Effect of oxygen and titanium contents on the stability of nanocrystalline Ti-Ru-Fe-O cathode materials for chlorate electrolysis

摘要

Electrodes made from nanocrystalline Ti:Ru:Fe (2 - y:1 + y/2:1 + y/2), with y varying from 0 to 1 by step of 0.25, and Ti:Ru:Fe:O (2:1:1:w), with w varying from 0 to 2 by step of 0.5, were prepared and tested as activated cathodes for the hydrogen evolution reaction in typical chlorate electrolysis conditions. These electrodes were subjected to an accelerated aging test, consisting of a succession of cycles of hydrogen discharge (HER) and open-circuit (OCP) conditions. In addition to monitoring the cathodic overpotential value during the aging test, visual inspection and mass loss measurements were performed on the electrodes at the end of the test to assess their stability. In the case of Ti:Ru:Fe (2:1:1), a large increase of the cathodic overpotential value is observed after 20 cycles. Adding O to the formulation causes a remarkable improvement of the long-term stability of the electrodes. As little as [O] = 10 at.% in nanocrystalline Ti:Ru:Fe:O (2:1:1:w) materials is sufficient for the electrode to show absolutely no sign of degradation after 50 cycles of HER/OCP, the longest accelerated test conducted. Adding more O to the formulation of the material does not lead to further stability improvement. A better stability under the conditions of the accelerated aging test can also be observed for nanocrystalline Ti:Ru:Fe (2 - y:1 + y/2:1 + y/2) materials with y > 0. In that case however, the level of improvement is dependent on the value of y. The best results are obtained for y = 0.75. A hypothesis is proposed to explain the improved stability obtained by lowering the Ti content and/or by adding O. The similarity and difference between both ways of improving the stability of the nanocrystalline Ti:Ru:Fe materials are also discussed. [References: 14]