Atomic Level In Situ Observation of Surface Amorphization in Anatase Nanocrystals During Light Irradiation in Water Vapor

An in situ atomic level investigation of the surface structure of anatase nanocrystals has been conducted under conditions relevant to gas phase photocatalytic splitting of water. The experiments were carried out in a modified environmental transmission electron microscope fitted with a high intensity broadband light source with an illumination intensity of 1430 mW/cm(2) close to 10 suns. When the titania is exposed to light and water vapor, the initially crystalline surface converts to an amorphous phase one to two monolayers thick. Spectroscopic analyses show that the amorphous layer contains titanium in a +3 oxidation state. The amorphous layer is stable and does not increase in thickness with time and is heavily hydroxylated. This disorder layer will be present on the anatase surface under reaction conditions relevant to photocatalytic splitting of water.