Marley Peter M, Abtew Tesfaye A, Farley Katie E, Horrocks Gregory A, Dennis Robert V, Zhang Peihong, Banerjee Sarbajit
Department of Chemistry , Texas A&M University , College Station , TX 77842-3012 , USA . Email:
Department of Physics , University at Buffalo , The State University of New York , Buffalo , New York 14260 , USA.
Chem Sci. 2015 Mar 1;6(3):1712-1718. doi: 10.1039/c4sc03748k. Epub 2015 Jan 13.
The classical orthorhombic layered phase of VO has long been regarded as the thermodynamic sink for binary vanadium oxides and has found great practical utility as a result of its open framework and easily accessible redox states. Herein, we exploit a cation-exchange mechanism to synthesize a new stable tunnel-structured polymorph of VO (ζ-VO) and demonstrate the subsequent ability of this framework to accommodate Li and Mg ions. The facile extraction and insertion of cations and stabilization of the novel tunnel framework is facilitated by the nanometer-sized dimensions of the materials, which leads to accommodation of strain without amorphization. The topotactic approach demonstrated here indicates not just novel intercalation chemistry accessible at nanoscale dimensions but also suggests a facile synthetic route to ternary vanadium oxide bronzes (M VO) exhibiting intriguing physical properties that range from electronic phase transitions to charge ordering and superconductivity.
VO的经典正交层状相长期以来一直被视为二元钒氧化物的热力学阱，由于其开放框架和易于获得的氧化还原态，已发现其具有很大的实际用途。在此，我们利用阳离子交换机制合成了一种新的稳定的VO隧道结构多晶型物（ζ-VO），并证明了该框架随后容纳Li和Mg离子的能力。材料的纳米尺寸促进了阳离子的轻松提取和插入以及新型隧道框架的稳定，这导致在不发生非晶化的情况下容纳应变。这里展示的拓扑方法不仅表明了在纳米尺度上可实现的新型插层化学，还暗示了一种简便的合成路线，可用于制备具有从电子相变到电荷有序和超导等有趣物理性质的三元钒氧化物青铜（M VO）。
