Electrochemical production of high value-added CO from CO on transition metal-nitrogen-carbon (M−N−C) catalysts is a promising approach to achieve carbon neutral economy, yet the quest for robust catalysts is driven by achieving > 96 % CO faradaic efficiency (FE) under low overpotential and wide potential range. Herein, we report a novel synthetic approach involving post-metallization of the pre-synthesized N-doped carbon (NC-T) support for the fabrication of robust and efficient Ni@NC-T quasi-molecular catalysts toward CO electroreduction reaction (CORR). The optimum Ni@NC-1100 catalyst exhibited an extremely high FE > 99 % at −0.72 V reversible hydrogen electrode (RHE). Of interest is the FE maintained above 96 % over a wide potential window from −0.52 V to −1.12 V. Density functional theory (DFT) calculation validated that the presence of axial pyrrolic-N significantly enhances the Ni-N active site for CO activation, resulting in the lowest activation energy for the *COOH intermediate generation compared to other axial ligands.

中文翻译：

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高度协调的 Ni-N5 位点可有效电催化 CO2 还原为 CO，法拉第效率超过 99%

在过渡金属-氮-碳 (M−N−C) 催化剂上从 CO 电化学生产高附加值 CO 是实现碳中和经济的一种有前景的方法，但对稳健催化剂的追求是通过实现 > 96 % CO 法拉第来推动的低过电势和宽电势范围下的效率（FE）。在此，我们报告了一种新颖的合成方法，涉及预合成的氮掺杂碳（NC-T）载体的后金属化，用于制造坚固且高效的 Ni@NC-T 准分子催化剂，用于 CO 电还原反应（CORR） 。最佳Ni@NC-1100催化剂在-0.72 V可逆氢电极（RHE）下表现出极高的FE > 99%。令人感兴趣的是，FE 在 -0.52 V 至 -1.12 V 的宽电位窗口内保持在 96% 以上。密度泛函理论 (DFT) 计算验证了轴向吡咯-N 的存在显着增强了 CO 活化的 Ni-N 活性位点，与其他轴向配体相比，*COOH 中间体生成的活化能最低。