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Published on: April 7, 2017
Intensified Accumulation of OH- and Improved Electron Transfer by Reactive Chlorine-Resistant Layer Achieve
Jiawei Mu1, Shuo Liu1, Chang Yu1
1State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory For Energy Materials and Chemical Engineering, Frontier Science Center For Smart Materials, School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning, China.
Abstract:
The stability and efficiency of direct seawater electrolysis are constrained by competitive Cl- adsorption and corresponding chlorine oxidation reaction, which further restricts diffusion and accumulation of OH-, as well as transfer of electrons involved in counterpart oxygen evolution reaction (OER), leading to severe Cl--corrosion. Herein, intensified popular-OH- accumulation and electron transfer are achieved through Ag-mediated reactive chlorine-resistant AgCl layer integrated onto NiCo-oxyhydroxide (AgCl/NiCo-OOH). Specifically, under external electric field driving, Ag species on the NiCo-OOH surface undergo electrochemical transformation and free Cl--immobilization via in situ formation of robust AgCl layer, subsequently leveraging common-ion repulsion effect to sieve and control composition of ions in Stern layer, and thereby preventing Cl- corrosion. Simultaneously, the AgCl with high-curvature induces electric fields across scales, incorporating mesoscale proximal-tip and microscale built-in electric fields, which significantly accelerates OER kinetics by intensifying diffusion and accumulation of reactant OH- and transfer of electron. Resultantly, the AgCl/NiCo-OOH achieves an ultralow overpotential of 331 mV in alkaline simulated seawater and sustains stable operation for over 2200 h at Ampere-level current density in alkaline seawater without Cl--related corrosion. Further, the corresponding anion-exchange membrane electrolyzer demonstrates a low energy consumption (4.50 kWh m-3 H2) and long-term durability (over 1500 h) at 500 mA cm-2.
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