Titanate perovskite (ATiO3) semiconductors show prospects of being active photocatalysts in the conversion of CO2 to chemical fuels such as methanol (CH3OH) in the aqueous phase. Some of the challenges in using ATiO3 are limited light-harvesting capability, rapid bulk charge recombination, and the low density of catalytic sites participating in CO2 reduction. To address these challenges, Ga-doped NiTiO3 (GNTO) photocatalysts in which Ga ions substitute for Ti ions in the crystal lattice to form electron trap states and oxygen vacancies have been synthesized in this work. The synthesized GNTO was then loaded with Ru nanoparticles to accelerate charge separation and enable excellent CO2 photoreduction activity under visible light. CO2 photoreduction was conducted in a batch photoreactor charged with a 0.1 M NaHCO3 aqueous solution at room temperature and a 3.5 bar pressure using a 1.0 wt % Ru-GNTO photocatalyst to yield methanol at a rate of 84.45 μmol g-1 h-1. A small amount of methane was produced as a side product at 21.35 μmol g-1 h-1, which is also a fuel molecule. We attribute this high catalytic activity toward CO2 photoreduction to a synergistic combination of our novel heterostructured 1.0 wt % Ru-GNTO photocatalyst and the implementation of a pressurized photoreactor. This work demonstrates an effective strategy for metal doping with active nanospecies functionality to improve the performance of ATiO3 photocatalysts in valorizing CO2 to solar fuels.
Keywords: Ga doping; Ru cocatalysts; carbon dioxide reduction; photocatalysis; titanate perovskites.