Wien Effect in Interfacial Water Dissociation Through Proton-Permeable Graphene Electrodes

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Abstract

Strong electric fields can accelerate molecular dissociation reactions. The phenomenon known as the Wien effect was previously observed using high-voltage electrolysis cells that produced fields of about 107 V m−1, sufficient to accelerate the dissociation of weakly bound molecules (e.g., organics and weak electrolytes). The observation of the Wien effect for the common case of water dissociation (H2O ⇆ H+ + OH−) has remained elusive. Here we study the dissociation of interfacial water adjacent to proton-permeable graphene electrodes and observe strong acceleration of the reaction in fields reaching above 108 V m−1. The use of graphene electrodes allows measuring the proton currents arising exclusively from the dissociation of interfacial water, while the electric field driving the reaction is monitored through the carrier density induced in graphene by the same field. The observed exponential increase in proton currents is in quantitative agreement with Onsager’s theory. Our results also demonstrate that graphene electrodes can be valuable for the investigation of various interfacial phenomena involving proton transport.

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This work was supported by The Royal Society (URF\R1\201515, M.L.-H.), Lloyd’s Register Foundation and European Research Council (VANDER) (A.K.G.). J.C. acknowledges a full scholarship from the Chinese Scholarship Council (CSC). E.G. and D.B. acknowledge the EPSRC NOWNano programme (EP/L01548X/1) for funding. Part of this work was supported by the Flemish Science Foundation (FWO-Vl) and a BAGEP Award of the Turkish Academy of Sciences with funding from the Sevinc-Erdal Inonu Foundation.

Keywords

Wien effect, Graphene, Electric fields, Reaction rate, Electrokinesis, Dissociation (chemistry), Quantum Coherence in Photosynthesis and Aqueous Systems, Science, Electrode, Chemical physics, Materials Science, FOS: Physical sciences, Organic chemistry, Quantum mechanics, Article, Electrolysis, Atomic physics, Analytical Chemistry (journal), Physics - Chemical Physics, Electrolyte, Mesoscale and Nanoscale Physics (cond-mat.mes-hall), Electric field, Electrochemistry, Materials Chemistry, Nanotechnology, Graphene: Properties, Synthesis, and Applications, Chemical Physics (physics.chem-ph), FOS: Nanotechnology, Condensed Matter - Mesoscale and Nanoscale Physics, Physics, Q, Molecule, Atomic and Molecular Physics, and Optics, Materials science, Chemistry, Electrochemical Detection of Heavy Metal Ions, Physics and Astronomy, Physical chemistry, Physical Sciences, Ion Effects, Proton, Graphene, Engineering sciences. Technology

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03 medical and health sciences, 0302 clinical medicine, 0301 basic medicine, 0303 health sciences

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13

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1

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534

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539
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