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In the face of global climate change and the need for energy diversification, electrocatalytic technology emerges as an eco‐friendly solution. However, persistent electrode failures hinder long‐term stability. This review comprehensively outlines the primary causes leading to the failure of self‐supported electrodes, encompassing substrate passivation, substrate/catalyst dissolution, CO poisoning, catalyst migration and agglomeration, as well as cathodic etching. Proposed strategies center on material design, emphasizing anchoring, lattice matching, substrate stability, and morphological control. Advanced characterization techniques and in situ technologies offer promising ways. The integrated deployment of these strategies will provide crucial guidance and support for the sustainable advancement of electrocatalytic technology. [ABSTRACT FROM AUTHOR]

The electrocatalytic selective oxidation of 5‐hydroxymethylfurfural (HMF) presents a highly efficient and eco‐friendly method for biomass utilization. Herein, we synthesized pure β‐Ni(OH)2 and amorphous Ni(OH)2 on nickel foam (NF) using a facile stepwise electrodeposition technique and evaluated their catalytic performances for the oxidation of HMF to 2,5‐furan dicarboxylic acid (FDCA). The β‐Ni(OH)2 nanosheets‐decorated electrode (β‐NiNS/NF) exhibited excellent interfacial lattice matching with the substrate nickel, resulting in enhanced electron transfer at the catalyst‐substrate interface, as confirmed by electrochemical analysis. Consequently, the β‐NiNS/NF electrode displayed improved intrinsic electrocatalytic activity and interfacial stability. Additionally, it demonstrated effective HMF adsorption capability. These advantageous properties led to enhanced HMF conversion, selectivity, and structural stability. Notably, the β‐NiNS/NF electrode achieved an unprecedented FDCA yield of 80.6 % under relatively large current density galvanostatic electrolysis commonly used in industry. Moreover, our investigation identified a novel possible oxidation pathway during HMF electrocatalysis. This study not only showcases an efficient and scalable synthetic approach but also highlights the potential of the β‐NiNS/NF electrode for industrial HMF electrocatalytic oxidation under conditions involving relatively large applied currents. [ABSTRACT FROM AUTHOR]