Tunable green syngas generation from CO₂ and H₂O with sunlight as the only energy input

The carbon-neutral synthesis of syngas from CO₂ and H₂O powered by solar energy holds grand promise for solving critical issues such as global warming and the energy crisis. Here we report photochemical reduction of CO₂ with H₂O into syngas using core/shell Au@Cr₂O₃ dual cocatalyst-decorated multistacked InGaN/GaN nanowires (NWs) with sunlight as the only energy input. First-principle density functional theory calculations revealed that Au and Cr₂O₃ are synergetic in deforming the linear CO₂ molecule to a bent state with an O-C-O angle of 116.5°, thus significantly reducing the energy barrier of CO₂RR compared with that over a single component of Au or Cr₂O₃. Hydrogen evolution reaction was promoted by the same cocatalyst simultaneously. By combining the cooperative catalytic properties of Au@Cr₂O₃ with the distinguished optoelectronic virtues of the multistacked InGaN NW semiconductor, the developed photocatalyst demonstrated high syngas activity of 1.08 mol/g_cat/h with widely tunable H₂/CO ratios between 1.6 and 9.2 under concentrated solar light illumination. Nearly stoichiometric oxygen was evolved from water splitting at a rate of 0.57 mol/g_cat/h, and isotopic testing confirmed that syngas originated from CO₂RR. The solar-to-syngas energy efficiency approached 0.89% during overall CO₂ reduction coupled with water splitting. The work paves a way for carbon-neutral synthesis of syngas with the sole inputs of CO₂, H₂O, and solar light.