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Proton-free electron-trapping feature of titanium dioxide nanoparticles without the characteristic blue color

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Most solar-energy conversion applications are based on trapping and transferring photoinduced electrons on oxide semiconductor nanoparticles, such as titanium dioxide, and broad UV-vis absorption (400~800 nm) and monotonic IR absorption (1100~3000 cm−1)… Click to show full abstract

Most solar-energy conversion applications are based on trapping and transferring photoinduced electrons on oxide semiconductor nanoparticles, such as titanium dioxide, and broad UV-vis absorption (400~800 nm) and monotonic IR absorption (1100~3000 cm−1) signals have long been considered signatures of the electron-trapping state on titanium dioxide nanoparticles. Here we show that, under proton-free conditions and using iodide ions in acetonitrile as the hole scavenger, the intrinsic electron-trapping feature of titanium dioxide nanoparticles does not exhibit the characteristic UV-vis absorption and infrared absorption signatures. Further electron spin resonance studies identify the proton-free electron-trapping state as the lattice octahedral Ti6c3+ species, differing from the traditional proton-participating surface tetrahedral Ti4c3+ species. Synchronized radiation ultraviolet photoelectron spectroscopy results also show that the internal electron-trapping state without protons has a larger Ti3d binding energy (1.8 eV) than the blue electron-trapping state (1.3 eV) that forms when protons participate and thus shows different electron transfer abilities.Irradiation of titanium dioxide creates electronically trapped states which play a key role in solar energy conversion. Here, intrinsic electron trapping under aprotic conditions is experimentally shown to exhibit different spectroscopic properties than the conventional blue colour observed under protic conditions.

Keywords: electron; titanium dioxide; dioxide nanoparticles; electron trapping

Journal Title: Communications Chemistry
Year Published: 2019

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