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In this study, we investigate noble metal free photocatalytic water splittingon natural anatase single crystal facets and on wafer slices of the [001] planebefore and after these surfaces have been modified by high pressurehydrogenation (HPH) and hydrogen ion-implantation. We find that on the natural,intact low index planes photocatalytic H$_2$ evolution (in absence of noblemetal co-catalyst) can only be achieved when the hydrogenation treatment isaccompanied by the introduction of crystal damage, such as simple scratching,miscut in the wafer or by implantation damage. X-ray reflectivity (XRR), Raman,and optical reflection measurements show that plain hydrogenation leads to a ~1 nm thick black titania surface layer without activity, while a colorless,density modified and ~ 7 nm thick layer with broken crystal symmetry is presentin the ion implanted surface. These results demonstrate that i) the H-treatmentof an intact anatase surface needs to be combined with defect formation forcatalytic activation, and ii) activation does not necessarily coincide with thepresence of black color.

Noble metal free photocatalytic H$_2$ generation on black TiO$_2$: On the influence of crystal facets vs. crystal damage