School of Materials Science and Engineering, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Institutes of Physical Science and Information Technology, Department of Chemistry and Center for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of the Ministry of Education, Anhui University, Hefei 230601, China
College of Pharmaceutical and Chemical Enginnering, Huanghuai University, Zhumadian 463000, China
§ Yapei Yun and Lin Li contributed equally to this work.
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The coreless bimetallic nanoclusters (NCs) catalyst Au4Cu5/activated carbon (AC) and Au4Cu4/AC exhibit superior performance for Ullmann C–O coupling of phenol due to the exposure of all metal atoms and the synergism of adjacent atoms. Moreover, the coreless Au4Cu5/AC catalyst efficiently catalysed the Ullmann C–O coupling of benzyl alcohol for the first time. Our experiments and density functional theory (DFT) studies reveal that the catalytic performances of coreless bimetallic NCs are higher than those of coreless monometallic NCs and core–shell NCs.
Abstract
Bimetallic nanocluster with atomic precision has gained widespread attention due to its unique synergism. The coreless Au4Cu5 bimetallic nanoclusters were selected as models to explore the relationship between their microstructure and performance, and compare with the coreless monometallic nanoclusters, core–shell nanoclusters, and single atom catalyst (SAC). The experimental results show that the coreless bimetallic nanocluster catalyst Au4Cu5/activated carbon (AC) exhibits high activity and stability in the Ullmann C–O coupling reaction, much higher than coreless monometallic nanoclusters (Au11/AC and Cu11/AC), core–shell nanoclusters (Au25/AC, Cu25/AC, and Au1Cu24/AC), and single atom catalysts (Au SAC and Cu SAC). Moreover, the coreless Au4Cu5/AC catalyst efficiently catalyzed the Ullmann C–O coupling of benzyl alcohol for the first time. This structure–activity relationship was successfully extended to other coreless bimetallic systems, such as Au4Cu4/AC nanocluster, and it is expected to provide new insights for the design of bimetallic catalysts with well-defined performance.
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