CN111589448A - A carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity - Google Patents

Abstract

The invention discloses a carbon dioxide electro-reduction catalyst with ultrahigh gas phase selectivity, which is prepared by adding copper chloride into deionized water, then adding sodium hydroxide aqueous solution, and violently stirring; adding sodium borohydride aqueous solution, and carrying out suction filtration and drying on the obtained solution; and then, carrying out air burning on the obtained solid sample in a tubular furnace, and carrying out air burning on the sample in the tubular furnace under the nitrogen atmosphere to obtain the target material. The invention has the advantages of good catalytic effect and high Faraday efficiency of gas-phase products.

Description

Translated fromChinese

一种具有超高气相选择性的二氧化碳电还原催化剂A carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity

技术领域technical field

本发明属于新能源化学与电催化交叉技术领域，涉及一种具有超高气相选择性的二氧化碳电还原催化剂及其制备方法。The invention belongs to the cross technical field of new energy chemistry and electrocatalysis, and relates to a carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity and a preparation method thereof.

背景技术Background technique

煤，石油，天然气等传统化石燃料的燃烧，会在空气中排放出大量的CO₂,空气中的CO₂浓度过高会造成全球变暖，海平面上升等一系列环境问题，同时空气中的大量CO₂也是储量非常丰富的C源，如果能够将CO₂转化为具有经济效益的化学品，也能有效的缓解人类所面临的能源危机等一些列问题。目前，能源结构正处于由高碳利用向低碳利用转换的关键时期，CO₂引起的全球变暖已成为全世界最关心的环保问题之一。为减少大气中的CO₂含量，大力发展低碳技术、通过多种技术手段将CO₂进行回收利用是最为有效的方法。在众多CO₂转化技术中，电催化CO₂还原由于其常温常压下即可实现反应，反应条件温和、操作简单；且在电还原过程中可通过控制电极及反应条件实现对产物的选择性合成。因此相对于其它还原方法，电化学还原CO₂具有更好的应用前景。在用于催化CO₂还原的许多催化剂中，铜基材料受到了最广泛的关注，铜基材料能够有效的将CO₂转化为烃类产品。Peter Broekmann等人用动态氢气泡模板，利用添加剂辅助电沉积法制备了双金属AgCu泡沫材料。该材料中银和铜保持完全的相位分离，纳米银高度分散在铜基体中。将其在温和条件下(200℃,12小时)热退火，可以提高CO₂RR产乙醇的选择性。中国科学院化学所韩布兴研究组发现了硒化铜纳米催化剂在二氧化碳电化学还原法生产甲醇过程中的出色表现，在285mV的低过电压下，电流密度可高达41.5mA·cm-2并且法拉第效率为77.6％。该电流密度比目前报道的电流密度高，并且甲醇生产的法拉第效率非常高。复旦大学化学系郑耿锋教授设计合成了一种铜取代的氧化铈纳米棒材料(Cu-CeO₂)，实现了Cu在氧化铈上的高度分散；同时，氧化铈纳米棒特异性暴露的(110)面是最易生成氧空穴的晶面，多氧空穴的结构会有利于材料催化还原反应。Cu-CeO₂催化ECR反应生成甲烷的法拉第效率达到58％。The combustion of traditional fossil fuels such as coal, oil and natural gas will emit a large amount of CO₂ in the air. Excessive CO₂ concentration in the air will cause a series of environmental problems such as global warming and sea level rise. A large amount of CO₂ is also a very abundant C source. If CO₂ can be converted into chemicals with economic benefits, it can also effectively alleviate a series of problems such as the energy crisis faced by human beings. At present, the energy structure is in a critical period of transition from high-carbon utilization to low-carbon utilization, and global warming caused by CO₂ has become one of the most concerned environmental issues in the world. In order to reduce the CO₂ content in the atmosphere, vigorously developing low-carbon technologies and recycling CO₂ through various technical means are the most effective methods. Among many CO₂ conversion technologies, electrocatalytic CO₂ reduction can realize the reaction under normal temperature and pressure, with mild reaction conditions and simple operation; and in the electroreduction process, the selectivity to products can be realized by controlling electrodes and reaction conditions. synthesis. Therefore, compared with other reduction methods, electrochemical reduction of_CO2 has better application prospects. Among the many catalysts used to catalyze_CO2 reduction, copper-based materials have received the most attention, which can efficiently convert_CO2 to hydrocarbon products. Bimetallic AgCu foams were prepared by additive-assisted electrodeposition using dynamic hydrogen bubble templates by Peter Broekmann et al. In this material, silver and copper maintain complete phase separation, and nano-silver is highly dispersed in the copper matrix. Thermal annealing under mild conditions (200 °C, 12 h) can improve the selectivity of CO₂ RR for ethanol production. The research group of Han Buxing from the Institute of Chemistry, Chinese Academy of Sciences discovered the excellent performance of copper selenide nanocatalysts in the production of methanol by electrochemical reduction of carbon dioxide. At a low overvoltage of 285mV, the current density can be as high as 41.5mA·cm-2 and the Faradaic efficiency is 77.6%. This current density is higher than that reported so far, and the Faradaic efficiency of methanol production is very high. Prof. Gengfeng Zheng from the Department of Chemistry, Fudan University designed and synthesized a copper-substituted cerium oxide nanorod material (Cu-CeO₂ ) to achieve a high degree of dispersion of Cu on cerium oxide; at the same time, the specific exposure of cerium oxide nanorods (110) The crystal face is the most likely to generate oxygen vacancies, and the structure of multiple oxygen vacancies will be beneficial to the catalytic reduction reaction of the material. The faradaic efficiency of Cu_- CeO2 to catalyze the ECR reaction to methane reaches 58%.

发明内容SUMMARY OF THE INVENTION

本发明的目的在于提供一种具有超高气相选择性的二氧化碳电还原催化剂，本发明的有益效果是催化效果好，具有高效的气相产物的法拉第效率能。The purpose of the present invention is to provide a carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity. The beneficial effects of the present invention are good catalytic effect and high Faradaic efficiency of gas-phase products.

本发明所采用的技术方案是按照以下步骤：The technical scheme adopted in the present invention is according to the following steps:

步骤1：在去离子水中加入氯化铜，然后加入氢氧化钠水溶液，剧烈搅拌；Step 1: Add copper chloride to deionized water, then add sodium hydroxide aqueous solution, and stir vigorously;

步骤2：再加入硼氢化钠水溶液，将所得溶液抽滤干燥；Step 2: Add sodium borohydride aqueous solution again, and filter the obtained solution to dry;

步骤3：然后将所得固体样品在管式炉内空烧，再将样品在管式炉内氮气氛围下空烧，即得目标材料。Step 3: Then, the obtained solid sample is air-fired in a tube furnace, and then the sample is air-fired in a nitrogen atmosphere in the tube furnace to obtain the target material.

进一步，去离子水中加入50-80mg氯化铜，然后加入20-30ml 0.5mol/L的氢氧化钠水溶液，剧烈搅拌，再加入20-30ml 0.03mol/L硼氢化钠水溶液，将所得溶液抽滤干燥。Further, add 50-80mg copper chloride in deionized water, then add the sodium hydroxide aqueous solution of 20-30ml 0.5mol/L, stir vigorously, then add 20-30ml 0.03mol/L sodium borohydride aqueous solution, the gained solution is suction filtered dry.

进一步，固体样品在管式炉内200℃空气氛围下空烧3小时，再将样品在管式炉内300℃氮气氛围下空烧3小时，即得目标材料。Further, the solid sample was air-fired in a tube furnace at 200°C for 3 hours in an air atmosphere, and then the sample was air-fired in a tube furnace at 300°C under a nitrogen atmosphere for 3 hours to obtain the target material.

附图说明Description of drawings

图1是材料透射电镜形貌示意图；Fig. 1 is the schematic diagram of material transmission electron microscope morphology;

图2是电压和法拉第效率关系图。Figure 2 is a graph of voltage versus Faradaic efficiency.

具体实施方式Detailed ways

下面结合具体实施方式对本发明进行详细说明。The present invention will be described in detail below with reference to specific embodiments.

实施例1Example 1

在去离子水中加入50-80mg氯化铜，然后加入20-30ml 0.5mol/L的氢氧化钠水溶液，剧烈搅拌，再加入20-30ml 0.03mol/L硼氢化钠水溶液，将所得溶液抽滤干燥。然后将所得固体样品在管式炉内200℃空气氛围下空烧3小时，再将样品在管式炉内300℃氮气氛围下空烧3小时，即得目标材料。将材料进行电催化二氧化碳还原测试，在-1.3V vsRHE下，气相产物的法拉第效率能达到70％。Add 50-80mg cupric chloride in deionized water, then add 20-30ml 0.5mol/L sodium hydroxide aqueous solution, stir vigorously, then add 20-30ml 0.03mol/L sodium borohydride aqueous solution, the obtained solution is suction filtered and dried . Then, the obtained solid sample was air-fired in a tube furnace at 200°C for 3 hours in an air atmosphere, and then the sample was air-fired in a tube furnace at 300°C under a nitrogen atmosphere for 3 hours to obtain the target material. The material was tested for electrocatalytic carbon dioxide reduction, and the Faradaic efficiency of the gas-phase product could reach 70% at -1.3V vs RHE.

实施例2Example 2

在去氮掺杂石墨烯水溶液中加入50-80mg氯化铜，然后加入20-30ml 0.5mol/L的氢氧化钠水溶液，剧烈搅拌，再加入20-30ml 0.03mol/L硼氢化钠水溶液，将所得溶液抽滤干燥。然后将所得固体样品在管式炉内200℃空气氛围下空烧3小时，再将样品在管式炉内300℃氮气氛围下空烧3小时，即得目标材料。将材料进行电催化二氧化碳还原测试，在-1.3V vsRHE下，气相产物的法拉第效率能达到96％。Add 50-80mg cupric chloride in the denitrogenation-doped graphene aqueous solution, then add 20-30ml 0.5mol/L sodium hydroxide aqueous solution, stir vigorously, then add 20-30ml 0.03mol/L sodium borohydride aqueous solution, The resulting solution was suction filtered and dried. Then, the obtained solid sample was air-fired in a tube furnace at 200°C for 3 hours in an air atmosphere, and then the sample was air-fired in a tube furnace at 300°C under a nitrogen atmosphere for 3 hours to obtain the target material. The material was tested for electrocatalytic carbon dioxide reduction, and the Faradaic efficiency of the gas-phase product could reach 96% at -1.3V vs RHE.

实施例3Example 3

在去氮掺杂石墨烯水溶液中加入50-80mg氯化铜，然后加入20-30ml 0.5mol/L的氢氧化钠水溶液，剧烈搅拌，再加入20-30ml 0.03mol/L硼氢化钠水溶液，将所得溶液抽滤干燥。然后将所得固体样品在管式炉内200℃空气氛围下空烧3小时，再将样品在200℃氮气氛围下对材料处理，所得材料催化二氧化碳电还原，在-1.3V下，气相产物的法拉第效率能达到73％。Add 50-80mg cupric chloride in the denitrogenation-doped graphene aqueous solution, then add 20-30ml 0.5mol/L sodium hydroxide aqueous solution, stir vigorously, then add 20-30ml 0.03mol/L sodium borohydride aqueous solution, The resulting solution was suction filtered and dried. Then, the obtained solid sample was air-fired in a tube furnace at 200°C in an air atmosphere for 3 hours, and then the sample was treated under a nitrogen atmosphere at 200°C, and the obtained material catalyzed the electroreduction of carbon dioxide. The efficiency can reach 73%.

图1为材料透射电镜形貌示意图。图2是电压和法拉第效率关系图。以上所述仅是对本发明的较佳实施方式而已，并非对本发明作任何形式上的限制，凡是依据本发明的技术实质对以上实施方式所做的任何简单修改，等同变化与修饰，均属于本发明技术方案的范围内。Figure 1 is a schematic diagram of the TEM morphology of the material. Figure 2 is a graph of voltage versus Faradaic efficiency. The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention belong to the present invention. within the scope of the technical solution of the invention.

Claims (3)

Translated fromChinese

1.一种具有超高气相选择性的二氧化碳电还原催化剂，其特征在于按照以下步骤进行：1. a carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity is characterized in that carrying out according to the following steps:步骤1：在去离子水中加入氯化铜，然后加入氢氧化钠水溶液，剧烈搅拌；Step 1: Add copper chloride to deionized water, then add sodium hydroxide aqueous solution, and stir vigorously;步骤2：再加入硼氢化钠水溶液，将所得溶液抽滤干燥；Step 2: Add sodium borohydride aqueous solution again, and filter the obtained solution to dry;步骤3：然后将所得固体样品在管式炉内空烧，再将样品在管式炉内氮气氛围下空烧，即得目标材料。Step 3: Then, the obtained solid sample is air-fired in a tube furnace, and then the sample is air-fired in a nitrogen atmosphere in the tube furnace to obtain the target material.2.按照权利要求1所述一种具有超高气相选择性的二氧化碳电还原催化剂，其特征在于：所述去离子水中加入50-80mg氯化铜，然后加入20-30ml 0.5mol/L的氢氧化钠水溶液，剧烈搅拌，再加入20-30ml 0.03mol/L硼氢化钠水溶液，将所得溶液抽滤干燥。2. according to a kind of carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity according to claim 1, it is characterized in that: described deionized water adds 50-80mg cupric chloride, then adds the hydrogen of 20-30ml 0.5mol/L Sodium oxide aqueous solution, vigorously stirred, and then 20-30 ml of 0.03 mol/L sodium borohydride aqueous solution was added, and the obtained solution was suction filtered and dried.3.按照权利要求1所述一种具有超高气相选择性的二氧化碳电还原催化剂，其特征在于：所述固体样品在管式炉内200℃空气氛围下空烧3小时，再将样品在管式炉内300℃氮气氛围下空烧3小时，即得目标材料。3. A carbon dioxide electroreduction catalyst with ultra-high gas-phase selectivity according to claim 1, characterized in that: the solid sample is air-fired for 3 hours in a tube furnace at 200°C in an air atmosphere, and then the sample is placed in a tube furnace. The target material was obtained by firing in a vacuum furnace at 300°C under nitrogen atmosphere for 3 hours.

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