Cooperation of cerium oxide nanoparticles and soluble molecular catalysts for alcohol oxidation
Cooperation of cerium oxide nanoparticles and soluble molecular catalysts for alcohol oxidation
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DOI：
10.1039/c9qi01640f
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发表时间：
2020-03-21
影响因子：
7
通讯作者：
Mayer, James M.
中科院分区：
文献类型：
--
作者：
Laga, Stephanie M.;Townsend, Tanya M.;Mayer, James M.
氧化铈（二氧化铈，CeO 2-x）传统上用作用金属纳米颗粒官能化或用金属掺杂剂合成的催化剂载体，用于从催化转化器到固体氧化物燃料电池的各种应用。在离开这些典型的异质图案，我们探讨了纳米CeO 2-x系统与有机金属氧化催化剂在有机溶剂中的相互作用。二氧化铈在此既用作有机封端的胶体又用作未封端的不溶性纳米粉末。胶体和纳米粉末都通过接受来自钌Noyori-Ikariya氢化物络合物的氢原子作为终端氧化剂。据我们所知，这是第一次证明CeO 2-x可以氧化有机金属氢化物。基于这一概念，我们表明未加盖的CeO 2-x粉末也作为终端受体在催化醇脱氢反应，利用铱吡啶磺酰胺催化剂在厌氧和有氧条件下。均相氧化催化剂与氧化铈的耦合展示了CeO 2-x的多功能性以及均相和多相催化概念的桥接。
Cerium oxide (ceria, CeO2-x) has been traditionally used as a catalyst support functionalized with metal nanoparticles or synthesized with metal dopants for a variety of applications ranging from catalytic converters to solid oxide fuel cells. In a departure from these typical heterogeneous motifs, we explore the interactions of nano-CeO2-x systems with organometallic oxidation catalysts in organic solvents. Ceria is used here both as an organically-capped colloid and as an uncapped insoluble nanopowder. Both the colloid and nanopowder act as terminal oxidants by accepting hydrogen atoms from a ruthenium Noyori-Ikariya hydride complex. To our knowledge, this is the first demonstration that CeO2-x can oxidize an organometallic hydride. Building on this concept, we show the uncapped CeO2-x powder also acts as the terminal acceptor in catalytic alcohol dehydrogenation reactions, utilizing iridium pyridine sulfonamide catalysts under anaerobic and aerobic conditions. The coupling of homogeneous oxidation catalysts with cerium oxide demonstrates the versatility of CeO2-x and a bridging of concepts in homogeneous and heterogeneous catalysis.