Stable Water Oxidation in Acid Using Manganese-Modified TiO₂ Protective Coatings

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O _x, topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O _x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O _x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO₂ coatings, annealed (Ti,Mn)O _x films can make direct charge transfer to a Fe(CN)₆^3-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN)₆^3-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O _x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO₂. We correlated changes in the crystallinity (amorphous to rutile TiO₂) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O _x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O _x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.