Enhanced Photocatalytic CO₂ Reduction over TiO₂ Using Metalloporphyrin as the Cocatalyst

Abstract

The photocatalytic reduction of carbon dioxide (CO2) into CO and hydrocarbon fuels has been considered as an ideal green technology for solar-to-chemical energy conversion. The separation/transport of photoinduced charge carriers and adsorption/activation of CO2 molecules play crucial roles in photocatalytic activity. Herein, tetrakis (4-carboxyphenyl) porphyrin (H2TCPP) was incorporated with different metal atoms in the center of a conjugate macrocycle, forming the metalloporphyrins TCPP-M (M = Co, Ni, Cu). The as-obtained metalloporphyrin was loaded as a cocatalyst on commercial titania (P25) to form TCPP-M@P25 (M = Co, Ni, Cu) for enhanced CO2 photoreduction. Among all of the TCPP-M@P25 (M = Co, Ni, Cu), TCPP-Cu@P25 exhibited the highest evolution rates of CO (13.6 μmol⋅g−1⋅h−1) and CH4 (1.0 μmol⋅g−1⋅h−1), which were 35.8 times and 97.0 times those of bare P25, respectively. The enhanced photocatalytic activity could be attributed to the improved photogenerated electron-hole separation efficiency, as well as the increased adsorption/activation sites provided by the metal centers in TCPP-M (M = Co, Ni, Cu). Our study indicates that metalloporphyrin could be used as a high-efficiency cocatalyst to enhance CO2 photoreduction activity.

Keywords

• photocatalysis
• metalloporphyrin
• cocatalyst
• TiO₂
• CO₂ reduction