Atomically Defined Undercoordinated Copper Active Sites over Nitrogen‐Doped Carbon for Aerobic Oxidation of Alcohols. Issue 11 (20th January 2022)

• Record Type: Journal Article
• Authors: Li, Zhijun; Fan, Tingting; Li, Honghong; Lu, Xiaowen; Ji, Siqi; Zhang, Jiangwei; Horton, J. Hugh; Xu, Qian; Zhu, Junfa
• Is Part Of: Small. Volume 18:Issue 11(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-20
• Subjects: aerobic oxidation of alcohols -- catalytic activity -- coordination environment -- copper single atom catalysts -- heterogeneous catalysis; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.202106614
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract: Selective aerobic oxidation of alcohols offers an attractive means to address challenges in the modern chemical industry, but the development of non‐noble metal catalysts with superior efficacy for this reaction remains a grand challenge. Here, this study reports on such a catalyst based on atomically defined undercoordinated copper atoms over nitrogen‐doped carbon support as an efficient, durable, and scalable heterogeneous catalyst for selective aerobic oxidation of alcohols. This catalyst exhibits extremely high intrinsic catalytic activity (TOF of 7692 h −1 ) in the oxidation of cinnamyl alcohol to afford cinnamaldehyde, along with exceptional recyclability (at least eight cycles), scalability, and broad substrate scope. DFT calculations suggest that the high activity derives from the low oxidation state and the unique coordination environment of the copper sites in the catalyst. These findings pave the way for the design of highly active and stable single atom catalysts to potentially address challenges in synthetic chemistry. Abstract : Here, a combined in situ assembly and pyrolysis approach, to construct singly dispersed Cu atoms supported over nitrogen‐doped carbon, is reported. The catalyst manifests exceptional catalytic performance in the oxidation of alcohols, and the DFT calculations reveal that the high activity originates from the unique coordination structure of isolated copper atoms confined in the NC support.