Eco-Friendly Photochemical Production of H2O2 through O2 Reduction over Carbon Nitride Frameworks Incorporated with Multiple Heteroelements

Abstract

We report that in situ incorporation of both potassium and phosphate species into a polymeric carbon nitride (CN) framework highly enhanced the photoproduction of hydrogen peroxide (H 2 O 2 ) without the use of any noble-metal cocatalysts. The incorporation of earth-abundant heteroelements (K, P, and O) (i) introduced the negative surface charge over the entire pH range through surface functionalization by phosphate species, (ii) increased the lifetime of the transient species to a picosecond time scale via the formation of charge separation states, (iii) facilitated the interfacial electron transfer to dioxygen, and (iv) inhibited the decomposition of in situ generated H 2 O 2 . As a result, the modified CN showed apparent quantum yields (Φ, for H 2 O 2 production) that are enhanced by about 25 and 17 times (Φ 420 = 8.0%; Φ 320 = 26.2%) from those of bare CN (Φ 420 = 0.32%; Φ 320 = 1.55%) under monochromatic irradiation of 420 and 320 nm, respectively. This study clearly demonstrated a simple way to design multiple heteroelement-incorporated CN compounds that consist of earth-abundant elements only (C, N, K, P, O) for the development of practical and economical solar conversion photocatalytic materials.