Champsaur Anouck M, Yu Jaeeun, Roy Xavier, Paley Daniel W, Steigerwald Michael L, Nuckolls Colin, Bejger Christopher M
Department of Chemistry, and Columbia Nano Initiative, Columbia University, New York, New York 10027, United States.
Department of Chemistry, The University of North Carolina at Charlotte, Charlotte, North Carolina 28223, United States.
ACS Cent Sci. 2017 Sep 27;3(9):1050-1055. doi: 10.1021/acscentsci.7b00328. Epub 2017 Aug 30.
We describe a new approach to synthesize two-dimensional (2D) nanosheets from the bottom-up. We functionalize redox-active superatoms with groups that can direct their assembly into multidimensional solids. We synthesized CoSe[PEt(4-CHCOOH)] and found that it forms a crystalline assembly. The solid-state structure is a three-dimensional (3D) network in which the carboxylic acids form intercluster hydrogen bonds. We modify the self-assembly by replacing the reversible hydrogen bonds that hold the superatoms together with zinc carboxylate bonds via the solvothermal reaction of CoSe[PEt(4-CHCOOH)] with Zn(NO). We obtain two types of crystalline materials using this approach: one is a 3D solid and the other consists of stacked layers of 2D sheets. The dimensionality is controlled by subtle changes in reaction conditions. These 2D sheets can be chemically exfoliated, and the exfoliated, ultrathin 2D layers are soluble. After they are deposited on a substrate, they can be imaged. We cast them onto an electrode surface and show that they retain the redox activity of the superatom building blocks due to the porosity in the sheets.
我们描述了一种自下而上合成二维（2D）纳米片的新方法。我们用能够引导其组装成多维固体的基团对氧化还原活性超原子进行功能化。我们合成了CoSe[PEt(4-CHCOOH)]，发现它形成了一种晶体组装体。固态结构是一种三维（3D）网络，其中羧酸形成簇间氢键。我们通过CoSe[PEt(4-CHCOOH)]与Zn(NO)的溶剂热反应，用羧酸锌键取代将超原子结合在一起的可逆氢键，从而对自组装进行了改性。我们用这种方法获得了两种类型的晶体材料：一种是3D固体，另一种由2D片层的堆叠层组成。维度由反应条件的细微变化控制。这些2D片层可以进行化学剥离，剥离后的超薄2D层是可溶的。将它们沉积在基板上后，可以对其进行成像。我们将它们浇铸在电极表面，并表明由于片层中的孔隙率，它们保留了超原子构建块的氧化还原活性。
