Ide Yusuke, Tominaka Satoshi, Yoneno Yumi, Komaguchi Kenji, Takei Toshiaki, Nishida Hidechika, Tsunoji Nao, Machida Akihiko, Sano Tsuneji
International Center for Materials Nanoarchitectonics (MANA) , National Institute for Materials Science , 1-1 Namiki , Tsukuba , Ibaraki 305-0044 , Japan . Email:
Department of Earth Sciences , Waseda University , 1-6-1 Nishiwaseda, Shinjuku-ku , Tokyo 165-8050 , Japan.
Chem Sci. 2019 Jun 12;10(27):6604-6611. doi: 10.1039/c9sc01253b. eCollection 2019 Jul 21.
Although iron oxides have been extensively studied as photocatalysts because of their abundance and environmental compatibility, their performance is notoriously low due to factors such as low photoinduced charge-separation efficiency. Iron oxides, thus, must be modified with expensive and/or toxic materials to attain higher performances, which devalues their appeal as sustainable materials. Here, we design an iron oxide exhibiting an unprecedentedly high photocatalytic performance unrealized by previous photocatalysts such as TiO for reactions including the selective oxidation of cyclohexane to industrial nylon precursors. The iron oxide photocatalyst consists of ferric dimers, otherwise extremely unstable, formed etching of Fe and O sites from ferric oxide nanoparticles immobilized within porous silica. We demonstrate a remarkably high photoinduced charge-separation efficiency (long lifetime of active species) of the ferric dimers due to their electronic structure and the potential of this supported photocatalyst for many more reactions.
尽管氧化铁因其储量丰富且与环境兼容而被广泛研究用作光催化剂，但其性能因光致电荷分离效率低等因素而极低。因此，必须用昂贵和/或有毒材料对氧化铁进行改性以获得更高性能，这降低了它们作为可持续材料的吸引力。在此，我们设计了一种氧化铁，其表现出前所未有的高光催化性能，这是以前的光催化剂（如TiO）在包括环己烷选择性氧化为工业尼龙前体的反应中所未实现的。该氧化铁光催化剂由铁二聚体组成，铁二聚体原本极不稳定，是通过对固定在多孔二氧化硅内的氧化铁纳米颗粒的Fe和O位点进行蚀刻而形成的。由于其电子结构，我们证明了铁二聚体具有极高的光致电荷分离效率（活性物种的长寿命），以及这种负载型光催化剂在更多反应中的潜力。
