Work Function‐Guided Tandem Ohmic‐PN Heterojunctions on Nanoporous Scaffolds for Industrial Oxygen Evolution

Developing robust non‐precious electrocatalysts for oxygen evolution reaction is essential for widespread use of alkaline water electrolysis. However, the intrinsic trade‐off between structural durability and catalytic activity under harsh industrial conditions remains a formidable challenge. Herein, we report a synergistic tandem Ohmic‐PN heterojunction architecture monolithically integrated on a nanoporous Ni scaffold, enabling work function‐guided interfacial electronic‐state engineering to break this dilemma. Specifically, the sequential np‐Ni/NiS Ohmic contact and NiS/NiFe LDH PN junction establish a dual‐interface kinetic modulation. The Ohmic interface facilitates low‐resistance charge extraction, while the NiS/NiFe LDH PN junction promotes interfacial charge redistribution, accompanied by changes in the electronic state and local coordination environment of the NiFe LDH layer. The 3D bicontinuous nanoporous framework simultaneously confers a super‐hydrophilic and underwater aerophobic surface that promote rapid micro‐bubble detachment. As a result, the electrode requires an overpotential of only 343 mV to deliver 1000 mA cm −2 in 1.0 m KOH. Under industrial conditions, the electrolyzer not only sustains for 572 h under 500 mA cm −2 , but also exhibits exceptional resilience against start‐stop voltage reversals and dynamic power fluctuations. This work offers a general strategy that bridges atomic‐level interfacial engineering with macroscopic mass transport for scalable and sustainable hydrogen production.