Author:

Keywords:

Science & Technology, Physical Sciences, Chemistry, Multidisciplinary, Chemistry, CO2 Reduction, Gold Photocatalysis, Materials Gene Engineering, Phase Doping, Twinning Defects, ELECTROCHEMICAL REDUCTION, METHANE, TIO2, PHOTOCATALYSIS, G098319N#54967826, 12Y7221N#55744511, 1242922N#56309783, 1280021N#55741780, G0B3915N#53229076, G0B4915N#53227843, C14/19/079#55221587, IBOF/21/085#56129725, C3/19/046#55510265, 03 Chemical Sciences, Organic Chemistry, 34 Chemical sciences

Abstract:

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.