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Engineering W-O-Co interfacial electron bridge in transition metal phosphide/tungsten oxide heterostructure enables ampere-level hydrogen production from seawater electrolysis

Dong Yan,Xuetao Cheng,Xiaoxiao Dong,Han Wang,Xingchen Chang,Chenghui Xia,Yongcheng Jin,Chun-Chao Hou

Electrolysis of seawater driven by renewable energy holds great promise for sustainable hydrogen production. However, both catalyst corrosion caused by competitive Cl − adsorption and sluggish reaction kinetics are major challenges in seawater electrolysis. Here, inspired by the concept of hard and soft acids and bases (HSAB), a unique interfacial W-O-Co electron bridge is constructed on the catalyst surface to achieve the electronic coupling of hard-acid W site and borderline-acid Co site via the oxygen bridge, which demonstrates exceptional performance for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline water and seawater, as well as high anti-corrosion stability. Remarkably, WO 3 /CoP electrode requires low overpotentials of merely 154 mV (alkaline freshwater) and 189 mV (alkaline seawater) for HER, and 334 mV (alkaline freshwater) and 343 mV (alkaline seawater) for OER to achieve 100 mA cm −2 , respectively. When deployed our bifunctional catalyst as both anode and cathode in an alkaline anion-exchange membrane seawater electrolyzer, the system achieves 1 A cm −2 at a low cell voltage of 1.80 V and maintains stable electrolysis for over 250 h at 100 mA cm −2 . Theoretical and experimental investigations reveal that the hard-acid W site of the electronic W-O-Co bonded bridge prefers adsorption of hard-base OH - rather than soft-base Cl - , thereby mitigating Cl - interference and suppressing chloride corrosion. Simultaneously such interfacial W-O-Co bridging significantly accelerates charge transfer from Co site to W site, thereby regulating the electronic structures of catalysts and optimizing the sorption behaviors of reaction intermediates. This work provides a feasible anti-corrosion engineering strategy to design efficient and robust electrocatalysts for practical seawater electrolysis.