Department of Chemistry, Oregon State University, Corvallis, Oregon 97331-4003, United States.
Inorg Chem. 2013 Jun 17;52(12):7139-44. doi: 10.1021/ic400733k. Epub 2013 May 31.
Graphite intercalation compounds (GICs) of a series of symmetric or asymmetric tetraalkylammonium (TAA) intercalates are obtained from stage-1 [Na(en)1.0]C15 via cation exchange. The prepared dull-black TAA-GICs contain either flattened monolayer or bilayer galleries, with significant cointercalation of the dimethylsulfoxide (DMSO) solvent in the bilayer galleries. The TAA-GIC products obtained are characterized by X-ray diffraction and related structural modeling, compositional analyses, and Raman spectroscopy. [(C4H9)4N]C43 is obtained as a pure stage-1 GIC with the flattened monolayer structure. The larger symmetric TAA cations, (C6H13)4N, (C7H15)4N, (C8H17)4N, and the asymmetric TAA cations, (C12H25)(CH3)3N, (C18H37)(CH3)3N, (C18H37)2(CH3)2N, all form pure stage-1 GICs with flattened bilayer conformations. Thermogravimetric analyses combined with mass spectrometry and elemental analyses indicate the presence of ∼1-2 DMSO cointercalates per bilayer cation. The intercalate layers in these TAA-GICs have expansions along the stacking direction of ∼0.40 nm. Raman data confirm the low graphene sheet charge densities in the obtained TAA-GICs.
通过阳离子交换，从阶段-1 [Na(en)1.0]C15 获得了一系列对称或不对称四烷基铵（TAA）插层的石墨插层化合物（GIC）。所制备的暗黑色 TAA-GIC 含有扁平的单层或双层孔道，在双层孔道中有二甲亚砜（DMSO）溶剂的显著共插层。通过 X 射线衍射和相关结构建模、成分分析和拉曼光谱对 TAA-GIC 产物进行了表征。[(C4H9)4N]C43 作为具有扁平单层结构的纯阶段-1 GIC 获得。较大的对称 TAA 阳离子（C6H13）4N、（C7H15）4N、（C8H17）4N 和不对称 TAA 阳离子（C12H25）（CH3）3N、（C18H37）（CH3）3N、（C18H37）2（CH3）2N 都形成了具有扁平双层构象的纯阶段-1 GIC。热重分析结合质谱和元素分析表明，每个双层阳离子存在约 1-2 个 DMSO 共插层。这些 TAA-GIC 中的插层层沿堆积方向扩展约 0.40nm。拉曼数据证实了在获得的 TAA-GIC 中石墨烯片电荷密度较低。
