Synergies of phenolic-acids’ surface-modified titanate nanotubes (TiNT) for enhanced photo-catalytic activities

• New modification strategy for stable and VIS-light responded TiNTs is presented.
• Phenolic acids surface-modified TiNTs narrowed the band gaps from 2.9 to 1.55 eV.
• Particles photo-activity and stability depends on the modification mechanism.

The adsorption of chemically similar but differently oxygen reactive phenolic-acid derivatives on the Ti-nanotubes (TiNTs) surfaces to increase and/or broaden their photo-induced activity was studied using Raman and X-ray photoelectron spectroscopies combined with zeta-potential analyses. Photo-catalytic activities and stabilities of newly synthesized particles were evaluated by using high-resolution capillary electrophoresis in combination with cyclic voltammetry and spin-trapping EPR spectroscopy.The modification with caffeic acid (CA) resulted in well-oriented and dense but oxygen semi-stable thin layer (1–3 nm) of self-assembled mono-molecular and/or bi-dentate coordinated molecules on the TiNTs’ surfaces, which narrowed the band gap from 2.9 eV (for un-modified TiNTs) to 1.55 eV, but however restrict the hydroxyl radicals generation under both UV (320 nm) and VIS (450 nm) source radiations. On the other hand, the gallic acid (GA) resulted in situ polymerized GA layer through bi-dentate binding as highly-oxygen-stabilized surface structure, yielding narrower band gap of 2.25 eV and increased hydroxyl radical’s generation under both exposure lights. The third tested hydroxybenzoic acid (HA), resulted to an unstable layer bonded thorough single-hydrogen bonding mechanism.This work offers a new modification strategy for stable (oxygen and photo-induction related) and highly visible–light responded TiNTs as photocatalyst.

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