Our study achieves efficient electrocatalysis for the electrooxidation reaction in multi-electrolyte systems by synergistically modulating structure and electronic coupling through rational design. We establish novel principles for controlling the morphology and performance of MOFs: formation of nano-flower structure requires co-existence of Ni site and Fc ligand, doping of Fe sites promotes 3D crystal morphology development, which marks a pioneering advance in the field. Among them, the Bimetallic Dual-Ligand MOF: NFBF (6:2) exhibits outstanding electrocatalytic performance (210 mV at 10 mA·cm^-2). Operando Raman spectroscopy and XAFS reveal the electronic restructuring feature of NFBF (6:2) during the catalytic OER process. Combined with DFT calculations, which identify Ni as the catalytic active site, these investigations uncover significant electronic migration and redistribution, substantially reducing the reaction energy barrier and accelerating the catalytic process. Comprehensive exploration demonstrates that NFBF (6:2) not only performs well under various multi-electrolyte conditions but also maintains a nearly consistent catalytic mechanism. Furthermore, when applied to overall water splitting, (+) NFBF (6:2) | | NFBF (6:2) (-) achieves significant catalytic effects in both alkaline freshwater (1.40 V at 10 mA·cm^-2) and seawater (1.44 V at 10 mA ·cm^-2) electrolyzers. This work highlights the crucial role of electronic coupling in optimizing electrocatalytic performance and offers new insights for addressing mitigating environmental pollution, embodying substantial practical and research potential.

Photoelectrochemical (PEC) water splitting presents a promising approach for harnessing solar energy and converting it into hydrogen energy. However, the limited water oxidation activity of semiconductor photoanodes has severely hampered the overall conversion efficiency. In this study, a hollow dodecahedral structure of NiCo-LDH (HD-NiCo-LDH) was designed using the metal-organic framework ZIF-67 as a precursor. HD-NiCo-LDH was employed to modify the BiVO₄ photoanode, serving as an oxygen evolution cocatalyst. HD-NiCo-LDH can enhance light absorption, accelerate photogenic hole extraction, promote photogenic charge separation and improve the kinetics of water oxidation reaction. Significantly, the unique hollow dodecahedral structure of HD-NiCo-LDH possesses a larger specific surface areas, which provides additional active sites for the water oxidation reaction and facilitates the adsorption of water molecules. The photocurrent density of the optimized HD-NiCo-LDH/BiVO₄ photoanode reaches 4.54 mA/cm² at 1.23 V vs. RHE, which is 3.3 times greater than the bare BiVO₄ photoanode. This presented work introduces an innovative design concept for photoanodes supported by oxygen evolution cocatalysts with multi-active sites.