Xin Kong, Bin Liu, Zhongqiu Tong, Rui Bao, Jianhong Yi, Shuyu Bu, Yunpeng Liu, Pengfei Wang, Chun‐Sing Lee, Wenjun Zhang
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引用次数: 0
摘要
金属酞菁是一种很有前景的二氧化碳还原反应(CO2RR)电催化剂。然而,它们的催化活性和稳定性(尤其是在高电位下)仍不尽如人意。在此,我们通过在酞菁钴(CoPc)中引入电荷可切换的紫胶配体,合成了一种共价有机聚合物(COP-CoPc)。COP-CoPc 在 CO2RR 方面表现出极高的活性,包括在较宽的电位窗口内具有较高的法拉第效率,以及在 H 型电池中,在所有配体调谐酞菁催化剂中具有最高的 CO 部分电流密度。特别是,COP-CoPc 还显示出巨大的实际应用潜力,例如,在双电极膜电极组装反应器中,150 mA/cm2 的大电流密度下实现了 >95% 的 FECO。原位和原位 X 射线吸收精细结构光谱测量和理论计算表明,当电荷转换型紫胶配体转换为中性态配体时,它们可以充当电子供体,丰富 COP-CoPc 中 Co 中心的电子密度,增强 *CO 的解吸能力,从而提高 CO 的选择性。此外,紫胶配体优异的可逆氧化还原能力和 Co-N4 位点中 Co-N 键强度的增加,使 COP-CoPc 在高电位和高电流条件下具有出色的稳定性,丰富了电荷转换配体定制 CO2RR 性能的知识。
Charge‐switchable ligand ameliorated cobalt polyphthalocyanine polymers for high‐current‐density electrocatalytic CO2 reduction
Metallic phthalocyanines are promising electrocatalysts for CO2 reduction reaction (CO2RR). However, their catalytic activity and stability (especially under high potential) are still unsatisfactory. Herein, we synthesized a covalent organic polymer (COP‐CoPc) by introducing charge‐switchable viologen ligands into cobalt phthalocyanine (CoPc). The COP‐CoPc exhibits great activity for CO2RR, including a high Faradaic efficiency over a wide potential window and the highest CO partial current density among all ligand‐tuned phthalocyanine catalysts reported in the H‐type cell. Particularly, COP‐CoPc also shows great potential for practical applications, for example, a FECO of >95% is realized at a large current density of 150 mA/cm2 in a two‐electrode membrane electrode assembly reactor. Ex situ and in situ X‐ray absorption fine structure spectroscopy measurements and theory calculations reveal that when the charge‐switchable viologen ligands switch to neutral‐state ones, they can act as electron donors to enrich the electron density of Co centers in COP‐CoPc and enhance the desorption of *CO, thus improving the CO selectivity. Moreover, the excellent reversible redox capability of viologen ligands and the increased Co–N bonding strength in the Co–N4 sites enable COP‐CoPc to possess outstanding stability under elevated potentials and currents, enriching the knowledge of charge‐switchable ligands tailored CO2RR performance.