CN113249743B - Catalyst for electrocatalytic oxidation of glycerol and preparation method thereof - Google Patents

Abstract

The invention discloses a catalyst for electrocatalysis glycerin oxidation and a preparation method thereof, and the method comprises the following steps: (1) Putting a nickel carrier into a mixed solution containing ferric salt and a precipitator, and growing NiFe (OH) on the nickel carrier by adopting a solvothermal method or a hydrothermal method _x A catalyst precursor; (2) Growing NiFe (OH) on the obtained product in the step (1) _x And (3) roasting the nickel carrier of the catalyst precursor in a roasting atmosphere to obtain the electro-catalytic glycerol oxidation catalyst. The preparation method of the invention has simple steps and low cost; the obtained catalyst for electrocatalytic oxidation of glycerin has high electrocatalytic activity (when glycerin is oxidized into formic acid, the Faraday efficiency of the obtained formic acid can reach 95%, and the yield of the formic acid can reach 1169 mu mol cm ^‑2 ·h ^‑1 ) The stability is strong; and at 100mA cm ^‑2 After the electrolysis is continued for 240 hours under the current density, the potential of the electrolytic cell is almost not attenuated, and the service life is long.

Description

一种电催化甘油氧化的催化剂及其制备方法Catalyst for electrocatalytic glycerin oxidation and preparation method thereof

技术领域technical field

本发明属于无机纳米催化材料技术领域，特别涉及一种电催化甘油氧化的催化剂及其制备方法。The invention belongs to the technical field of inorganic nanometer catalytic materials, and in particular relates to a catalyst for electrocatalyzing glycerin oxidation and a preparation method thereof.

背景技术Background technique

随着化石能源的不断消耗，对可再生的生物柴油产生的巨大市场需求不仅促进了生物柴油工业的快速发展，同时也导致了甘油作为生物柴油生产副产物的大量过剩，如何综合利用过剩的大量甘油，避免资源浪费，也成为了当前需要解决的难题之一。With the continuous consumption of fossil energy, the huge market demand for renewable biodiesel not only promotes the rapid development of the biodiesel industry, but also leads to a large excess of glycerol as a by-product of biodiesel production. How to comprehensively utilize the excess Glycerin, to avoid resource waste, has also become one of the current problems that need to be solved.

甘油可作为原材料，通过氧化、加氢、脱水、醚化、酯化和低聚等方法来获得高附加值化学品。其中，甘油的氧化方法包括：生物发酵法、化学氧化法和电化学氧化法等等，甘油氧化后可获得如甘油酸、二羟基丙酮、甘油醛、乙醇酸和甲酸等高附加值化学品。Glycerol can be used as a raw material to obtain high value-added chemicals through oxidation, hydrogenation, dehydration, etherification, esterification and oligomerization. Among them, glycerin oxidation methods include: biological fermentation, chemical oxidation and electrochemical oxidation, etc. After oxidation of glycerol, high value-added chemicals such as glyceric acid, dihydroxyacetone, glyceraldehyde, glycolic acid and formic acid can be obtained.

其中，电化学氧化法操作简便、消耗电能、反应条件温和、对环境无污染，可以很好地避免化学氧化法(氧化剂污染环境)和发酵法(效率低、产物分离困难)带来的很多缺陷，是一种可持续发展方式。此外，电化学氧化法还可以通过调控电极电势、电解质溶液、甘油浓度、催化剂的结构和组成来控制甘油的氧化产物，较高的产物选择性是重要的优势。但是，目前甘油电催化氧化所使用的催化剂主要是贵金属催化剂，如Au、Pt、Pd等，这些贵金属储量有限、价格昂贵，无法实现大规模的商业化使用。Among them, the electrochemical oxidation method is easy to operate, consumes electric energy, has mild reaction conditions, and has no pollution to the environment. It can well avoid many defects caused by chemical oxidation (oxidant pollution of the environment) and fermentation (low efficiency, difficult product separation) , is a way of sustainable development. In addition, the electrochemical oxidation method can also control the oxidation product of glycerol by adjusting the electrode potential, electrolyte solution, glycerol concentration, and catalyst structure and composition. Higher product selectivity is an important advantage. However, currently, the catalysts used in the electrocatalytic oxidation of glycerol are mainly noble metal catalysts, such as Au, Pt, Pd, etc. These noble metals are limited in reserves and expensive, and cannot be used commercially on a large scale.

为解决上述问题，公开号为CN112481656A的中国发明专利申请公开了一种具有高选择性电催化甘油氧化转化生产甲酸以及高效电解水产氢的双功能催化剂，该双功能催化剂的制备方法包括：(1)在导电三维衬底上电沉积Ni/Ni(OH)₂纳米片，得到沉积Ni/Ni(OH)₂纳米片后的衬底；(2)将步骤(1)所述的沉积Ni/Ni(OH)₂纳米片后的衬底浸泡在乙酸钴溶液中，升温进行阳离子交换处理，取出，即得到所述的高选择性电催化甘油氧化转化产甲酸和高效电解水产氢的双功能催化剂。In order to solve the above problems, the Chinese invention patent application with the publication number CN112481656A discloses a bifunctional catalyst with high selectivity electrocatalyzed oxidation conversion of glycerol to produce formic acid and efficient electrolysis of water to produce hydrogen. The preparation method of the bifunctional catalyst comprises: (1 ) electrodeposit Ni/Ni(OH) ₂ nanosheets on the conductive three-dimensional substrate, obtain the substrate after depositing Ni/Ni(OH) ₂ nanosheets; (2) deposit Ni/Ni described in step (1) The substrate after the (OH) ₂ nanosheets was soaked in cobalt acetate solution, heated up for cation exchange treatment, and taken out to obtain the bifunctional catalyst for the high-selectivity electrocatalyzed oxidation conversion of glycerol to produce formic acid and the high-efficiency electrolysis of water to produce hydrogen.

上述的电催化剂在电催化甘油氧化后，获得的甲酸的法拉第效率达到97.25％，但该电催化剂在100mA/cm²电流密度下能够对甘油进行持续电解的时间较短(约90h)，超过90h后，恒电流计时电位将逐渐衰减。After the above-mentioned electrocatalyst is electrocatalyzed to oxidize glycerol, the faradaic efficiency of the obtained formic acid reaches 97.25%, but the electrocatalyst can carry out the continuous electrolysis time of glycerol under the current density of 100mA/cm ² (about 90h), more than 90h After that, the galvanostatic chronopot will gradually decay.

发明内容Contents of the invention

本发明的发明目的是提供一种电催化甘油氧化的催化剂及其制备方法，该电催化甘油氧化的催化剂不仅电催化活性高，而且能够对甘油持续电解达240小时以上。The object of the present invention is to provide a catalyst for electrocatalyzing glycerol oxidation and its preparation method. The catalyst for electrocatalyzing glycerol oxidation not only has high electrocatalytic activity, but also can continuously electrolyze glycerin for more than 240 hours.

为实现上述发明目的，本发明的技术方案如下：For realizing the above-mentioned purpose of the invention, the technical scheme of the present invention is as follows:

一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：A preparation method of a catalyst for electrocatalytic glycerol oxidation, comprising the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用溶剂热法或水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and grow NiFe(OH) _x catalyst precursor on the nickel carrier by solvothermal or hydrothermal method;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油的氧化催化剂。(2) The NiFe(OH) _x catalyst precursor grown on the nickel carrier obtained in step (1) is placed in a calcination atmosphere for calcination, that is, the electrocatalyzed glycerol oxidation catalyst is obtained.

本发明通过水热法直接在镍载体上生长NiFe(OH)_x催化剂前驱体，而后对生长有NiFe(OH)_x催化剂前驱体的镍载体进行焙烧，使NiFe(OH)_x催化剂前驱体转化为NiFe₂O₄纳米片，步骤简便、成本低廉；由于具有尖晶石结构的NiFe₂O₄纳米片具有优异的氧化性和导电性，使获得的电催化甘油氧化的催化剂不仅电催化活性高(当将甘油氧化为甲酸时，获得的甲酸的法拉第效率可达到95％，甲酸产率可达到1169μmol·cm^-2·h^-1)、稳定性强；而且在100mA·cm^-2的电流密度下持续电解240小时后，其电位几乎无衰减，使用寿命长。The present invention directly grows the NiFe(OH) _x catalyst precursor on the nickel carrier through the hydrothermal method, and then roasts the NiFe(OH)x catalyst precursor grown on the NiFe(OH) _x catalyst precursor, so that the NiFe(OH) _x catalyst precursor is converted into NiFe ₂ O ₄ nanosheets, with simple steps and low cost; due to the excellent oxidation and electrical conductivity of NiFe ₂ O ₄ nanosheets with spinel structure, the obtained catalyst for electrocatalytic glycerin oxidation not only has high electrocatalytic activity ( When glycerol is oxidized to formic acid, the faradaic efficiency of the obtained formic acid can reach 95%, and the yield of formic acid can reach 1169μmol·cm ^-2 ·h ^-1 ), with strong stability; and at a current density of 100mA·cm ^-2 After continuous electrolysis for 240 hours, its potential has almost no attenuation and its service life is long.

因此，本发明还提供了一种电催化甘油氧化的催化剂，该催化剂即采用上述的制备方法制得。该催化剂的基底镍表面垂直生长了很多相互交错的超薄NiFe₂O₄纳米片，NiFe₂O₄纳米片之间形成很多纳米多孔结构，这样的纳米多孔结构可以增大催化剂的比表面积，暴露更多的活性位点，而且孔结构有利于电解液进入与催化剂充分接触，更有利于电催化氧化甘油。Therefore, the present invention also provides a catalyst for electrocatalyzing the oxidation of glycerol, which is prepared by the above-mentioned preparation method. Many interlaced ultra-thin NiFe ₂ O ₄ nanosheets are vertically grown on the nickel surface of the catalyst, and many nanoporous structures are formed between NiFe ₂ O ₄ nanosheets. Such nanoporous structures can increase the specific surface area of the catalyst and expose More active sites, and the pore structure is conducive to the full contact between the electrolyte and the catalyst, which is more conducive to the electrocatalytic oxidation of glycerol.

在采用该催化剂电催化甘油氧化时，反应条件优选设定为：电解液中甘油浓度为0.005-5mol/L，电解液pH为9-14，反应温度为10-60℃，施加电势为0-2V。When the catalyst is used to electrocatalyze the oxidation of glycerol, the reaction conditions are preferably set as follows: the concentration of glycerol in the electrolyte is 0.005-5mol/L, the pH of the electrolyte is 9-14, the reaction temperature is 10-60°C, and the applied potential is 0- 2V.

作为进一步优选，反应条件设定为：电解液为含有0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，反应温度为常温，施加电势为0.3-1.0V。反应条件温和，绿色环保。As a further preference, the reaction conditions are set as follows: the electrolyte is a mixed aqueous solution containing 0.1 mol/L glycerin and 1 mol/L sodium hydroxide, the reaction temperature is normal temperature, and the applied potential is 0.3-1.0V. The reaction conditions are mild and environmentally friendly.

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(1)中，所述的水热法是指将所述的镍载体和所述的混合溶液共同转移至水热反应釜中，于20-300℃下水热反应1-48h。In the above-mentioned preparation method of the catalyst for electrocatalyzing glycerol oxidation, in step (1), the hydrothermal method refers to transferring the nickel carrier and the mixed solution to the hydrothermal reaction kettle together, and then Hydrothermal reaction at 20-300°C for 1-48h.

作为优选，所述的水热反应在60-150℃下进行5-30h。Preferably, the hydrothermal reaction is carried out at 60-150° C. for 5-30 hours.

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(1)中，所述的铁盐为硝酸铁、氯化铁、氯化亚铁和硫酸铁中的至少一种；优选为硝酸铁、氯化铁和硫酸铁中的至少一种；这是因为三价铁离子更易与镍基底反应以获得Ni²⁺。In the above-mentioned preparation method of the catalyst for electrocatalytic glycerol oxidation, in step (1), the iron salt is at least one of ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate; preferably ferric nitrate , at least one of ferric chloride and ferric sulfate; this is because ferric ions are more likely to react with the nickel substrate to obtain Ni ²⁺ .

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(1)中，所述的沉淀剂为尿素和六次甲基四胺中的至少一种。In the above method for preparing a catalyst for electrocatalytic glycerol oxidation, in step (1), the precipitating agent is at least one of urea and hexamethylenetetramine.

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(1)中，所述的混合溶液的溶剂为甲醇、乙醇和水中的至少一种；In the above method for preparing a catalyst for electrocatalytic glycerin oxidation, in step (1), the solvent of the mixed solution is at least one of methanol, ethanol and water;

所述的混合溶液中，铁离子的摩尔浓度为0.01-0.1mol/L，沉淀剂的摩尔浓度为0.01-0.1mol/L。In the mixed solution, the molar concentration of iron ions is 0.01-0.1 mol/L, and the molar concentration of precipitating agent is 0.01-0.1 mol/L.

作为优选，步骤(1)中，所述的混合溶液的溶剂由水与醇(甲醇和/或乙醇)混合而成，混合比例为2:8～8:2。反应溶剂的组成对催化剂的形貌存在影响，当采用上述混合溶剂时，获得的催化剂形貌更佳。Preferably, in step (1), the solvent of the mixed solution is formed by mixing water and alcohol (methanol and/or ethanol), and the mixing ratio is 2:8˜8:2. The composition of the reaction solvent has an influence on the morphology of the catalyst. When the above mixed solvent is used, the obtained catalyst has a better morphology.

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(1)中，先依次采用有机溶剂和酸性溶剂对镍载体进行超声清洗，而后再进行水热反应；In the above preparation method of the catalyst for electrocatalytic glycerin oxidation, in step (1), the nickel support is firstly ultrasonically cleaned with an organic solvent and an acidic solvent, and then the hydrothermal reaction is carried out;

所述的有机溶剂为丙酮、乙醇和乙酸乙酯中的至少一种，优选为丙酮和乙醇中的至少一种；Described organic solvent is at least one in acetone, ethanol and ethyl acetate, is preferably at least one in acetone and ethanol;

所述的酸性溶剂为盐酸、硫酸和硝酸中的至少一种，优选为盐酸和硝酸中的至少一种。The acidic solvent is at least one of hydrochloric acid, sulfuric acid and nitric acid, preferably at least one of hydrochloric acid and nitric acid.

在上述的电催化甘油氧化的催化剂的制备方法中，步骤(2)中，所述的焙烧气氛为空气气氛、氯气气氛和氧气气氛中的至少一种。In the above method for preparing a catalyst for electrocatalytic glycerol oxidation, in step (2), the calcination atmosphere is at least one of air atmosphere, chlorine atmosphere and oxygen atmosphere.

在上述的电催化甘油氧化的催化剂的制备方法中，所述的氧气气氛中含有惰性稀释气体，该惰性稀释气体为氮气、氩气、氦气、氪气、氖气和氙气中的至少一种。惰性气体的添加是为了稀释氧气浓度，避免在高温下长时间反应造成过度氧化而影响催化剂的导电性；同时在低浓度氧气气氛下进行反应更佳安全。In the above preparation method of the catalyst for electrocatalytic glycerol oxidation, the oxygen atmosphere contains an inert diluent gas, and the inert diluent gas is at least one of nitrogen, argon, helium, krypton, neon and xenon . The addition of inert gas is to dilute the oxygen concentration and avoid excessive oxidation caused by long-term reaction at high temperature and affect the conductivity of the catalyst; at the same time, it is safer to conduct the reaction under a low-concentration oxygen atmosphere.

在上述的电催化甘油氧化的催化剂的制备方法中，所述的焙烧在100-500℃、0-3MPa下进行1-50h；即，将焙烧温度从室温以1-20℃/min的升温速率升至100-500℃，而后在0-3MPa下焙烧保温1-50h。In the preparation method of the catalyst for electrocatalytic glycerin oxidation mentioned above, the calcination is carried out at 100-500°C and 0-3MPa for 1-50h; Rise to 100-500°C, then bake and keep at 0-3MPa for 1-50h.

作为优选，将焙烧温度从20-30℃以1-10℃/min的升温速率升至250-350℃，而后在0-1MPa下焙烧保温1-20h。Preferably, the calcination temperature is increased from 20-30° C. to 250-350° C. at a rate of 1-10° C./min, and then the calcination temperature is kept at 0-1 MPa for 1-20 hours.

与现有技术相比，本发明的有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are reflected in:

(1)本发明通过水热法直接在镍载体上生长NiFe(OH)_x催化剂前驱体，而后对生长有NiFe(OH)_x催化剂前驱体的镍载体进行焙烧，使NiFe(OH)_x催化剂前驱体转化为NiFeO₄纳米片，步骤简便、成本低廉；由于具有尖晶石结构的NiFeO₄纳米片具有优异的氧化性和导电性，使获得的电催化甘油氧化的催化剂不仅电催化活性高(当将甘油氧化为甲酸时，获得的甲酸的法拉第效率可达到95％，甲酸产率可达到1169μmol·cm^-2·h^-1)、稳定性强；而且在100mA·cm^-2的电流密度下持续电解240小时后，其电位几乎无衰减，使用寿命长。(1) The present invention directly grows the NiFe(OH) _x catalyst precursor on the nickel carrier by the hydrothermal method, and then roasts the NiFe(OH) _x catalyst precursor grown on the nickel carrier to make the NiFe(OH) _x catalyst precursor NiFeO 4 nanosheets are converted into NiFeO ₄ nanosheets with simple steps and low cost; due to the excellent oxidation and electrical conductivity of NiFeO ₄ nanosheets with spinel structure, the obtained catalyst for electrocatalytic glycerol oxidation not only has high electrocatalytic activity (when When glycerol is oxidized to formic acid, the ^faradaic efficiency of the obtained formic acid can reach 95%, and the yield of formic acid can reach 1169 μmol·cm ^-2 ·h ^-1 ), with strong stability; After 240 hours of electrolysis, its potential has almost no decay, and its service life is long.

(2)本发明中，催化剂的基底镍表面垂直生长了很多相互交错的超薄NiFe₂O₄纳米片，NiFe₂O₄纳米片之间形成很多纳米多孔结构，这样的纳米多孔结构可以增大催化剂的比表面积，暴露更多的活性位点，而且孔结构有利于电解液进入与催化剂充分接触，更有利于电催化氧化甘油。(2) In the present invention, a lot of interlaced ultrathin NiFe ₂ O ₄ nanosheets are vertically grown on the base nickel surface of the catalyst, and a lot of nanoporous structures are formed between NiFe ₂ O ₄ nanosheets, and such nanoporous structures can be enlarged The specific surface area of the catalyst exposes more active sites, and the pore structure is conducive to the full contact between the electrolyte and the catalyst, which is more conducive to the electrocatalytic oxidation of glycerol.

附图说明Description of drawings

图1为本发明制备的电催化甘油氧化的催化剂的扫描电镜图；Fig. 1 is the scanning electron micrograph of the catalyst of electrocatalytic glycerol oxidation prepared by the present invention;

图2为在不同电压下本发明制备的电催化甘油氧化的催化剂的催化效率测试图；Fig. 2 is the catalytic efficiency test figure of the catalyst of electrocatalytic glycerol oxidation prepared by the present invention under different voltages;

图中，Petantial V(vs.Ag/AgCl)表示电压(伏特，Ag/AgCl电极)，Faradayefficiency(％)表示法拉第效率(百分比)，Current density(mA/cm^-2)表示电流密度(毫安/平方厘米)，下同；In the figure, Petantial V (vs.Ag/AgCl) represents voltage (volts, Ag/AgCl electrode), Faradayefficiency (%) represents Faraday efficiency (percentage), Current density (mA/cm ^-2 ) represents current density (mA/ square centimeter), the same below;

图3为本发明制备的电催化甘油氧化的催化剂的稳定性测试结果图；Fig. 3 is the stability test result figure of the catalyst of electrocatalytic glycerol oxidation prepared by the present invention;

图中，Time(h)表示电解时间(小时)，Glycerol concentration(mM)表示甲酸浓度(毫摩尔每升)；Among the figure, Time (h) represents electrolysis time (hour), and Glycerol concentration (mM) represents formic acid concentration (mmol per liter);

图4为本发明制备的电催化甘油氧化的催化剂经过240h使用后的扫描电镜图。Fig. 4 is a scanning electron micrograph of the electrocatalyzed glycerol oxidation catalyst prepared in the present invention after 240 hours of use.

具体实施方式detailed description

下面结合附图和具体实施方式对本发明的技术方案做进一步详细说明。The technical solution of the present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.

实施例1Example 1

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍片依次置于丙酮、2M盐酸中超声清洗15min；然后，将经过上述处理的镍片放置于含有0.01M Fe(NO₃)₃和0.02M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在80℃烘箱中水热反应12h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍片清洗干净，烘干备用；Specifically include: placing the nickel sheet in acetone and 2M hydrochloric acid for 15 minutes for ultrasonic cleaning; then, placing the above-mentioned treated nickel sheet in a mixed solution containing 0.01M Fe(NO ₃ ) ₃ and 0.02M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 80°C for 12h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel sheet, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍片在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以10℃/min的升温速率升至250℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel sheet with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 250 °C at a heating rate of 10 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.4V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为79％，产率为80μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.4V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 79%, and the yield is 80μmol·cm ^-2 ·h ^-1 .

实施例2Example 2

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、2M盐酸中超声清洗15min；然后，将经过上述处理的镍箔放置于含有0.01M Fe(NO₃)₃和0.02M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在80℃烘箱中水热反应16h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 2M hydrochloric acid for 15 minutes for ultrasonic cleaning; then, placing the above-mentioned treated nickel foil in a mixed solution containing 0.01M Fe(NO ₃ ) ₃ and 0.02M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 80°C for 16h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以10℃/min的升温速率升至250℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFeO₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 250 °C at a rate of 10 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFeO ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.4V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为82％，产率为100μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.4V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 82%, and the yield is 100 μmol·cm ^-2 ·h ^-1 .

实施例3Example 3

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍网依次置于丙酮、2M盐酸中超声清洗15min；然后，将经过上述处理的镍网放置于含有0.01M Fe(NO₃)₃和0.02M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应12h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍网清洗干净，烘干备用；Specifically include: placing the nickel mesh in acetone and 2M hydrochloric acid for 15 minutes for ultrasonic cleaning; then, placing the above-mentioned treated nickel mesh in a mixed solution containing 0.01M Fe(NO ₃ ) ₃ and 0.02M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 30°C for 30 minutes, then transferred to a hydrothermal reaction kettle, and reacted in a 100°C oven for 12 hours. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel mesh, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍网在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以10℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel mesh with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 10 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.4V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为85％，产率为120μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.4V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 85%, and the yield is 120 μmol·cm ^-2 ·h ^-1 .

实施例4Example 4

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、2M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.01M Fe(NO₃)₃和0.04M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.01M Fe(NO ₃ ) ₃ and 0.04M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以10℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foam with the catalyst precursor in an air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 10 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.5V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为88％，产率为325μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.5V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 88%, and the yield is 325μmol·cm ^-2 ·h ^-1 .

实施例5Example 5

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、2M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.01M Fe(NO₃)₃和0.04M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应16h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 2M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.01M Fe(NO ₃ ) ₃ and 0.04M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 16h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以10℃/min的升温速率升至320℃，而后焙烧保温2h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。It specifically includes: roasting the nickel foam with the catalyst precursor in the air atmosphere, the gas flow rate of the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 320 °C at a heating rate of 10 °C/min, and then roasted and kept for 2 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.5V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为88％，产率为340μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.5V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 88%, and the yield is 340μmol·cm ^-2 ·h ^-1 .

实施例6Example 6

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.08M urea (solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.5V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为90％，产率为350μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.5V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 90%, and the yield is 350 μmol·cm ^-2 ·h ^-1 .

实施例7Example 7

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.06M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应16h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 3M hydrochloric _acid for ultrasonic cleaning for ₁₅ minutes; mixed with 15ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 16h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以10℃/min的升温速率升至300℃，而后焙烧保温2h，反应压力保持在0.4MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the foamed nickel with catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 10 °C/min, and then roasted and kept for 2 hours , the reaction pressure was kept at 0.4 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.5V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为91.6％，产率为360μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.5V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 91.6%, and the yield is 360μmol·cm ^-2 ·h ^-1 .

实施例8Example 8

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in ethanol and 3M hydrochloric _acid for ultrasonic cleaning for ₁₅ minutes; mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)，该催化剂的扫描电镜图如图1所示。Specifically include: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerol oxidation of this example was obtained after the reaction, and the scanning electron microscope image of the catalyst was shown in FIG. 1 .

由图1可已看出，本发明制备的催化剂中，基底镍表面垂直生长了很多相互交错的超薄NiFeO₄纳米片，NiFeO₄纳米片之间形成很多纳米多孔结构，这样的纳米多孔结构可以增大催化剂的比表面积，暴露更多的活性位点，而且孔结构有利于电解液进入与催化剂充分接触，更有利于电催化氧化甘油。As can be seen from Fig. 1, in the catalyst prepared by the present invention, a lot of interlaced ultrathin _NiFeO nanosheets are vertically grown on the nickel surface of the substrate, and many nanoporous structures are formed between the _NiFeO nanosheets, such nanoporous structures can be The specific surface area of the catalyst is increased to expose more active sites, and the pore structure is conducive to the full contact between the electrolyte and the catalyst, which is more conducive to the electrocatalytic oxidation of glycerol.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加不同的电压，测试催化剂在不同电压下甘油氧化为甲酸的催化效率，测试结果见图2。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1 mol/L glycerin and 1 mol/L sodium hydroxide, and different voltages are applied at room temperature , to test the catalytic efficiency of the catalyst for oxidation of glycerol to formic acid at different voltages, and the test results are shown in Figure 2.

由图2可见，当施加0.6V的恒电位时，甲酸的法拉第效率最高，达到为95％，产率为750μmol·cm^-2·h^-1。It can be seen from Figure 2 that when a constant potential of 0.6V is applied, the faradaic efficiency of formic acid is the highest, reaching 95%, and the yield is 750 μmol·cm ^-2 ·h ^-1 .

进一步地，以本实施例制得的催化剂为例，对本发明催化剂的稳定性进行测试，测试方法为：将催化剂置于电解液(含有0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液)中，施加0.6V恒定电压进行电解；每12小时更换一次电解液，持续电解240个小时，测试结果见图3；测试完成后再次观察催化剂形貌，观察结果见图4。Further, taking the catalyst prepared in this embodiment as an example, the stability of the catalyst of the present invention is tested. The test method is: the catalyst is placed in an electrolyte solution (a mixed aqueous solution containing 0.1mol/L glycerin and 1mol/L sodium hydroxide ), a constant voltage of 0.6V was applied for electrolysis; the electrolyte solution was replaced every 12 hours, and the electrolysis was continued for 240 hours. The test results are shown in Figure 3; after the test was completed, the morphology of the catalyst was observed again, and the observation results were shown in Figure 4.

由图3可见，在100mA·cm^-2的电流密度下持续电解240小时后，其电位几乎无衰减，使用寿命长。而且从图4也可以看出，在经过240小时稳定性测试反应后，催化剂的形貌几乎无变化，NiFe₂O₄纳米片结构仍保持完好。It can be seen from Figure 3 that after continuous electrolysis for 240 hours at a current density of 100mA·cm ^-2 , the potential has almost no attenuation and the service life is long. And it can also be seen from Fig. 4 that after 240 hours of stability test reaction, the morphology of the catalyst hardly changed, and the structure of NiFe ₂ O ₄ nanosheets remained intact.

实施例9Example 9

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.04M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing foamed nickel in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned treated foamed nickel in a mixed solution containing 0.04M Fe(NO ₃ ) ₃ and 0.08M urea (solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温2h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foam with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 2 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为92％，产率为675μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 92%, and the yield is 675μmol·cm ^-2 ·h ^-1 .

实施例10Example 10

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、1M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.04M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在40℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应18h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 1M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.04M Fe(NO ₃ ) ₃ and 0.08M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 40°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 18h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温2h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 2 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为86％，产率为625μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 86%, and the yield is 625μmol·cm ^-2 ·h ^-1 .

实施例11Example 11

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.08M urea (solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.7V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为87％，产率为980μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.7V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 87%, and the yield is 980μmol·cm ^-2 ·h ^-1 .

实施例12Example 12

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.08M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 20h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为89％，产率为655μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 89%, and the yield is 655μmol·cm ^-2 ·h ^-1 .

实施例13Example 13

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应10h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in ethanol and 3M hydrochloric _acid for ultrasonic cleaning for ₁₅ minutes; mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 10h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以10℃/min的升温速率升至250℃，而后焙烧保温2h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。It specifically includes: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 250 °C at a rate of 10 °C/min, and then roasted and kept for 2 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为84％，产率为615μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 84%, and the yield is 615μmol·cm ^-2 ·h ^-1 .

实施例14Example 14

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.02M Fe(NO₃)₃和0.06M尿素的混合溶液(溶剂由24ml甲醇和6ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应18h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in ethanol and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.02M Fe(NO ₃ ) ₃ and 0.06M urea (the solvent consists of 24ml methanol mixed with 6ml of water), ultrasonicated at 30°C for 30 minutes, then transferred to a hydrothermal reaction kettle, and reacted in a 100°C oven for 18 hours. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为82％，产率为595μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 82%, and the yield is 595μmol·cm ^-2 ·h ^-1 .

实施例15Example 15

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、1M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.06M Fe(NO₃)₃和0.06M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在40℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应24h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 1M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.06M Fe(NO ₃ ) ₃ and 0.06M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 40°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 24h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.7V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为85％，产率为940μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.7V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 85%, and the yield is 940μmol·cm ^-2 ·h ^-1 .

实施例16Example 16

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将泡沫镍依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.02M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在40℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应18h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的泡沫镍清洗干净，烘干备用；Specifically include: placing the nickel foam in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the nickel foam treated above in a mixed solution containing 0.02M Fe(NO ₃ ) ₃ and 0.08M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 40°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 18h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foam and dry it for subsequent use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的泡沫镍在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至250℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。It specifically includes: roasting the nickel foam with catalyst precursor in air atmosphere, the gas flow rate in air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 250 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.7V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为82％，产率为865μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.7V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 82%, and the yield is 865μmol·cm ^-2 ·h ^-1 .

实施例17Example 17

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in ethanol and 3M hydrochloric _acid in sequence for ultrasonic cleaning for 15min _; mixed with 15ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 100°C for 20h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.7V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为85％，产率为900μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.7V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 85%, and the yield is 900 μmol·cm ^-2 ·h ^-1 .

实施例18Example 18

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.06M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应24h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.06M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 24h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为86％，产率为920μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 86%, and the yield is 920μmol·cm ^-2 ·h ^-1 .

实施例19Example 19

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.08M Fe(NO₃)₃和0.08M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应10h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.08M Fe(NO ₃ ) ₃ and 0.08M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, hydrothermally reacted in an oven at 100°C for 10h, after the reaction was completed, cooled to room temperature, taken out, and decontaminated with ethanol Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以5℃/min的升温速率升至280℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 280 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为89％，产率为665μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 89%, and the yield is 665μmol·cm ^-2 ·h ^-1 .

实施例20Example 20

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.06M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在20℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应20h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in ethanol and 3M hydrochloric acid for 15 minutes to be ultrasonically cleaned; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.06M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 20°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 100°C for 20h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.1MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 300 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.1 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.8V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为80％，产率为1169μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.8V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 80%, and the yield is 1169 μmol·cm ^-2 ·h ^-1 .

实施例21Example 21

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.04M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应18h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.04M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 100°C for 18h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为150ml/min，焙烧温度从室温以10℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 150ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 10 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.8V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为78％，产率为1103μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.8V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 78%, and the yield is 1103 μmol·cm ^-2 ·h ^-1 .

实施例22Example 22

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于丙酮、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.06M Fe(NO₃)₃和0.04M尿素的混合溶液(溶剂由15ml甲醇和15ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应18h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in acetone and 3M hydrochloric acid for ultrasonic cleaning for 15 minutes; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.06M Fe(NO ₃ ) ₃ and 0.04M urea (the solvent consists of 15ml methanol mixed with 15ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in an oven at 100°C for 18h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至300℃，而后焙烧保温3h，反应压力保持在0.3MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 300 °C at a heating rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.3 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.8V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为76％，产率为1002μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerol to produce formic acid. The conditions for the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.8V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 76%, and the yield is 1002 μmol·cm ^-2 ·h ^-1 .

实施例23Example 23

本实施例一种电催化甘油氧化的催化剂的制备方法，包括以下步骤：In this embodiment, a preparation method of a catalyst for electrocatalytic glycerin oxidation comprises the following steps:

(1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)_x催化剂前驱体；(1) Place the nickel carrier in a mixed solution containing iron salt and a precipitant, and use a hydrothermal method to grow NiFe(OH) _x catalyst precursor on the nickel carrier;

具体包括：将镍箔依次置于乙醇、3M盐酸中超声清洗15min；然后，将经过上述处理的泡沫镍放置于含有0.03M Fe(NO₃)₃和0.04M尿素的混合溶液(溶剂由6ml甲醇和24ml水混合而成)中，先在30℃下超声30min，而后转移至水热反应釜中，在100℃烘箱中水热反应24h，待反应结束后，冷却至室温取出，用乙醇和去离子水将生长有NiFe(OH)_x催化剂前驱体的镍箔清洗干净，烘干备用；Specifically include: placing the nickel foil in ethanol and 3M hydrochloric acid for 15 minutes to be ultrasonically cleaned; then, placing the above-mentioned foamed nickel in a mixed solution containing 0.03M Fe(NO ₃ ) ₃ and 0.04M urea (the solvent consists of 6ml methanol mixed with 24ml of water), ultrasonicated at 30°C for 30min, then transferred to a hydrothermal reaction kettle, and hydrothermally reacted in a 100°C oven for 24h. Ionized water will grow the NiFe(OH) _x catalyst precursor to clean the nickel foil, and dry it for later use;

(2)将步骤(1)获得的生长有NiFe(OH)_x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH) _x catalyst precursor grown in step (1) on the nickel carrier to be roasted under a roasting atmosphere, so as to obtain the catalyst for the electrocatalytic oxidation of glycerol;

具体包括：将长有催化剂前驱体的镍箔在空气气氛下进行焙烧，空气气氛的气体流速为200ml/min，焙烧温度从室温以5℃/min的升温速率升至320℃，而后焙烧保温3h，反应压力保持在0.2MPa；反应结束后即获得本实施例的电催化甘油氧化的催化剂(NiFe₂O₄)。Specifically include: roasting the nickel foil with the catalyst precursor in the air atmosphere, the gas flow rate in the air atmosphere is 200ml/min, the roasting temperature is raised from room temperature to 320 °C at a rate of 5 °C/min, and then roasted and kept for 3 hours , the reaction pressure was kept at 0.2 MPa; the catalyst (NiFe ₂ O ₄ ) for electrocatalytic glycerin oxidation of this embodiment was obtained after the reaction.

将本实施例获得的催化剂用于电催化甘油氧化以产甲酸，电催化氧化反应的条件为：电解液为0.1mol/L甘油和1mol/L氢氧化钠的混合水溶液，常温下施加0.6V的恒电位，甘油被氧化为甲酸，甲酸的法拉第效率为92.5％，产率为685μmol·cm^-2·h^-1。The catalyst obtained in this example is used to electrocatalyze the oxidation of glycerin to produce formic acid. The conditions of the electrocatalytic oxidation reaction are: the electrolyte is a mixed aqueous solution of 0.1mol/L glycerin and 1mol/L sodium hydroxide, and 0.6V is applied at room temperature. At constant potential, glycerol is oxidized to formic acid, the faradaic efficiency of formic acid is 92.5%, and the yield is 685μmol·cm ^-2 ·h ^-1 .

Claims (6)

1.一种电催化甘油氧化的催化剂的制备方法，其特征在于，包括以下步骤：1. a preparation method of a catalyst for electrocatalytic glycerin oxidation, characterized in that, comprising the following steps: (1)将镍载体置于含有铁盐和沉淀剂的混合溶液中，采用水热法使镍载体上生长NiFe(OH)x催化剂前驱体；(1) The nickel carrier is placed in a mixed solution containing iron salt and a precipitant, and a NiFe(OH)x catalyst precursor is grown on the nickel carrier by a hydrothermal method; 所述的混合溶液的溶剂由水与醇混合而成，混合比例为2:8～8:2；The solvent of the mixed solution is formed by mixing water and alcohol, and the mixing ratio is 2:8～8:2; 所述的混合溶液中，铁离子的摩尔浓度为0.01-0.1mol/L，沉淀剂的摩尔浓度为0.01-0.1mol/L；In the mixed solution, the molar concentration of iron ions is 0.01-0.1mol/L, and the molar concentration of precipitating agent is 0.01-0.1mol/L; 所述的水热法是指将所述的镍载体和所述的混合溶液共同转移至反应釜中，于60-150℃下水热反应5-30h；The hydrothermal method refers to transferring the nickel carrier and the mixed solution to a reaction kettle together, and reacting hydrothermally at 60-150° C. for 5-30 hours; (2)将步骤(1)获得的生长有NiFe(OH)x催化剂前驱体的镍载体置于焙烧气氛下进行焙烧，即获得所述的电催化甘油氧化的催化剂；(2) placing the NiFe(OH)x catalyst precursor grown in step (1) on the nickel support that is obtained in a calcination atmosphere and roasting to obtain the catalyst for the electrocatalytic oxidation of glycerin; 所述的焙烧在250-350℃、0.1-1MPa下进行1-20h。The calcination is carried out at 250-350° C. and 0.1-1 MPa for 1-20 hours. 2.如权利要求1所述的电催化甘油氧化的催化剂的制备方法，其特征在于，步骤(1)中，所述的铁盐为硝酸铁、氯化铁、氯化亚铁和硫酸铁中的至少一种；所述的沉淀剂为尿素和六次甲基四胺中的至少一种。2. the preparation method of the catalyst of electrocatalytic glycerol oxidation as claimed in claim 1, is characterized in that, in step (1), described iron salt is ferric nitrate, ferric chloride, ferrous chloride and ferric sulfate at least one of; the precipitation agent is at least one of urea and hexamethylenetetramine. 3.如权利要求1-2中任意一项所述的电催化甘油氧化的催化剂的制备方法，其特征在于，步骤(1)中，先依次采用有机溶剂和酸性溶剂对镍载体进行超声清洗，而后再进行水热反应；3. the preparation method of the catalyst of the electrocatalytic glycerin oxidation as described in any one in claim 1-2, it is characterized in that, in step (1), first adopt organic solvent and acidic solvent to carry out ultrasonic cleaning to nickel support successively, Then carry out hydrothermal reaction; 所述的有机溶剂为丙酮、乙醇和乙酸乙酯中的至少一种；Described organic solvent is at least one in acetone, ethanol and ethyl acetate; 所述的酸性溶剂为盐酸、硫酸和硝酸中的至少一种。The acidic solvent is at least one of hydrochloric acid, sulfuric acid and nitric acid. 4.如权利要求1-2中任意一项所述的电催化甘油氧化的催化剂的制备方法，其特征在于，步骤(2)中，所述的焙烧气氛为空气气氛、氯气气氛和氧气气氛中的至少一种。4. the preparation method of the catalyst of the electrocatalytic glycerin oxidation as described in any one in claim 1-2, it is characterized in that, in step (2), described roasting atmosphere is in air atmosphere, chlorine atmosphere and oxygen atmosphere at least one of . 5.如权利要求4所述的电催化甘油氧化的催化剂的制备方法，其特征在于，所述的氧气气氛中含有惰性稀释气体，该惰性稀释气体为氮气、氩气、氦气、氪气、氖气和氙气中的至少一种。5. the preparation method of the catalyst of electrocatalytic glycerin oxidation as claimed in claim 4 is characterized in that, in described oxygen atmosphere, contains inert diluent gas, and this inert diluent gas is nitrogen, argon, helium, krypton, At least one of neon gas and xenon gas. 6.催化剂在电催化甘油氧化中的应用，其特征在于，所述的催化剂采用如权利要求1-5中任意一项所述的电催化甘油氧化的催化剂的制备方法制得。6. The application of the catalyst in the electrocatalytic glycerol oxidation, characterized in that, the catalyst is prepared by the preparation method of the catalyst for the electrocatalytic glycerol oxidation as described in any one of claims 1-5.

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