Electrochemical glycerol oxidation reaction (GOR) is a promising candidate to couple with cathodic reaction, like hydrogen evolution reaction, to produce high‐value product with less energy consumption. Two‐dimensional conjugated metal‐organic frameworks (2D c‐MOFs), comprising square‐planar metal‐coordination motifs (e.g., MO4, M(NH)4, MS4), are notable for their programable active sites, intrinsic charge transport, and excellent stability, making them promising catalyst candidates for GOR. Here, we introduce a novel class of 2D c‐MOFs electrocatalysts, M2[NiPcS8] (M=Co/Ni/Cu), which are synthesized via coordination of octathiolphthalocyaninato nickel (NiPc(SH)8) with various metal centers. Due to a fast kinetic and high activity of CoS4 sites for GOR, the electrocatalytic tests demonstrate that Co2[NiPcS8] supported on carbon paper displays a low GOR potential of 1.35 V vs. RHE at 10 mA cm‐2, significantly reducing the overall water‐electrolysis‐voltage reduction by 0.27 V from oxygen evolution reaction to GOR, thereby outperforming Ni2[NiPcS8] and Cu2[NiPcS8]. Additionally, we have determined that the GOR activity of CoX4 linkage sites varies with different heteroatoms, following an experimentally and theoretically confirmed activity order of CoS4>CoO4>Co(NH)4. The GOR performance of Co2[NiPcS8] not only demonstrate superior performance among non‐noble metal complex, but also provides critical insights on designing high‐performance MOF electrocatalysts upon optimizing the electronic environment of active sites.

中文翻译：

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金属-酞菁基二维共轭金属-有机框架用于电化学甘油氧化反应


电化学甘油氧化反应 （GOR） 是与阴极反应（如析氢反应）偶联以产生能耗较低的高价值产物的有前途的候选者。二维共轭金属有机框架 （2D c-MOF） 由方形平面金属配位基序（例如 MO4、M（NH）4、MS4）组成，以其可编程的活性位点、本征电荷传输和出色的稳定性而著称，使其成为 GOR 的有前途的催化剂候选者。在这里，我们介绍了一类新型的 2D c-MOF 电催化剂 M2[NiPcS8] （M=Co/Ni/Cu），它是通过八硫代酞氰基镍 （NiPc（SH）8） 与各种金属中心配位合成的。由于 CoS4 位点对 GOR 的快速动力学和高活性，电催化测试表明，在 10 mA cm-2 下，负载在碳纸上的 Co2[NiPcS8] 显示出 1.35 V 的低 GOR 电位，与 RHE 相比，显著降低了从析氧反应到 GOR 的整体水电解电压降低 0.27 V， 从而优于 Ni2[NiPcS8] 和 Cu2[NiPcS8]。此外，我们已经确定 CoX4 键位点的 GOR 活性随不同的杂原子而变化，遵循实验和理论证实的 CoS4>Co4>Co（NH）4 的活性顺序。CO2[NiPcS8] 的 GOR 性能不仅在非贵金属配合物中表现出优异的性能，而且为在优化活性位点的电子环境后设计高性能 MOF 电催化剂提供了重要见解。