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Updated: May 12, 2026

Hydrogen Production and Utilization in a Membrane Reactor
Published on: March 10, 2023
Direct Seawater Hydrogen Evolution via Atomically Precise Regulation of Interfacial pH and Ion-Water Interactions
Zhipu Zhang1,2, Shanshan Lu1,2, Qisheng Yan3
1State Key Laboratory of Advanced Materials For Intelligent Sensing & Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin, China.
None:
Direct seawater electrolysis offers a sustainable route to green hydrogen production from abundant saline water resources, yet industrial applications are limited by sluggish kinetics and catalyst deactivation caused by Mg(OH)2/Ca(OH)2 precipitation or Cl- corrosion. Here, we report a pH-gradient-mediated interfacial engineering strategy that simultaneously enhances activity and stability of metal nanocatalysts for the hydrogen evolution reaction (HER) in natural seawater. By using atomically precise Pt6(TPP)4Cl5 nanoclusters (NCs) (Pt6-TPP, TPP = triphenylphosphine) as paradigm catalysts, we demonstrate self-organized TPP ligands on cluster surface tether Na+/K+ via cation-π interactions. The locally concentrated Na+/K+ cations disrupt the hydrogen-bond network of water molecules for accelerating HER kinetics, and electrostatically attract OH- to establish an alkaline interfacial pH, which can propagate into a diffuse pH gradient toward the bulk of the solution. This pH gradient drives Mg2+/Ca2+ precipitation away from the catalytic surface, preventing site blockage. The enriched OH- can also resist Cl- corrosion of Pt6-TPP NCs. Consequently, Pt6-TPP achieves 10 mA cm-2 at an overpotential of 292 mV and retains exceptional stability (> 500 h) under intermittent renewable-energy operation, with one-tenth the Pt loading of commercial Pt/C. This work establishes a pH gradient-mediated interfacial chemistry framework enabled by atomically precise engineering, providing guidance for sustainable and efficient direct seawater hydrogen evolution.
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