Site-Sensitive Selective CO₂ Photoreduction to CO over Gold Nanoparticles

We demonstrate a new case of materials-gene engineering to precisely design photocatalysts with the prescribed properties. Based on theoretical calculations, a phase-doping strategy was proposed to regulate the pathways of CO₂ conversion over Au nanoparticles (NPs) loaded TiO₂ photocatalysts. As a result, the thermodynamic bottleneck of CO₂ -to-CO conversion is successfully unlocked by the incorporation of stable twinning crystal planes into face-centered cubic (fcc) phase Au NPs. Compared to bare pristine TiO₂ , the activity results showed that the loading of regular fcc-Au NPs raised the CO production by 18-fold but suppressed the selectivity from 84 % to 75 %, whereas Au NPs with twinning (110) and (100) facets boosted the activity by nearly 40-fold and established near unity CO selectivity. This enhancement is shown to originate from a beneficial shift in the surface reactive site energetics arising at the twinned stacking fault, whereby both the CO reaction energy and desorption energy were significantly reduced.