Electrocatalytic CO₂ reduction provides a possible method for carbon neutralization. Electrode materials with efficient electron transfer, high selectivity and large current density are highly desirable. Herein, we have developed a couple of tetraphenyl-p-phenylenediamine and metalloporphyrin-based 2D COFs for the electrocatalytic CO₂ reduction. TPPDA-MPor-COFs (M = Co and Ni) were obtained by the cross-condensation of tetraphenyl-p-phenylenediamine (TPPDA) and 5,10,15,20-tetrakis(4-formylphenyl)-metalloporphyrin (MPor). The as-prepared TPPDA-CoPor-COF shows high CO faradaic efficiencies of 87–90% from −0.6 to −0.9 V vs. RHE, and the largest CO partial current density (j_CO) of TPPDA-CoPor-COF (−22.2 mA cm⁻² at −1.0 V vs. RHE) exceeds those of most of the reported COF-based electrocatalysts. Notably, exfoliated TPPDA-CoPor-COF nanosheets (TPPDA-CoPor-COF-NSs) show much better electrocatalytic performance. The CO faradaic efficiencies of TPPDA-CoPor-COF-NSs are over 90% in a wider voltage range (−0.7 to −0.9 V), and the maximum j_CO reaches up to −29.2 mA cm⁻² at −1.0 V. Density functional theory calculations have been performed to rationalize the improved CO₂RR performance of TPPDA-CoPor-COF.

中文翻译：

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基于四苯基对苯二胺和金属卟啉的共价有机骨架用于将 CO2 电化学转化为 CO

电催化CO ₂还原为碳中和提供了一种可能的方法。具有高效电子转移、高选择性和大电流密度的电极材料是非常需要的。在此，我们开发了几种用于电催化 CO ₂还原的四苯基对苯二胺和金属卟啉基二维 COF 。TPPDA-MPor-COFs (M = Co 和 Ni) 是通过四苯基-对苯二胺 (TPPDA) 和 5,10,15,20-四(4-甲酰基苯基)-金属卟啉 (MPor)的交叉缩合获得的。所制备的 TPPDA-CoPor-COF 在 -0.6 至 -0.9 V与RHE 之间显示出 87-90% 的高 CO 法拉第效率，以及最大的 CO 分流密度 ( j _CO）的TPPDA-CoPor-COF（-22.2 mA cm ^-2 at -1.0 V vs. RHE）超过了大多数报道的基于COF的电催化剂。值得注意的是，剥离的 TPPDA-CoPor-COF 纳米片（TPPDA-CoPor-COF-NSs）显示出更好的电催化性能。TPPDA-CoPor-COF-NSs 的 CO 法拉第效率在更宽的电压范围（-0.7 至 -0.9 V）内超过 90%，最大j _CO在 -1.0 V 时达到 -29.2 mA cm ^-2 。已进行泛函理论计算以合理化TPPDA-CoPor-COF 改进的CO ₂ RR 性能。