Dieu Thuy Ung Thi, Huan Tran Ngoc, Zanna Sandrine, Wilson Karen, Lee Adam F, Le Ngoc-Diep, Mensah Jim, Dasireddy Venkata D B C, Liem Nguyen Quang
Institute of Materials Science, Vietnam Academy of Science and Technology 18 Hoang Quoc Viet, Cau Giay Hanoi Vietnam
Laboratoire de Chimie des Processus Biologiques, Collège de France, Sorbonne Université 11 Place Marcelin Berthelot 75231 Paris Cedex 05 France
RSC Adv. 2024 Jan 22;14(5):3489-3497. doi: 10.1039/d3ra07639c. eCollection 2024 Jan 17.
Metal organic frameworks (MOFs) are attractive materials to generate multifunctional catalysts for the electrocatalytic reduction of CO to hydrocarbons. Here we report the synthesis of Cu and Zn modified Al-fumarate (Al-fum) MOFs, in which Zn promotes the selective reduction of CO to CO and Cu promotes CO reduction to oxygenates and hydrocarbons in an electrocatalytic cascade. Cu and Zn nanoparticles (NPs) were introduced to the Al-fum MOF by a double solvent method to promote in-pore metal deposition, and the resulting reduced Cu-Zn@Al-fum drop-cast on a hydrophobic gas diffusion electrode for electrochemical study. Cu-Zn@Al-fum is active for CO electroreduction, with the Cu and Zn loading influencing the product yields. The highest faradaic efficiency (FE) of 62% is achieved at -1.0 V RHE for the conversion of CO into CO, HCOOH, CH, CH and CHOH, with a FE of 28% to CH, CH and CHOH at pH 6.8. Al-fum MOF is a chemically robust matrix to disperse Cu and Zn NPs, improving electrocatalyst lifetime during CO reduction by minimizing transition metal aggregation during electrode operation.
金属有机框架材料（MOFs）是制备用于将CO电催化还原为碳氢化合物的多功能催化剂的有吸引力的材料。在此，我们报道了铜和锌修饰的富马酸铝（Al-fum）MOFs的合成，其中锌促进CO选择性还原为CO，而铜在电催化级联反应中促进CO还原为含氧化合物和碳氢化合物。通过双溶剂法将铜和锌纳米颗粒（NPs）引入Al-fum MOF中以促进孔内金属沉积，并将所得的还原态Cu-Zn@Al-fum滴铸在疏水气体扩散电极上进行电化学研究。Cu-Zn@Al-fum对CO电还原具有活性，铜和锌的负载量会影响产物产率。在-1.0 V（相对于可逆氢电极，RHE）下，将CO转化为CO、HCOOH、CH、CH和CHOH的法拉第效率（FE）最高可达62%，在pH 6.8时，CH、CH和CHOH的FE为28%。Al-fum MOF是一种化学稳定性良好的基质，可分散铜和锌纳米颗粒，通过在电极操作过程中最小化过渡金属聚集来提高CO还原过程中的电催化剂寿命。
