Out-of-Plane Single-Copper-Site Catalysts for Room-Temperature Benzene Oxidation.
Angew Chem Int Ed Engl
; 63(20): e202403017, 2024 May 13.
Article
em En
| MEDLINE
| ID: mdl-38429994
ABSTRACT
Crafting single-atom catalysts (SACs) that possess "just right" modulated electronic and geometric structures, granting accessible active sites for direct room-temperature benzene oxidation is a coveted objective. However, achieving this goal remains a formidable challenge. Here, we introduce an innovative in situ phosphorus-immitting strategy using a new phosphorus source (phosphorus nitride, P3N5) to construct the phosphorus-rich copper (Cu) SACs, designated as Cu/NPC. These catalysts feature locally protruding metal sites on a nitrogen (N)-phosphorus (P)-carbon (C) support (NPC). Rigorous analyses, including X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS), validate the coordinated bonding of nitrogen and phosphorus with atomically dispersed Cu sites on NPC. Crucially, systematic first-principles calculations, coupled with the climbing image nudged-elastic-band (CI-NEB) method, provide a comprehensive understanding of the structure-property-activity relationship of the distorted Cu-N2P2 centers in Cu/NPC for selective oxidation of benzene to phenol production. Interestingly, Cu/NPC has shown more energetically favorable C-H bond activation compared to the benchmark Cu/NC SACs in the direct oxidation of benzene, resulting in outstanding benzene conversion (50.3 %) and phenol selectivity (99.3 %) at room temperature. Furthermore, Cu/NPC achieves a remarkable turnover frequency of 263â
h-1 and mass-specific activity of 35.2â
mmol g-1 h-1, surpassing the state-of-the-art benzene-to-phenol conversion catalysts to date.
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01-internacional
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MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2024
Tipo de documento:
Article