Interface interaction mediated surface plasmon resonance enhancement promoted visible-light-driven CO2 reduction with water

Abstract

The conversion of carbon dioxide (CO2) into fuel using solar energy holds significant promise. However, the inefficient use of light and poor production activity have hindered its development. Here, we propose a simple in situ annealing oxidation method by coating a layer of TiO2 outside TiN, a material with a favorable price and localized surface plasmon resonance (LSPR) effect, to create an L-TiNO composite. The yield of CO over L-TiNO (50.8 μmol g−1 h−1) is 56.4 times that over TiO2 (0.9 μmol g−1 h−1) under visible light irradiation in pure aqueous environment, with a selectivity of 95.98%. In-situ Fourier transform infrared (FTIR) measurements reflect the CO2-COOH*-CO conversion route happening on L-TiNO. Characterizations like the Kelvin probe force microscopy (KPFM) technique confirm the generation of built-in electric field, which facilitates efficient carrier separation and migration. Density functional theory (DFT) calculations support that L-TiNO with LSPR effect alters the shape of absorbed CO2 to facilitate generation COOH* via forming hydroxyl end group (Ti-OH) and promotes CO* desorption to CO(g). This work provides valuable insights into the coupling of plasmonic materials with semiconductors to achieve efficient solar energy utilization.