C(sp³)–H Bond Activation by Perovskite Solar Photocatalyst Cell

Abstract

Inspired by efficient perovskite solar cells, we developed a threecomponent hybrid perovskite-based solar photocatalyst cell, NiO x /FAPbBr 3 /TiO 2 , for C(sp 3 )−H bond activation with high selectivity (∼90%) and high conversion rates (3800 μmol g −1 h −1 ) under ambient conditions. Time-resolved spectroscopy on our photocatalytic cell reveals efficient exciton dissociation and charge separation, where TiO 2 and NiO x serve as the electron-and hole-transporting layers, respectively. The photogenerated charge carriers injected into TiO 2 and NiO x drive the challenging C− H activation reaction via the synergetic effects of their band alignment relative to FAPbBr 3 . The reaction pathway is investigated by controlling the free-radical formation, and we find that C−H activation is mainly triggered by hole oxidation. Besides aromatic alkanes, also the C(sp 3 )−H bond in cycloalkanes can be oxidized selectively. This work demonstrates a generic strategy for engineering highperformance photocatalysts based on the perovskite solar cell concept.

Recent Progress in Engineering Metal Halide Perovskites for Efficient Visible‐Light‐Driven Photocatalysis

“…For instance, Roeffaers et al. developed a three‐component NiO x /FAPbBr 3 /TiO 2 hybrid for the activation of C(sp 3 )−H bonds in toluene or substituted toluenes with high conversion rates (5610 μmol g −1 h −1 ; Figure d) . The introduced TiO 2 and NiO x , acting as the electron‐ and hole‐transporting layers of FAPbBr 3 , respectively, dramatically enhanced the charge‐carrier transfer and photoactivity efficiency (Figure e).…”

Metal Halide Perovskites for Solar‐to‐Chemical Fuel Conversion

“…The shells could further facilitate charge carrier transfer via interfacial or band‐alignment engineering across the core–shell structures. Functionalization of the shells with nanoparticles or ligands will enhance the efficiency of solar‐to‐chemical fuel conversion and enable a wide scope of photocatalytic applications (for example organic reactions) beyond water splitting and CO 2 reduction. However, construction of perovskite@shell structures remains challenging, largely because halide perovskite materials are incompatible with the polar solvents that are typically used for shell formation reactions. 2)New protective layers or ligands should be developed for halide perovskites by exploring various coating and growth methodologies.…”

Photoredox Organic Synthesis Employing Heterogeneous Photocatalysts with Emphasis on Halide Perovskite

“…[102] Entry . [103] They demonstrated that combining the merits of photovoltaics in the photocatalyst architecture improvest he overall performance of such as ystem. At hree-component photocatalyst cell was created for the CÀHf unctionalization of tolueneand cycloalkanes by using FAPbBr 3 perovskite as the main light harvesting material, TiO 2 as the electron transporting layer,a nd NiO x as the hole transporting layer.T his hybrid 2D nanocomposite was first explored in the photo-oxidation of the methyl group in toluenei nw hich an optimal 5wt% NiO x loading onto FAPbBr 3 /TiO 2 was shown to oxidize toluene to benzaldehyde at ar ate of 3800 mmol g À1 h À1 with a selectivity of 86 %f avoring the formation of benzaldehyde over benzylalcohol.…”