Metal–organic frameworks (MOFs) have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity, but the limited catalytic activity and stability has hampered their practical use in water splitting. Herein, we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs (donated as AE-CoNDA) to serve as efficient catalyst for water splitting. AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm⁻² and a small Tafel slope of 62 mV dec⁻¹ with excellent stability over 100 h. After integrated AE-CoNDA onto BiVO₄, photocurrent density of 4.3 mA cm⁻² is achieved at 1.23 V. Experimental investigations demonstrate that the stretched Co–O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p, which accounts for the fast kinetics and high activity. Theoretical calculations reveal that the stretched Co–O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

金属有机框架（MOF）已被开发为探索内在结构与催化活性之间关系的理想平台，但有限的催化活性和稳定性阻碍了其在水分解中的实际应用。在此，我们开发了一种键长调整策略，用于优化通过酸蚀刻合成的萘基 MOFs（以 AE-CoNDA 形式捐赠），作为水分解的有效催化剂。 AE-CoNDA 表现出 260 mV 的低过电位，可达到 10 mA cm ^{-2和 62 mV dec -1}的小塔菲尔斜率，在 100 小时内具有出色的稳定性。将 AE-CoNDA 集成到 BiVO ₄上后，在 1.23 V 下实现了 4.3 mA cm ^-2的光电流密度。实验研究表明，拉伸的 Co-O 键长可以优化 Co 3 d和 O 2 p的轨道杂化，这解释了快速动力学和高活性。理论计算表明，拉伸的Co-O键长增强了Co活性位点上含氧中间体的吸附，从而实现高效的水分解。