Accelerated self-cleaning by Cu promoted semiconductor binary-oxides under low intensity sunlight irradiation

• TiO2–ZrO2 discolors MB within 120 min monitored at the air-solid interface.
• Cu doping accelerates the MB-discoloration kinetics compared to TiO2–ZrO2.
• Peak shift and stretching of the symmetric MB (CH2)-vibrations was followed.
• IFCT mechanism is suggested to account for the photocatalytic discoloration of MB.

Uniform adhesive TiO2–ZrO2 films co-sputtered on polyester (PES) under low intensity sunlight irradiation discolored methylene blue (MB) within 120 min. The discoloration kinetics was seen to be accelerated by a factor four by TiO2–ZrO2–Cu containing ∼0.01% Cu, as determined by X-ray fluorescence (XRF). TiO2–ZrO2–Cu also increased also accelerated by a factor the discoloration of MB compared to TiO2/Cu(PES). MB discoloration was also monitored under visible light in the solar cavity by using a 400 nm cutoff filter. Photocatalyst surfaces were characterized by spectroscopic methods showing the film optical absorption and by X-ray photoelectron spectroscopy (XPS), the surface atomic percentage concentration up to 120 nm (∼600 layers). The band-gaps of TiO2–ZrO2 and TiO2–ZrO2–Cu were estimated for films co-sputtered for different times. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR), the systematic shift of the predominating νs(CH2) vibration-rotational MB bands was monitored up to complete MB discoloration under low intensity solar simulated light. Evidence is presented for the OH generation by TiO2–ZrO2–Cu participating in the self-cleaning mechanism. The photo-induced interfacial charge transfer (IFCT) on the TiO2–ZrO2–Cu is discussed in terms of the electronic band positions of the binary oxides and Cu intra-gap states. This study presents the first evidence for a Cu-promoted composed of two binary oxide semiconductors accelerating the self-cleaning performance.

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