Zhou Jing, Zhao Jiani, Liu Jiquan, Song Dengmeng, Xu Wenhua, Yang Anjin, Li Jun, Wang Ning
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China.
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710069, China.
J Colloid Interface Sci. 2024 Oct 15;672:512-519. doi: 10.1016/j.jcis.2024.05.223. Epub 2024 Jun 6.
Conversion of NO to NH proceeds stepwise in natural system under two different enzymes involving intermediate NO. Artificial electro-driven NO reduction also faces the obstacle of low faradaic efficiency due to insufficient utilization of this intermediate. Herein, we demonstrate a bimetallic COF-based electrocatalyst for the cascade catalysis of NO-to-NO-to-NH for the first time. TpBpy-CuCo exhibits a significantly improved performance, with an enhancement factor of 1.4-2 compared to monometallic TpBpy-M. The NH yield rate achieves 25.6 mg h mg at -0.55 V vs RHE over TpBpy-CuCo, together with excellent faradaic efficiency (93.4 %). This achievement demonstrates cascade catalysis between Co and Cu units, and their distinct roles are investigated through electrochemical experiments and theory calculations. In electrocatalytic process, Cu site facilities *NO-to-*NOH step, while the Co site significantly decreases the energy barrier of *NHOH-to-*NH. The present work provides a valuable inspiration in designing efficient catalysts for cascade reaction.
在自然体系中，一氧化氮（NO）向氨（NH）的转化在两种不同的酶作用下逐步进行，涉及中间体NO。人工电驱动的NO还原也面临着法拉第效率低的障碍，因为这种中间体的利用不充分。在此，我们首次展示了一种基于双金属共价有机框架（COF）的电催化剂，用于NO到NH的级联催化。与单金属的TpBpy-M相比，TpBpy-CuCo表现出显著提高的性能，增强因子为1.4至2。在相对于可逆氢电极（RHE）为-0.55 V的电压下，TpBpy-CuCo上的NH产率达到25.6 mg h mg，同时具有优异的法拉第效率（93.4%）。这一成果证明了Co和Cu单元之间的级联催化作用，并通过电化学实验和理论计算研究了它们各自不同的作用。在电催化过程中，请确认原文中“Cu site facilities NO-to-NOH step”是否有误，推测可能是“Cu site facilitates NO-to-NOH step”，即Cu位点促进NO到NOH的步骤，而Co位点显著降低了NHOH到NH的能垒。本工作为设计用于级联反应的高效催化剂提供了宝贵的灵感。
