Noble-Metal-Free Photocatalytic H2Generation: Active and Inactive ‘Black’ TiO2Nanotubes and Synergistic Effects

Abstract

Over the past five years a number of different synthesis approaches has been reported to obtain so-called ‘black’ titania. One of the outstanding features of the material is that certain synthesis processes lead to the formation of an intrinsic co-catalytic center and thus enable noble-metal free photocatalytic H2-generation. In the present work, using TiO2nanotube layers, we compare three common ‘blackening’ approaches, namely i) the original high-pressure hydrogenation (HPT-H2), ii) a classic high temperature reduction in Ar, and iii) an electrochemical (cathodic) reduction. We demonstrate that except for high pressure hydrogenation also cathodic reduction leads to an activation of TiO2- that is, it exhibits noble-metal-free photocatalytic H2generation. Moreover, we show that a combination of cathodic reduction/high pressure hydrogenation leads to a synergistic effect, that is, a significant enhancement of the combined co-catalytic activity.