One-pot hydrothermal preparation of Ni and I co-doped brookite-anatase TiO2 nanoparticles with remarkably enhanced photoreduction activity of CO2 to CH4

Ni and I co-doped TiO2 nanoparticles with mixed anatase-brookite phase (Ni/I-TiO2) were synthesized by the hydrothermal-calcination method for photocatalytic CO2 reduction with H2O vapor. The I and Ni co-doping, anatase-brookite phase junction, as well as the presence of Ti(III) and Ni(III) endowed the catalyst with promoted visible light absorption, increased reduction ability of photogenerated electrons, facilitated charge separation and migration along with modulated CO2 adsorption mode and capacity, ultimately resulting in boosted photocatalytic activity and product selectivity as compared with those of pure TiO2. The CO, CH4 and O2 yields of the optimized Ni/I-TiO2 reached 3.49, 158.25 and 246.30 μmol/gcat after 15 h of light illumination, which decreased slightly after 9 cycles, and the product selectivity was above 98 % for photocatalytic reduction of CO2 to CH4 with Ni and I co-doping. The in-situ FTIR results with the observation of CH3O and CH3 intermediates confirmed CH4 formation, and the possible mechanism of photocatalytic CO2 reduction over Ni/I-TiO2 was elucidated. This work provides new insights to pursue efficient catalysts for the selective photocatalytic CO2 reduction to CH4.