Boosted Inner Surface Charge Transfer in Perovskite Nanodots@Mesoporous Titania Frameworks for Efficient and Selective Photocatalytic CO₂ Reduction to Methane

Abstract

Exploring high-efficiency and stable halide perovskite-based photocatalysts for the selective reduction of CO₂ to methane is a challenge because of the intrinsic photo- and chemical instability of halide perovskites. In this study, halide perovskites (Cs₃ Bi₂ Br₉ and Cs₂ AgBiBr₆ ) were grown in situ in mesoporous TiO₂ frameworks for an efficient CO₂ reduction. Benchmarked CH₄ production rates of 32.9 and 24.2 μmol g^-1 h^-1 with selectivities of 88.7 % and 84.2 %, were achieved, respectively, which are better than most reported halide perovskite photocatalysts. Focused ion-beam sliced-imaging techniques were used to directly image the hyperdispersed perovskite nanodots confined in mesopores with tunable sizes ranging from 3.8 to 9.9 nm. In situ X-ray photoelectronic spectroscopy and Kelvin probe force microscopy showed that the built-in electric field between the perovskite nanodots and mesoporous titania channels efficiently promoted photo-induced charge transfer. Density functional theory calculations indicate that the high methane selectivity was attributed to the Bi-adsorption-mediated hydrogenation of *CO to *HCO that dominates CO desorption.