State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
The School of Materials Science and Engineering, Harbin Institute of Technology, Shenzhen, 518055, China.
Nat Commun. 2022 May 11;13(1):2591. doi: 10.1038/s41467-022-30345-0.
Single cluster catalysts (SCCs) are considered as versatile boosters in heterogeneous catalysis due to their modifiable single cluster sites and supports. In this work, we report subnanometric Cu clusters dispersed on Fe-doped MoO support for biomass-derived furfural upgrading. Systematical characterizations suggest uniform Cu clusters (composing four Cu atoms in average) are homogeneously immobilized on the atomically Fe-doped ultrafine MoO nanocrystals (Cu/FeMoO@C). The atomic doping of Fe into MoO leads to significantly modified electronic structure and consequently charge redistribution inside the supported Cu clusters. The as-prepared Cu/FeMoO@C shows superior catalytic performance in the oxidative coupling of furfural with CC primary/secondary alcohols to produce CC aldehydes/ketones (aviation biofuel intermediates), outperforming the conventionally prepared counterparts. DFT calculations and control experiments are further carried out to interpret the structural and compositional merits of Cu/FeMoO@C in the oxidative coupling reaction, and elucidate the reaction pathway and related intermediates.
单原子簇催化剂（SCCs）因其可修饰的单原子簇位和载体而被认为是多用途的异相催化剂。在这项工作中，我们报道了分散在 Fe 掺杂 MoO 载体上的亚纳米 Cu 簇，用于生物质衍生糠醛的升级。系统的表征表明，均匀的 Cu 簇（平均由四个 Cu 原子组成）均匀地固定在原子级 Fe 掺杂的超细 MoO 纳米晶上（Cu/FeMoO@C）。Fe 原子掺杂到 MoO 中会导致其电子结构发生显著变化，从而导致负载的 Cu 簇内部的电荷重新分布。所制备的 Cu/FeMoO@C 在糠醛与 CC 伯/仲醇的氧化偶联反应中表现出优异的催化性能，可生成 CC 醛/酮（航空生物燃料中间体），优于传统制备的催化剂。进一步进行了 DFT 计算和控制实验，以解释 Cu/FeMoO@C 在氧化偶联反应中的结构和组成优点，并阐明了反应途径和相关中间体。
