Tantalum oxynitride nanotube film arrays for unconventional nanostructured photo-electrodes active with visible light

• Published in: Catalysis today 2023-06, Vol.418, p.114146, Article 114146
• Main Authors: Tavella, Francesco, Genovese, Chiara, Andrés Garcés Pineda, Felipe, Centi, Gabriele, Perathoner, Siglinda, Ampelli, Claudio
• Format: Article
• Language: English
• Subjects: Ethanol photo-reforming; H2 production; Nanostructured film electrodes; Tantalum oxynitride; TaON nanotube arrays; Visible-light photocatalysis
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2023.114146

Tantalum-oxy-nitride nanotubes (TaOxNy NTs) ordered in 1D were successfully synthesized through controlled anodic oxidation of metallic Ta foils followed by high-temperature annealing under NH3 flow to prepare unconventional nanostructured photo-electrodes active with visible light. For the synthesis, a two-step anodization process was adopted: i) the first step in ethylene glycol with 0.33 % NH4F and 3 % H2O, ii) the second step in H2SO4 (98 %) with 1 % HF and 4 % H2O, by applying different voltages and anodization times. Scanning Electron Microscopy integrated with Energy Dispersive X-ray spectroscopy (SEM-EDX) revealed the NTs length ranging from 2 to 5 µm, and the inner tube diameter from 20 to 100 nm, in good correlation with the synthesis parameters. The N-content (from 2.7 % to 19.1 %) was dependent on the nitridation temperature (from 500° to 900°C), and the conversion of bare Ta2O5 into TaOxNy strongly influenced the absorption in the visible region with a bandgap shift from 4.0 to 2.1 eV, respectively. Photo-electrochemical and catalytic performances were evaluated with chronoamperometric measurements and tests in different photo-reactions using AM 1.5 G simulated sunlight: (i) degradation of methylene blue (MB), (ii) ethanol gas-phase photo-reforming and (iii) bias-assisted photoelectrochemical water splitting. The TaOxNy NTs film-type electrode obtained by nitriding at 800 °C showed the highest photocurrent value (0.1 mA∙cm-2), and the highest rates of MB degradation (k1 of 0.0189 min-1) and H2 photo-production. [Display omitted] •A double-step anodization technique is developed to prepare Ta2O5 nanotube arrays.•Oxygen is partially replaced by N atoms by ammonia treatment at high temperature.•Ta-oxy-nitride shows a more favorable band gap (2.1 eV) than bare Ta2O5 (4.0 eV).•TaOxNy nanotube-arrays provides high performance in degradation of methylene blue.•H2 production by photo-catalytic water splitting and ethanol reforming is enhanced.