Visible light activation of photocatalysts formed from the heterojunction of sludge-generated TiO2 and g-CN towards NO removal

Highlights: • N-doped TiO₂ and TiO₂/g-CN composites were prepared from dye wastewater sludge. • There was an enhanced photooxidation of NO at TiO₂ to melamine ratio of 1:2.33. • TiO₂/g-CN composite showed substantial NO removal under visible light irradiation. • Superior nitrate selectivity of 92% from successful TiO₂/g-CN heterojunction was obtained. The feasibility of preparing TiO₂/g-CN heterojunction from Ti-incorporated dried dye wastewater sludge is explored in this study. Two reaction routes of composite formation were evaluated. In the initial approach, one-step calcination of dried sludge and melamine mixture @600 °C was carried out. Detailed morphological and chemical characterizations showed that the one-step calcination route did not create TiO₂/g-CN composites; instead, only N-doped anatase TiO₂ composites were formed. Moreover, due to the non-uniform composition of organic content in the dried sludge, it was not easy to control the N doping level by varying melamine content (0–100%) in the precursor mix. However, successful formation of anatase TiO₂ and g-CN was observed when a two-step calcination route was followed, i.e., via synthesis of anatase TiO₂ from dried sludge, and later development of heterojunction by calcining (@550 °C) the TiO₂ and melamine mixture. X-ray diffraction along with infrared and X-ray photoelectron spectroscopy verified the effective heterojunction. In addition, maximum atmospheric NO removal under UV and visible light were observed for the prepared composite when the melamine content in the precursor mixture was 70%. After 1 h of UV and visible light irradiation, the best TiO₂/g-CN composite removed 25.71% and 13.50% of NO, respectively. Optical characterization suggested that the enhanced NO oxidation under UV/visible light was due to the bandgap narrowing and diminished photogenerated electron-hole recombination.