共价键
共价有机骨架
部分
氧气
氧化还原
密度泛函理论
化学
酞菁
分子
法拉第效率
共轭体系
金属有机骨架
电化学
无机化学
光化学
立体化学
电极
有机化学
物理化学
计算化学
吸附
聚合物
作者
Hui Guo,Duan‐Hui Si,Hongfei Zhu,Zi-Ao Chen,Rong Cao,Yuan‐Biao Huang
标识
DOI:10.1002/anie.202319472
摘要
Herein, we propose an oxygen-containing species coordination strategy to boost CO2 electroreduction in the presence of O2. A two-dimensional (2D) conjugated metal-covalent organic framework (MCOF), denoted as NiPc-Salen(Co)2-COF that is composed of the Ni-phthalocyanine (NiPc) unit with well-defined Ni-N4-O sites and the salen(Co)2 moiety with binuclear Co-N2O2 sites, is developed and synthesized for enhancing the CO2RR under aerobic condition. In the presence of O2, one of the Co sites in the NiPc-Salen(Co)2-COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO2 molecules and stabilize the key intermediate *COOH of the CO2RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni-N4-O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO2RR. Thus, NiPc-Salen(Co)2-COF exhibits high oxygen-tolerant CO2RR performance and achieves outstanding CO Faradaic efficiency (FECO) of 97.2 % at -1.0 V vs. the reversible hydrogen electrode (RHE) and a high CO partial current density of 40.3 mA cm-2 at -1.1 V in the presence of 0.5 % O2, which is superior to that in pure CO2 feed gas (FECO=94.8 %, jCO=19.9 mA cm-2). Notably, the NiPc-Salen(Co)2-COF achieves an industrial-level current density of 128.3 mA cm-2 in the flow-cell reactor with 0.5 % O2 at -0.8 V, which is higher than that in pure CO2 atmosphere (jCO=104.8 mA cm-2). It is worth noting that an excellent FECO of 86.8 % is still achieved in the presence of 5 % O2 at -1.0 V. This work provides an effective strategy to enable the CO2RR under O2 atmosphere by utilizing the *OOH intermediates of ORR to boost CO2 electroreduction.
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