常温条件下甲烷和二氧化碳同时制备甲醇的电化学反应系统和机理研究

It is important strategic significance for gaseous methane and carbon dioxide to be changed liquid methanol in energy utilization and storage and carbon dioxide emission reduction and transformation. In this subject, based on the finished work of the National Fund Project “Research on electrochemical reaction system and mechanism of directly preparing methanol from methane at room temperature”, the composition of the ethanol-based electrolyte containing ethanol, water, NaCl、NaOH and ionic liquids will be adjusted for carbon dioxide to be cathodic reduced to prepare methanol. In the preparation process of electrode which is used in cathodic reduction of carbon dioxide, cathodic electrodes will be modified by doping metal or metallic oxide which have catalytic activity for carbon dioxide to methanol. A series of hollow electrodes with much more micropores are prepared by pressure roasting, which have high adsorptivity and catalytic conversion of carbon dioxide to methanol. The optimal composition and preparation condition will be chosen by experiments. The reduction mechanism of carbon dioxide in cathode will be researched theoretically. In same electrolytic cell, anodic oxidation of methane to methanol and cathodic reduction of carbon dioxide to methanol will be combined. An electrochemical reaction system of preparing methanol directly from methane and carbon dioxide simultaneously in room temperature will be built.

将气体甲烷、二氧化碳转变为液体甲醇，在能源利用与存储，二氧化碳减排与转化方面具有重要的战略意义。本项目基于已完成的国家基金项目“常温条件下甲烷直接制备甲醇的电化学反应系统和机理研究”的工作基础上，对已获得的用于甲烷制取甲醇的以乙醇、水、NaCl、NaOH为基液，添加离子液体的乙醇基电解质溶液组成进行调整，用于二氧化碳阴极还原制取甲醇。在用于二氧化碳阴极还原的电极制备过程中，掺杂对二氧化碳转化为甲醇具有催化活性的金属或金属氧化物，对电极进行修饰改性。通过加压焙烧，制备系列不同的、具有微孔和中空的，对二氧化碳气体具有较高吸附能力和催化转化为甲醇能力的阴极电极，通过实验优选出最好的电极组成和制备条件。利用电化学工作站对二氧化碳阴极还原机理进行理论研究。在同一电解池中，将甲烷阳极氧化制取甲醇和二氧化碳阴极还原制取甲醇进行组合，建立常温条件下甲烷和二氧化碳同时直接制备甲醇的电化学反应系统。

本项目基于已完成的国家基金项目“常温条件下甲烷直接制备甲醇的电化学反应系统和机理研究”的工作基础上，对已获得的用于甲烷制取甲醇的以乙醇、水、NaCl、NaOH为基液，添加离子液体的乙醇基电解质溶液组成进行调整，用于二氧化碳阴极还原制取甲醇。. 通过本项目的实施，对二氧化碳阴极还原生成甲醇的电催化机理，电极选择、改性、制备等作了细致研究，表明普通金属电极在碱性溶液中对二氧化碳的还原的产物主要是甲酸。通过电极的改性、复合电极的制备，二氧化碳的还原生成甲醇的法拉第效率（电流效率）可达50%以上，C-Cu2O电极上生成甲醇的法拉第效率高达90%以上，已具备工业应用价值。. 将二氧化碳阴极还原制备甲醇的电化学系统与甲烷阳极氧化制备甲醇的电化学系统结合，获得了甲烷和二氧化碳同时制备CH3OH 的电化学反应系统，生成甲醇的法拉第效率达80-160%。同时完成发明专利申请4项（已授权1项），已发表研究论文9篇，培养硕士研究生9名，完成了项目书的预期目标。