Zhou Shuai, Zhang Li-Jun, Zhu Lei, Tung Chen-Ho, Wu Li-Zhu
Laboratory of Photochemical Conversion and Optoelectronic Materials, New Cornerstone Science Laboratory, Technical Institute of Physics and Chemistry, Chinese Academy of Science, Beijing, 100190, P. R. China.
School of Future Technology, University of Chinese Academy of Sciences, Beijing, 101408, P. R. China.
Adv Mater. 2023 Oct;35(41):e2300923. doi: 10.1002/adma.202300923. Epub 2023 Aug 31.
Due to the easy accessibility, chemical stability, and structural tunability of the macrocyclic skeleton, cobalt phthalocyanines immobilized on carbon supports offer an ideal research model for advanced electrochemical carbon dioxide reduction reaction (eCO RR). In this work, an amphiphilic cobalt phthalocyanine (TC-CoPc) is loaded on multiwalled carbon nanotubes to reveal the roles of hydrophilic/hydrophobic properties on catalytic efficiency. Surprisingly, the resultant electrode exhibits a CO Faradaic efficiency (FE ) of 95% for CO RR with turnover frequency (TOF) of 29.4 s at an overpotential of 0.585 V over long-term electrolysis in a H-type cell. In the membrane electrode assembly (MEA) device, the boosted transport of water vapor to the catalyst layer slows down carbonate crystallization and enhances the stability of the electrode, with FE value of >99% over 27 h at -0.25 A, representing the best selectivity and stability among reported molecular catalysts in MEA devices. The amphiphilic cobalt phthalocyanine, which decreases interfacial charge and mass transfer resistance and maintains effective contact between active sites and the electrolyte, highlights the exceptional CO conversion from a molecular perspective.
由于大环骨架具有易于获取、化学稳定性和结构可调性，负载在碳载体上的钴酞菁为先进的电化学二氧化碳还原反应（eCO RR）提供了理想的研究模型。在这项工作中，一种两亲性钴酞菁（TC-CoPc）负载在多壁碳纳米管上，以揭示亲水/疏水性质对催化效率的作用。令人惊讶的是，在H型电池中进行长期电解时，所得电极在0.585 V的过电位下，对CO RR的CO法拉第效率（FE）为95%，周转频率（TOF）为29.4 s⁻¹。在膜电极组件（MEA）装置中，水蒸气向催化剂层的增强传输减缓了碳酸盐结晶并提高了电极的稳定性，在-0.25 A下27小时内FE值>99%，代表了MEA装置中报道的分子催化剂中最佳的选择性和稳定性。两亲性钴酞菁降低了界面电荷和传质电阻，并保持了活性位点与电解质之间的有效接触，从分子角度突出了卓越的CO转化性能。
