Chen Hao, Lin Wenwen, Zhang Zihao, Yang Zhenzhen, Jie Kecheng, Fu Jie, Yang Shi-Ze, Dai Sheng
Key Laboratory of Biomass Chemical Engineering of Ministry of Education , College of Chemical and Biological Engineering , Zhejiang University , Hangzhou 310027 , China . Email:
Department of Chemistry , University of Tennessee , Knoxville , TN 37996 , USA.
Chem Sci. 2020 May 22;11(22):5766-5771. doi: 10.1039/d0sc02238a. eCollection 2020 Jun 14.
Hydrogenation of aromatic rings promoted by earth-abundant metal composites under mild conditions is an attractive and challenging subject in the long term. In this work, a simple active site creation and stabilization strategy was employed to obtain a Cu-containing ternary mixed oxide catalyst. Simply by pre-treatment of the ternary metal oxide precursor under a H atmosphere, a Cu-derived heterogeneous catalyst was obtained and denoted as CuCoCeO . The catalyst showed (1) high Cu species content, (2) a uniform distribution of Cu doped into the lattices of CoO and CeO, (3) formation of CoO /CuO and CeO/CuO interfaces, and (4) a mesoporous structure. These unique properties of CuCoCeO endow it with pretty high hydrogenation activity for aromatic rings under mild conditions (100 °C with 5 bar H), which is much higher than that of the corresponding binary counterparts and even exceeds the performance of commercial noble metal catalysts ( Pd/C). The synergetic effect plays a crucial role in the catalytic procedure with CeO functioning as a hydrogen dissociation and transfer medium, Cu hydrogenating the benzene ring and CoO stabilizing the unstable Cu species. This will unlock a new opportunity to design highly efficient earth-abundant metal-derived heterogeneous catalysts interface interactions.
在地壳丰富的金属复合材料促进下，芳香环在温和条件下的氢化反应长期以来一直是一个引人关注且具有挑战性的课题。在这项工作中，采用了一种简单的活性位点创建和稳定化策略来获得含铜的三元混合氧化物催化剂。仅通过在氢气气氛下对三元金属氧化物前驱体进行预处理，就得到了一种源自铜的多相催化剂，并将其命名为CuCoCeO 。该催化剂表现出：（1）高铜物种含量；（2）铜均匀分布在CoO 和CeO晶格中；（3）形成CoO /CuO 和CeO/CuO 界面；（4）具有介孔结构。CuCoCeO 的这些独特性质使其在温和条件（100°C，5 bar氢气）下对芳香环具有相当高的氢化活性，这远高于相应的二元催化剂，甚至超过了商业贵金属催化剂（Pd/C）的性能。协同效应在催化过程中起着关键作用，其中CeO作为氢解离和转移介质，Cu使苯环氢化，CoO 稳定不稳定的铜物种。这将为设计高效的地壳丰富金属衍生的多相催化剂界面相互作用带来新的机遇。
