A Supported Bismuth Halide Perovskite Photocatalyst for Selective Aliphatic and Aromatic C–H Bond Activation. (23rd January 2020)

• Record Type: Journal Article
• Authors: Dai, Yitao; Poidevin, Corentin; Ochoa‐Hernández, Cristina; Auer, Alexander A.; Tüysüz, Harun
• Is Part Of: Angewandte Chemie. Volume 132:Number 14(2020)
• Page Start: 5837
• Page End: 5845
• Publication Date: 2020-01-23
• Subjects: Bismut -- Nanopartikel -- Perowskite -- Photokatalyse -- SBA-15-Siliciumdioxid; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201915034
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Direct selective oxidation of hydrocarbons to oxygenates by O2 is challenging. Catalysts are limited by the low activity and narrow application scope, and the main focus is on active C−H bonds at benzylic positions. In this work, stable, lead‐free, Cs3 Bi2 Br9 halide perovskites are integrated within the pore channels of mesoporous SBA‐15 silica and demonstrate their photocatalytic potentials for C−H bond activation. The composite photocatalysts can effectively oxidize hydrocarbons (C5 to C16 including aromatic and aliphatic alkanes) with a conversion rate up to 32900 μmol gcat −1 h −1 and excellent selectivity (>99 %) towards aldehydes and ketones under visible‐light irradiation. Isotopic labeling, in situ spectroscopic studies, and DFT calculations reveal that well‐dispersed small perovskite nanoparticles (2–5 nm) possess enhanced electron–hole separation and a close contact with hydrocarbons that facilitates C(sp 3 )−H bond activation by photoinduced charges. Abstract : Besser mit Bismut : Eine Reihe von kleinen Bismuthalogenid‐Perowskit‐Nanopartikeln auf einem Träger aus mesoporösem Siliciumdioxid wurde hergestellt. Sie stellen vielversprechende Photokatalysatoren für selektive aromatische und aliphatische C‐H‐Bindungsaktivierung unter Bestrahlung mit sichtbarem Licht dar.