Exceptional performance of photoelectrochemical water oxidation of single-crystal rutile TiO(2) nanorods dependent on the hole trapping of modified chloride

It is highly desired to effectively trap photogenerated holes for efficient photoelectrochemical (PEC) water oxidation to evolve O(2) on oxide semiconductors. Herein, it is found for the first time mainly based on the time-resolved- and atmosphere-controlled- surface photovoltage responses that the modified chloride would effectively trap photogenerated holes so as to prolong the charge lifetime and hence promote charge separation of single-crystal rutile TiO(2) nanorods. Its strong capacity to trap holes, comparable to the widely-used methanol and Co(II) phosphate, is well responsible for the exceptional photoactivities for PEC water oxidation to evolve O(2) on rutile nanorods with a proper amount of chloride modified, about 2.5-time high as that on the resulting anatase nanoparticles, even 10-time if the surface area is considered. Moreover, it is suggested that the hole trapping role of chemically-adsorbed chloride is related to its lonely-pair electrons, and to the subsequently-produced intermediate Cl atoms with proper electronegativity for evolving O(2). Interestingly, this finding is also applicable to the chloride-modified anatase TiO(2). This work will provide a feasible strategy to design high-activity nanostructured semiconductor photoanodes for PEC water oxidation, even for overall water splitting.