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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Chloride-Resistant CoO@Mo(OH)x Layered Heterostructure for Efficient Seawater Oxygen Evolution
Junyu Nie1, Ruiqing Zhang1, Haosheng Zhang2
1SJTU Paris Elite Institute of Technology, Shanghai Jiao Tong University, Shanghai200240, China.
Abstract:
Seawater electrolysis for large-scale hydrogen production is severely hindered by chloride ion (Cl-) poisoning and the competing chlorine evolution reaction (CER) against the oxygen evolution reaction (OER). In this work, a layered CoO@Mo(OH)x heterostructure with a crystalline CoO inner layer and an amorphous Mo(OH)x outer layer forming a close interface, with possible oxygen-mediated Mo-O-Co interactions, was constructed. Systematic evaluation reveals distinct activity trends in alkaline vs simulated seawater electrolytes. The reference MoCoOx catalyst degrades severely in seawater due to MoO-mediated Cl- adsorption promoting CER at adjacent CoO sites. In contrast, the layered CoO@Mo(OH)x structure exhibits excellent chloride tolerance and OER performance, achieving 312 mV at 50 mA cm-2 and outstanding stability (98.1% retention after 170 h at 10 mA cm-2). Using experiments, in situ Raman, and DFT, we reveal that the outer Mo(OH)x layer captures chloride (Mo binding: -3.71 eV vs -3.32 eV on Co), protecting inner CoO sites and enabling durable OER.
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