably 60 to 160°C; the time is preferably 6 to 48h, further preferably 10 to 40h, and more Preferably it is 15 to 35 hours. In the present invention, the complexing reaction is preferably carried out under stirring conditions; the rotating speed of the stirring is preferably 100 to 10000 rpm, more preferably 300 to 9000 rpm, and more preferably 800 to 8000 rpm. In the present invention, the complexation reaction is preferably carried out under reflux conditions.

所述络合反应完成后,本发明还优选包括将得到的产物进行离心分离、干燥和研磨。本发明对所述离心分离和研磨的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。在本发明中,所述干燥的温度优选为70℃;时间优选为12h。在本发明中,所述干燥优选在真空烘箱中进行。After the complexation reaction is completed, the present invention also preferably includes centrifuging, drying and grinding the obtained product. The present invention has no special limitations on the processes of centrifugal separation and grinding, and can be carried out using processes well known to those skilled in the art. In the present invention, the drying temperature is preferably 70°C; the drying time is preferably 12 hours. In the present invention, the drying is preferably performed in a vacuum oven.

得到所述前驱体材料后,本发明将所述前驱体材料进行焙烧和酸浸处理,得到所述多级孔材料。After obtaining the precursor material, the present invention performs roasting and acid leaching on the precursor material to obtain the hierarchical porous material.

在本发明中,所述焙烧的温度优选为600~1200℃,进一步优选为700~1100℃,更优选为800~1000℃;升温至所述焙烧温度的升温速率优选为10℃/min;保温时间优选为0.5~10h,进一步优选为1~9h,更优选为2~8h。在本发明中,所述焙烧优选在保护气氛下进行;所述保护气氛优选包括氮气、氩气、氦气和氖气中的一种或几种;当所述保护气氛为上述选择中的两种以上时,本发明对具体物质的比例没有特殊的限定,按照任意比例混合均可。在本发明中,所述保护气氛的通入速率优选为80mL/min。在本发明中,所述焙烧优选在管式炉中进行。In the present invention, the roasting temperature is preferably 600-1200°C, further preferably 700-1100°C, and more preferably 800-1000°C; the temperature rise rate to the roasting temperature is preferably 10°C/min; heat preservation The time is preferably 0.5 to 10 hours, more preferably 1 to 9 hours, and more preferably 2 to 8 hours. In the present invention, the roasting is preferably carried out under a protective atmosphere; the protective atmosphere preferably includes one or more of nitrogen, argon, helium and neon; when the protective atmosphere is two of the above choices, When there are more than three kinds, the present invention has no special limit on the proportion of specific substances, and they can be mixed in any proportion. In the present invention, the introduction rate of the protective atmosphere is preferably 80 mL/min. In the present invention, the roasting is preferably carried out in a tube furnace.

所述焙烧完成后,本发明还优选包括将得到的产物冷却至室温。本发明对所述冷却至室温的过程没有特殊的限定,采用本领域技术人员熟知的即可。After the roasting is completed, the present invention preferably also includes cooling the obtained product to room temperature. The present invention has no special limitations on the process of cooling to room temperature, and any process well known to those skilled in the art can be used.

在本发明中,所述酸浸处理采用的酸性试剂优选包括硫酸、盐酸和氢氟酸中的一种或几种;当所述酸性试剂为上述选择中的两种以上时,本发明对具体物质的比例没有特殊的限定,按照任意比例混合均可。In the present invention, the acidic reagent used in the acid leaching treatment preferably includes one or more of sulfuric acid, hydrochloric acid and hydrofluoric acid; when the acidic reagent is two or more of the above selections, the present invention is specific to There is no special limit on the proportion of substances, and they can be mixed in any proportion.

在本发明中,当所述模板剂为硅的氧化物时,所述酸性试剂优选为氢氟酸。In the present invention, when the template agent is silicon oxide, the acidic reagent is preferably hydrofluoric acid.

在本发明中,所述酸性试剂的浓度优选为0.5~5mol/L,进一步优选为2mol/L。本发明对所述酸性试剂的用量没有特殊的限定,能够将所述模板剂去除即可。In the present invention, the concentration of the acidic reagent is preferably 0.5 to 5 mol/L, and more preferably 2 mol/L. The present invention has no special limitation on the amount of the acidic reagent, as long as the template agent can be removed.

在本发明中,所述酸浸处理优选在搅拌的条件下进行;所述搅拌的转速优选为100~10000rpm,进一步优选为300~9000rpm,更优选为800~8000rpm;时间优选为24h。在本发明中,通过酸浸处理能够去除模板剂。In the present invention, the acid leaching treatment is preferably performed under stirring conditions; the stirring speed is preferably 100 to 10000 rpm, more preferably 300 to 9000 rpm, and more preferably 800 to 8000 rpm; the stirring time is preferably 24 hours. In the present invention, the template agent can be removed by acid leaching treatment.

所述酸浸处理完成后,本发明还优选包括将得到的产物进行过滤和干燥。After the acid leaching treatment is completed, the present invention also preferably includes filtering and drying the obtained product.

本发明对所述过滤的过程没有特殊的限定,采用本领域技术人员熟知的过程进行即可。在本发明中,所述干燥的温度优选为70℃,时间优选为10h。The present invention has no special limitations on the filtration process, and it can be carried out using processes well known to those skilled in the art. In the present invention, the drying temperature is preferably 70°C, and the drying time is preferably 10 hours.

作为本发明的另一个实施方案,所述模板剂替换为聚苯乙烯。在本发明中,当所述模板剂为聚苯乙烯时,所述多级孔材料的制备方法不包括酸浸处理。在本发明中,当所述模板剂为聚苯乙烯时,优选在焙烧的过程中除去模板剂。As another embodiment of the present invention, the template agent is replaced with polystyrene. In the present invention, when the template agent is polystyrene, the preparation method of the hierarchical porous material does not include acid leaching treatment. In the present invention, when the template agent is polystyrene, it is preferable to remove the template agent during the baking process.

本发明还提供了上述技术方案所述制备方法制备得到的多级孔材料,所述多级孔材料为金属掺杂的多级孔碳材料。The present invention also provides a hierarchical porous material prepared by the preparation method described in the above technical solution, where the hierarchical porous material is a metal-doped hierarchical porous carbon material.

在本发明中,所述金属优选包括镍、铁、钴、铜、锰、钌和银中的一种或几种。在本发明中,所述金属的质量百分含量优选为0.5~15.0%,进一步优选为1.0~14.0%,更优选为2.0~13.0%。In the present invention, the metal preferably includes one or more of nickel, iron, cobalt, copper, manganese, ruthenium and silver. In the present invention, the mass percentage of the metal is preferably 0.5-15.0%, more preferably 1.0-14.0%, and more preferably 2.0-13.0%.

在本发明中,所述多级孔碳材料的掺杂元素还优选包括氮。在本发明中,所述氮的质量百分含量优选为5.0~15.0%,进一步优选为6.0~14.0%,更优选为7.0~13.0%。In the present invention, the doping element of the hierarchical porous carbon material preferably also includes nitrogen. In the present invention, the mass percentage of nitrogen is preferably 5.0-15.0%, more preferably 6.0-14.0%, and more preferably 7.0-13.0%.

在本发明中,所述多级孔碳材料上的金属(M)优选以M-N4单位点的形式存在。In the present invention, the metal (M) on the hierarchical porous carbon material preferably exists in the form of MN 4 single sites.

在本发明中,通过对多级孔材料进行金属和氮元素的掺杂,能够调节多级孔材料的电子结构,从热力学层面改善多级孔材料的催化活性;结合多级孔结构的设置,能够进一步提升二氧化碳转化过程中的反应动力学,提高一氧化碳的法拉第效率和分电流密度。In the present invention, by doping the multi-level porous material with metal and nitrogen elements, the electronic structure of the multi-level porous material can be adjusted, and the catalytic activity of the multi-level porous material can be improved from the thermodynamic level; combined with the setting of the multi-level porous structure, It can further improve the reaction kinetics during the conversion of carbon dioxide and improve the Faradaic efficiency and partial current density of carbon monoxide.

在本发明中,所述多级孔材料的比表面积优选为500~2000m2/g,进一步优选为600~1900m2/g,更优选为700~1800m2/g;孔体积优选为0.2~2cm3/g,进一步优选为0.5~1.5cm3/g,更优选为0.8~1.2cm3/g。在本发明中,所述多级孔优选包括微孔结构、介孔结构和大孔结构。在本发明中,所述微孔结构、介孔结构和大孔结构的孔体积比优选为为1:(0.5~5):(0.5~5),进一步优选为1:(2~3):(2~3)。In the present invention, the specific surface area of the hierarchical porous material is preferably 500-2000m2 /g, more preferably 600-1900m2 /g, more preferably 700-1800m2 /g; the pore volume is preferably 0.2-2cm 3 /g, more preferably 0.5 to 1.5 cm 3 /g, more preferably 0.8 to 1.2 cm 3 /g. In the present invention, the hierarchical pores preferably include microporous structure, mesoporous structure and macroporous structure. In the present invention, the pore volume ratio of the microporous structure, mesoporous structure and macroporous structure is preferably 1: (0.5~5): (0.5~5), and further preferably 1: (2~3): (2~3).

本发明还提供了上述技术方案所述多级孔材料在催化二氧化碳还原反应中的应用。The present invention also provides the application of the hierarchical porous material described in the above technical solution in catalyzing carbon dioxide reduction reaction.

在本发明中,所述应用优选包括以下步骤:In the present invention, the application preferably includes the following steps:

将所述多级孔材料、乙醇和全氟磺酸型聚合物溶液混合,得到浆料;所述全氟磺酸型聚合物溶液的质量浓度优选为5%;所述所述多级孔材料、乙醇和全氟磺酸型聚合物溶液的用量比优选为1.2mg:564μL:36μL;Mix the hierarchical porous material, ethanol and perfluorosulfonic acid polymer solution to obtain a slurry; the mass concentration of the perfluorosulfonic acid polymer solution is preferably 5%; the hierarchical porous material , the dosage ratio of ethanol and perfluorosulfonic acid polymer solution is preferably 1.2 mg: 564 μL: 36 μL;

将所述浆料涂覆在1×3cm2的碳纸上(负载量为0.4mg/cm2),得到催化剂电极(即工作电极);The slurry is coated on 1× 3cm carbon paper (loading amount is 0.4mg/ cm2 ) to obtain a catalyst electrode (i.e. working electrode);

将所述催化剂电极作为阴极,以1mol/L的KOH溶液为电解液,以Ag/AgCl电极(其中的溶剂为3mol/L的KCl溶液)为参比电极,以泡沫镍为对电极,阴离子交换膜做隔膜,组装成气体扩散电极。在常温、常压的条件下,设置水循环转速为30mL/min;以20mL/min的速率通入CO2气流20min,使CO2气体达到饱和,再进行循环伏安扫描30圈,活化催化剂同时排出吸收的气体;通电12min稳定后,抽取1mL气体进行气相色谱检测,H2由色谱中的热导检测器(TCD)检测,CO由配备镍转化炉的氢火焰离子化检测器(FID)检测,通过测得的产物气体含量,计算产物的法拉第效率和分电流密度。Use the catalyst electrode as the cathode, 1 mol/L KOH solution as the electrolyte, Ag/AgCl electrode (the solvent in which is 3 mol/L KCl solution) as the reference electrode, and foam nickel as the counter electrode. Anion exchange The membrane is used as a separator and assembled into a gas diffusion electrode. Under normal temperature and pressure conditions, set the water circulation speed to 30mL/min; introduce CO2 gas flow at a rate of 20mL/min for 20min to make the CO2 gas saturated, and then perform cyclic voltammetry scanning for 30 cycles, and the activated catalyst will be discharged at the same time Absorbed gas; after powering on for 12 minutes and stabilizing, 1 mL of gas is extracted for gas chromatography detection. H 2 is detected by the thermal conductivity detector (TCD) in the chromatograph, and CO is detected by a hydrogen flame ionization detector (FID) equipped with a nickel conversion furnace. From the measured product gas content, the Faradaic efficiency and partial current density of the product are calculated.

为了进一步说明本发明,下面结合附图和实施例对本发明提供的一种多级孔材料及其制备方法和应用进行详细地描述,但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a multi-level porous material provided by the present invention and its preparation method and application are described in detail below with reference to the drawings and examples, but they should not be understood as limiting the scope of the present invention.

实施例1Example 1

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到621mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 621 mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸镍和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到混合液第一中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of nickel nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. ; Mix the cooled product with 100 mL of sulfuric acid solution with a concentration of 2 mol/L, stir at room temperature for 24 hours at a stirring speed of 300 rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10 hours to obtain nickel -Nitrogen-doped hierarchical porous carbon materials;

本实施例的合成路线示意图如图3所示;The schematic diagram of the synthesis route of this embodiment is shown in Figure 3;

本实施例得到的镍-氮掺杂的多级孔碳材料中镍的负载量为1.8wt.%,氮含量为7.8wt.%,比表面积为672m2/g,孔体积为1.49cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:3)。The nickel loading amount in the nickel-nitrogen doped hierarchical porous carbon material obtained in this example is 1.8wt.%, the nitrogen content is 7.8wt.%, the specific surface area is 672m 2 /g, and the pore volume is 1.49cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:3).

实施例2Example 2

将500mg疏松多孔结构的碱式碳酸镁、500mg十二烷基磺酸钠和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到634mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of sodium dodecyl sulfonate and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, stir at a stirring speed of 300 rpm for 6 h, and then centrifuge. , take out the lower sediment and obtain 634mg of matrix material;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸镍和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of nickel nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Nickel-nitrogen doped hierarchical porous carbon materials;

本实施例得到的镍-氮掺杂的多级孔碳材料中镍的负载量为1.7wt.%,氮含量为7.5wt.%,比表面积为654m2/g,孔体积为1.46cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:2)。The nickel loading amount in the nickel-nitrogen doped hierarchical porous carbon material obtained in this example is 1.7wt.%, the nitrogen content is 7.5wt.%, the specific surface area is 654m 2 /g, and the pore volume is 1.46cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:2).

实施例3Example 3

将500mg疏松多孔结构的氧化锌、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到586mg的基体材料;After mixing 500 mg of zinc oxide with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. 586 mg of base material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸镍和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of nickel nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Nickel-nitrogen doped hierarchical porous carbon materials;

本实施例得到的镍-氮掺杂的多级孔碳材料中镍的负载量为1.7wt.%,氮含量为7.2wt.%,比表面积为658m2/g,孔体积为1.37cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:1:2)。The nickel loading amount in the nickel-nitrogen doped hierarchical porous carbon material obtained in this example is 1.7wt.%, the nitrogen content is 7.2wt.%, the specific surface area is 658m 2 /g, and the pore volume is 1.37cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:1:2).

实施例4Example 4

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到623mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 623 mg of matrix material was obtained;

将得到的基体材料和250mLN,N-二甲基甲酰胺经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸镍和25mLN,N-二甲基甲酰胺混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mLN,N-二甲基甲酰胺混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在120℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL N, N-dimethylformamide to obtain a first mixed liquid; mix and dissolve 850 mg zinc nitrate hexahydrate, 50 mg nickel nitrate hexahydrate and 25 mL N, N-dimethylformamide. , obtain a second mixed liquid; mix and dissolve 1g 2-methylimidazole and 25mL N,N-dimethylformamide to obtain a third mixed liquid; add the second mixed liquid and the third mixed liquid at a rate of 5mL/min. Add dropwise to the first mixed solution, put the obtained mixed solution into an oil bath, heat to reflux, and perform a complexation reaction at 120°C for 12 hours; after the reaction is completed, centrifuge with a centrifuge, take out the lower precipitate, and place it in 70 Dry in a vacuum oven for 12 hours, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Nickel-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的镍-氮掺杂的多级孔碳材料中镍的负载量为1.2wt.%,氮含量为6.9wt.%,比表面积为608m2/g,孔体积为1.35cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:1:3)。The nickel loading amount in the nickel-nitrogen doped hierarchical porous carbon material obtained in this example is 1.2wt.%, the nitrogen content is 6.9wt.%, the specific surface area is 608m 2 /g, and the pore volume is 1.35cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:1:3).

实施例5Example 5

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到618mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 618 mg of matrix material was obtained;

将得到的前驱体材料和250mL甲醇经搅拌分散均匀,得到第四混合液;将50mg六水合硝酸镍和25mL甲醇混合溶解,得到第五混合液;将1g邻菲啰啉和25mL甲醇混合溶解,得到第六混合液;将第五混合液和第六混合液以5mL/min的滴加速度滴加到第四混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained precursor material and 250 mL of methanol to obtain a fourth mixed liquid; mix and dissolve 50 mg of nickel nitrate hexahydrate and 25 mL of methanol to obtain a fifth mixed liquid; mix and dissolve 1 g of phenanthroline and 25 mL of methanol. Obtain the sixth mixed solution; add the fifth mixed solution and the sixth mixed solution dropwise to the fourth mixed solution at a dropping speed of 5 mL/min, put the obtained mixed solution into an oil bath and heat to reflux, at 60°C Carry out the complexation reaction for 12 hours; after the reaction is completed, use a centrifuge to centrifuge and take out the lower precipitate, place it in a 70°C vacuum oven to dry for 12 hours, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Nickel-nitrogen doped hierarchical porous carbon materials;

本实施例得到的镍-氮掺杂的多级孔碳材料中镍的负载量为1.2wt.%,氮含量为7.1wt.%,比表面积为629m2/g,孔体积为1.68cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:0.5:2)。The nickel loading amount in the nickel-nitrogen doped hierarchical porous carbon material obtained in this example is 1.2wt.%, the nitrogen content is 7.1wt.%, the specific surface area is 629m 2 /g, and the pore volume is 1.68cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:0.5:2).

实施例6Example 6

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到615mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, obtaining 615 mg of matrix material;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg九水合硝酸铁和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of ferric nitrate nonahydrate, and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到铁-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Iron-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的铁-氮掺杂的多级孔碳材料中铁的负载量为1.82wt.%,氮含量为7.7wt.%,比表面积为696m2/g,孔体积为1.79cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:3:2)。The iron loading amount in the iron-nitrogen doped hierarchical porous carbon material obtained in this example is 1.82wt.%, the nitrogen content is 7.7wt.%, the specific surface area is 696m 2 /g, and the pore volume is 1.79cm 3 /g (The pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:3:2).

实施例7Example 7

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到609mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 609 mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸钴和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of cobalt nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到钴-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Cobalt-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的钴-氮掺杂的多级孔碳材料中钴的负载量为1.08wt.%,氮含量为8.6wt.%,比表面积为702m2/g,孔体积为1.82cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:0.5:3)。The cobalt-nitrogen-doped hierarchical porous carbon material obtained in this example has a cobalt loading of 1.08wt.%, a nitrogen content of 8.6wt.%, a specific surface area of 702m 2 /g, and a pore volume of 1.82cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:0.5:3).

实施例8Example 8

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到616mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 616mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸铜和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of copper nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到铜-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Copper-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的铜-氮掺杂的多级孔碳材料中铜的负载量为2.46wt.%,氮含量为5.1wt.%,比表面积为596m2/g,孔体积为1.15cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:1)。The copper loading amount in the copper-nitrogen doped hierarchical porous carbon material obtained in this example is 2.46wt.%, the nitrogen content is 5.1wt.%, the specific surface area is 596m 2 /g, and the pore volume is 1.15cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:1).

实施例9Example 9

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到629mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 629 mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸锰和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of manganese nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到锰-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Manganese-nitrogen doped hierarchical porous carbon materials;

本实施例得到的锰-氮掺杂的多级孔碳材料中锰的负载量为0.78wt.%,氮含量为10.4wt.%,比表面积为711m2/g,孔体积为1.79cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:2)。The manganese loading in the manganese-nitrogen doped hierarchical porous carbon material obtained in this example is 0.78wt.%, the nitrogen content is 10.4wt.%, the specific surface area is 711m 2 /g, and the pore volume is 1.79cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:2).

实施例10Example 10

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,再次常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到622mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature again with a power of 500 W for 30 min, and stir at a stirring speed of 300 rpm for 6 h. After centrifugation, take out the lower precipitate. material, 622 mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg氯化钌和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of ruthenium chloride and 25 mL of methanol to obtain a second mixed liquid; mix 1 g of 2-methylimidazole and Mix and dissolve 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath and heat to reflux. , carry out complexation reaction at 60℃ for 12h; after the reaction, centrifuge with a centrifuge and take out the lower precipitate, put it into a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到钌-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Ruthenium-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的钌-氮掺杂的多级孔碳材料中钌的负载量为0.64wt.%,氮含量为6.4wt.%,比表面积为634m2/g,孔体积为1.28cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:3)。The ruthenium-nitrogen-doped hierarchical porous carbon material obtained in this example has a ruthenium loading of 0.64wt.%, a nitrogen content of 6.4wt.%, a specific surface area of 634m 2 /g, and a pore volume of 1.28cm 3 / g (the pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:3).

实施例11Example 11

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到604mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. Material, 604 mg of matrix material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg硝酸银和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到第一混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of silver nitrate and 25 mL of methanol to obtain a second mixed liquid; mix 1 g of 2-methylimidazole and 25 mL of methanol. Methanol is mixed and dissolved to obtain a third mixed solution; the second mixed solution and the third mixed solution are added dropwise to the first mixed solution at a dropping speed of 5 mL/min, and the obtained mixed solution is placed in an oil bath and heated to reflux. Carry out the complexation reaction at 60°C for 12 hours; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70°C vacuum oven to dry for 12 hours, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到银-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Silver-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的银-氮掺杂的多级孔碳材料中银的负载量为1.36wt.%,氮含量为8.3wt.%,比表面积为664m2/g,孔体积为1.52cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:2:0.5)。The silver-nitrogen-doped hierarchical porous carbon material obtained in this example has a silver loading of 1.36wt.%, a nitrogen content of 8.3wt.%, a specific surface area of 664m 2 /g, and a pore volume of 1.52cm 3 /g. (The pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:2:0.5).

实施例12Example 12

将500mg疏松多孔结构的碱式碳酸镁、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到593mg的基体材料;After mixing 500 mg of basic magnesium carbonate with a loose porous structure, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. material, 593 mg of matrix material was obtained;

将得到的前驱体材料和250mL甲醇经搅拌分散均匀,得到第四混合液;将5mg硝酸银和25mL甲醇混合溶解,得到第五混合液;将1g邻菲啰啉和25mL甲醇混合溶解,得到第六混合液;将第五混合液和第六混合液以5mL/min的滴加速度滴加到第四混合液中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;The obtained precursor material and 250 mL of methanol were stirred and dispersed evenly to obtain the fourth mixed liquid; 5 mg of silver nitrate and 25 mL of methanol were mixed and dissolved to obtain the fifth mixed liquid; 1 g of phenanthroline and 25 mL of methanol were mixed and dissolved to obtain the third mixed liquid. Sixth mixed solution; add the fifth mixed solution and the sixth mixed solution dropwise to the fourth mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath and heat to reflux at 60°C. The complexation reaction was carried out for 12 hours; after the reaction, centrifuge with a centrifuge and take out the lower precipitate, put it into a 70°C vacuum oven to dry for 12 hours, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温后;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到银-氮掺杂的多级孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. Afterwards; mix the cooled product with 100mL of sulfuric acid solution with a concentration of 2mol/L, stir at room temperature for 24h at a stirring speed of 300rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10h to obtain Silver-nitrogen-doped hierarchical porous carbon materials;

本实施例得到的银-氮掺杂的多级孔碳材料中银的负载量为0.88wt.%,氮含量为6.3wt.%,比表面积为592m2/g,孔体积为1.77cm3/g(其中微孔结构、介孔结构和大孔结构的孔体积比为1:1:3)。The silver-nitrogen-doped hierarchical porous carbon material obtained in this example has a silver loading of 0.88wt.%, a nitrogen content of 6.3wt.%, a specific surface area of 592m 2 /g, and a pore volume of 1.77cm 3 /g. (The pore volume ratio of microporous structure, mesoporous structure and macroporous structure is 1:1:3).

对比例1Comparative example 1

将500mg块状实心的氧化铜、500mg聚乙烯吡咯烷酮和100mL甲醇混合后,在常温下、依次以500W的功率超声30min、以300rpm的搅拌速度搅拌6h,经离心机离心后,取出下层沉淀物,得到668mg的基体材料;After mixing 500 mg of solid copper oxide, 500 mg of polyvinylpyrrolidone and 100 mL of methanol, ultrasonicate at room temperature for 30 min at a power of 500 W, and stir for 6 h at a stirring speed of 300 rpm. After centrifugation, take out the lower precipitate. 668 mg of base material was obtained;

将得到的基体材料和250mL甲醇经搅拌分散均匀,得到第一混合液;将850mg六水合硝酸锌、50mg六水合硝酸镍和25mL甲醇混合溶解,得到第二混合液;将1g 2-甲基咪唑和25mL甲醇混合溶解,得到第三混合液;将第二混合液和第三混合液以5mL/min的滴加速度滴加到混合液第一中,将得到的混合溶液放入油浴锅中加热回流,在60℃条件下进行络合反应12h;反应结束后用离心机离心后取出下层沉淀物,放入70℃真空烘箱干燥12h,取出后研磨成粉,得到前驱体材料;Stir and disperse the obtained matrix material and 250 mL of methanol to obtain a first mixed liquid; mix and dissolve 850 mg of zinc nitrate hexahydrate, 50 mg of nickel nitrate hexahydrate and 25 mL of methanol to obtain a second mixed liquid; add 1 g of 2-methylimidazole Mix and dissolve with 25 mL of methanol to obtain a third mixed solution; add the second mixed solution and the third mixed solution dropwise to the first mixed solution at a dropping speed of 5 mL/min, and place the obtained mixed solution into an oil bath for heating Reflux and carry out complexation reaction at 60℃ for 12h; after the reaction is completed, centrifuge with a centrifuge and take out the lower precipitate, place it in a 70℃ vacuum oven to dry for 12h, take it out and grind it into powder to obtain the precursor material;

将得到的前驱体材料置于管式炉中,在80mL/min的氮气气流保护下,以10℃/min的升温速率升温至900℃后进行焙烧,保温时间为2h;焙烧完成后冷却至室温;将冷却后的产物和100mL浓度为2mol/L的硫酸溶液混合,室温下以300rpm的搅拌速度搅拌24h进行酸浸处理,溶去模板剂;然后经过滤后在70℃下干燥10h,得到镍-氮掺杂的块状实心的单一微孔碳材料;Place the obtained precursor material in a tube furnace, and under the protection of a nitrogen gas flow of 80 mL/min, heat it to 900°C at a heating rate of 10°C/min and then roast it. The holding time is 2 hours; after the roasting is completed, cool to room temperature. ; Mix the cooled product with 100 mL of sulfuric acid solution with a concentration of 2 mol/L, stir at room temperature for 24 hours at a stirring speed of 300 rpm for acid leaching treatment, and dissolve the template agent; then filter and dry at 70°C for 10 hours to obtain nickel - Nitrogen-doped bulk solid single microporous carbon material;

本实施例得到的镍-氮掺杂的块状实心的单一微孔碳材料中镍的负载量为1.22wt.%,氮含量为5.6wt.%,比表面积为617m2/g,孔体积为0.31cm3/g。The nickel loading amount in the nickel-nitrogen doped bulk solid single microporous carbon material obtained in this example is 1.22wt.%, the nitrogen content is 5.6wt.%, the specific surface area is 617m 2 /g, and the pore volume is 0.31cm 3 /g.

性能测试Performance Testing

测试例1Test example 1

将实施例1得到的多级孔材料进行扫描透射电镜检测,STEM检测结果如图1所示,从图1可以看出本实施例得到的多级孔材料具有丰富且均匀分散的镍金属单位点。The multi-level porous material obtained in Example 1 was subjected to scanning transmission electron microscopy. The STEM detection results are shown in Figure 1. It can be seen from Figure 1 that the multi-level porous material obtained in this Example has abundant and evenly dispersed nickel metal single sites. .

测试例2Test example 2

将实施例1得到的多级孔材料进行扫描电镜检测,SEM检测结果如图2所示,从图2可以看出本实施了得到的多级孔材料是由无数分层的纳米片组成的微米级多孔球;且具有丰富的孔道。The hierarchical porous material obtained in Example 1 was subjected to scanning electron microscopy. The SEM detection results are shown in Figure 2. It can be seen from Figure 2 that the hierarchical porous material obtained in this implementation is composed of numerous layered nanosheets. Grade porous balls; and have abundant pores.

测试例3Test example 3

以实施例1~12得到的多级孔材料为催化剂,催化二氧化碳还原制备一氧化碳,具体方法为:The hierarchical porous materials obtained in Examples 1 to 12 are used as catalysts to catalyze the reduction of carbon dioxide to produce carbon monoxide. The specific method is:

将1.2mg多级孔材料、564μL乙醇和36μL质量浓度为5%全氟磺酸型聚合物溶液混合,得到浆料;Mix 1.2 mg multi-stage porous material, 564 μL ethanol and 36 μL mass concentration of 5% perfluorosulfonic acid polymer solution to obtain a slurry;

将所述浆料涂覆在1×3cm2的碳纸上(负载量为0.4mg/cm2),得到催化剂电极(即工作电极);The slurry is coated on 1× 3cm carbon paper (loading amount is 0.4mg/ cm2 ) to obtain a catalyst electrode (i.e. working electrode);

将所述催化剂电极作为阴极,以1mol/L的KOH溶液为电解液,以Ag/AgCl电极(其中的溶剂为3mol/L的KCl溶液)为参比电极,以泡沫镍为对电极,阴离子交换膜做隔膜,组装成气体扩散电极。在常温、常压的条件下,设置水循环转速为30mL/min;以20mL/min的速率通入CO2气流20min,使CO2气体达到饱和,再进行循环伏安扫描30圈,活化催化剂同时排出吸收的气体;通电12min稳定后,抽取1mL气体进行气相色谱检测,H2由色谱中的热导检测器(TCD)检测,CO由配备镍转化炉的氢火焰离子化检测器(FID)检测,通过测得的产物气体含量,计算产物的法拉第效率和分电流密度。Use the catalyst electrode as the cathode, 1 mol/L KOH solution as the electrolyte, Ag/AgCl electrode (the solvent is 3 mol/L KCl solution) as the reference electrode, and foam nickel as the counter electrode. Anion exchange The membrane is used as a separator and assembled into a gas diffusion electrode. Under normal temperature and pressure conditions, set the water circulation speed to 30mL/min; introduce CO2 gas flow at a rate of 20mL/min for 20min to make the CO2 gas saturated, and then perform cyclic voltammetry scanning for 30 cycles, and the activated catalyst will be discharged at the same time Absorbed gas; after powering on for 12 minutes and stabilizing, 1 mL of gas is extracted for gas chromatography detection. H 2 is detected by the thermal conductivity detector (TCD) in the chromatograph, and CO is detected by a hydrogen flame ionization detector (FID) equipped with a nickel conversion furnace. From the measured product gas content, the Faradaic efficiency and partial current density of the product are calculated.

其中图4为实施例1的多级孔材料为催化剂时一氧化碳的法拉第效率图,图5为实施例1的多级孔材料为催化剂时的分电流密度图;从图4可以看出Ni-N-C的一氧化碳法拉第效率在-0.4~-1.3V的宽电压窗口下大于90%,在-0.7V时获得接近100%的最大值;从图5可以看出一氧化碳分电流密度在-0.6V后即超过100mA·cm-2,在-1.4V时达到最大值524mA·cm-2Figure 4 is a Faraday efficiency diagram of carbon monoxide when the multi-stage porous material of Example 1 is a catalyst, and Figure 5 is a partial current density diagram when the multi-stage porous material of Example 1 is a catalyst; it can be seen from Figure 4 that Ni-NC The faradaic efficiency of carbon monoxide is greater than 90% in the wide voltage window of -0.4 ~ -1.3V, and reaches a maximum value close to 100% at -0.7V; it can be seen from Figure 5 that the carbon monoxide partial current density exceeds -0.6V 100mA·cm -2 , reaching the maximum value of 524mA·cm -2 at -1.4V;

测试结果如表1所示。The test results are shown in Table 1.

表1实施例1~12得到的多级孔材料催化二氧化碳还原测试结果Table 1 Test results of catalytic carbon dioxide reduction of hierarchical porous materials obtained in Examples 1 to 12

从表1可以看出,利用本发明得到的多级孔材料作为催化剂,在催化二氧化碳还原制备一氧化碳的反应中,能够在较低的电位表现出较大的一氧化碳法拉第效率,同时具有较大的分电流密度。It can be seen from Table 1 that using the hierarchical porous material obtained by the present invention as a catalyst can exhibit a greater carbon monoxide Faradaic efficiency at a lower potential in the reaction of catalyzing the reduction of carbon dioxide to produce carbon monoxide, and at the same time has a greater separation efficiency. current density.

尽管上述实施例对本发明做出了详尽的描述,但它仅仅是本发明一部分实施例,而不是全部实施例,还可以根据本实施例在不经创造性前提下获得其他实施例,这些实施例都属于本发明保护范围。Although the above embodiments describe the present invention in detail, they are only part of the embodiments of the present invention, not all embodiments. Other embodiments can also be obtained according to this embodiment without any inventive step, and these embodiments are all It belongs to the protection scope of the present invention.

Claims (2)

1. The application of the hierarchical pore material in catalyzing carbon dioxide reduction reaction is characterized in that the preparation method of the hierarchical pore material comprises the following steps:
mixing a template agent, a surface modifier and a polar solvent to obtain a matrix material;
growing metal organic compounds on the surface of the matrix material in situ to obtain a precursor material;
sequentially roasting and acid leaching the precursor material to obtain the hierarchical pore material;
the template agent has a loose porous structure; the template agent comprises a metal oxide and/or a metal salt; the metal oxide comprises magnesium oxide and/or zinc oxide; the metal salt comprises basic magnesium carbonate;
the metal organic compound comprises a zeolite imidazole framework or a metal organic complex;
when the metal organic compound is a zeolite imidazole framework, the in-situ growth comprises the steps of: mixing a matrix material, a first soluble metal salt, a second soluble metal salt, 2-methylimidazole and a polar solvent, and carrying out a meridian combination reaction to obtain the precursor material;
the first soluble metal salt is a soluble zinc salt;
the second soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;
When the metal organic compound is a metal organic complex, the in situ growth comprises the steps of:
mixing a matrix material, soluble metal salt, an organic ligand and a polar solvent, and carrying out meridian combination reaction to obtain the precursor material;
the soluble metal salt comprises one or more of soluble nickel salt, soluble ferric salt, soluble cobalt salt, soluble copper salt, soluble manganese salt, soluble ruthenium salt and soluble silver salt;
the organic ligand comprises one or more of phenanthroline, formamide, melamine and polyaniline;
the multistage holes comprise a microporous structure, a mesoporous structure and a macroporous structure; the pore volume ratio of the microporous structure, the mesoporous structure and the macroporous structure is 1: (2-3): (2-3);
the hierarchical pore material is a metal-doped hierarchical pore carbon material, and the mass percentage of the metal is 0.5-15.0%.
2. The use according to claim 1, wherein the baking temperature is 600-1200 ℃ and the holding time is 0.5-10 h.
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