摘要
Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.
Interaction of hydrogen with TiO2 plays a vital role in TiO2-based photocatalysis and thermal catalysis. In this work, we compared thermal-, photo-, and electron-induced reactivity of various types of hydrogen species on a rutile TiO2（110） surface formed by atomic H exposure at 320 and 115 K by means of thermal desorption spectroscopy, X-ray photoelectron spectroscopy and low energy electron diffraction. Atomic H interaction with rutile TiO2（110） at 115 K forms surface TiààH hydride, surface hydroxyl group, and chemisorbed water. Upon heating, surface TiààH hydride reacts to produce H2 while surface hydroxyl groups react to form both water and H2. Atomic H interaction with rutile TiO2（110） at 320 K strongly reduces TiO2 due to the continuous formation and desorption of water and forms surface hydroxyl groups and likely subsurface/bulk hydrogen species. Upon heating, hydrogen forms as the only gas-phase product and its desorption activation energy decreases with the subsurface/bulk reduction extent of rutile TiO2（110）. Surface Ti-H hydride exhibits photo-induced reactivity while both surface TiààH hydride and surface hydroxyl group exhibit electro-induced reactivity. These results have important implications for understanding the hydrogen-involved thermal and photo reactions on TiO2-based catalysts.
基金
financially supported by the National Natural Science Foundation of China (Nos. 21525313, 21761132005)
Chinese Academy of Sciences (No. KJZD-EW-M03)
MOE Fundamental Research Funds for the Central Universities (No. WK2060030017)
Collaborative Innovation Center of Suzhou Nano Science and Technology
