Abstract

In order to meet large scale energy demands in a more sustainable way, water electrolysers could be coupled with the well-developed photovoltaic solar cell technology to provide the energy input for green H2 production. Commercial PEM (proton exchange membranes) electrolysers operate in acidic pH which favours H2 production at the cost of using IrO2 as catalyst for oxygen production at the anode representing a significant drawback for this technology. Contrary, an AEM (anionic exchange membranes) operates in alkaline electrolytes which enables the use of low cost and highly active OER catalyst such as NiCoFeOx,1 however at the expense of including an extra overpotential to drive the H2 production in the electrolyser.2 Using bipolar membranes (BPM), where a cationic exchange membrane CEM is used alongside an anionic exchange membrane, allows the electrolyser to operate at different pHs: at the cathode in an acidic environment to favour H2 production, and alkaline for O2 production at the anode. However, a BPM induces a significant increase in resistance across the electrolyser.2 Recently, it has been demonstrated that by adding metal oxides as water dissociation catalysts, the electrolyser overpotential significantly decreased passing from 8 V to 2.2 V at 500 mA cm-2.3 This milestone in the field was accomplished by using two metal oxides with different point of zero charge (PZC) 3 and 11 for IrO2 and NiO respectively. Interestingly, a similar performance was observed when only TiO2 was used as water dissociation catalyst which PZC sits between IrO2 and NiO.4 Indeed demonstrating the necessity of better understanding of the physicochemical phenomena that governs water dissociation interfaces.Using TiO2 as water dissociation catalyst provides a suitable platform to understand how properties such as conductivity or different doping content affect water dissociation during H2 production in the electrolyser. Therefore, in this work modifications of TiO2 were investigated and its impact on the cell voltage when used between Nafion 212 and Sustainion membranes as CEM and AEM respectively, in a commercial 5 cm2 electrolyser at 60 ⁰C that operates only with DI water. To only benchmark the performance of the BPM, Pt and IrO2 were chosen as H2 and O2 catalysts respectively.

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