Division of Nanomaterials & Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Suzhou Nano Science and Technology, CAS Centre for Excellence in Nanoscience, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
Division of Theoretical and Computational Sciences, Hefei National Laboratory for Physical Sciences at the Microscale, CAS Centre for Excellence and Synergetic Innovation Centre in Quantum Information and Quantum Physics, University of Science and Technology of China , Hefei, Anhui 230026, China.
J Am Chem Soc. 2016 Oct 5;138(39):12913-12919. doi: 10.1021/jacs.6b06609. Epub 2016 Aug 12.
Heteronanostructures have attracted intensive attention due to their electronic coupling effects between distinct components. Despite tremendous advances of nanostructure fabrication, combining independent polymorphs by forming heterojunction is still challenging but fascinating, such as copper sulfides (CuS), exhibiting varying band gaps and crystal structures with various stoichiometries. Herein, self-coupled CuS polymorphs (CuS-CuS) by a facile one-pot chemical transformation route have been reported for the first time. Unprecedentedly, a manganous precursor plays a crucial role in inducing and directing the formation of such a dumbbell-like architecture, which combines 1D CuS with 2D CuS. During the transformation, Mn ions mediate the Cu ions diffusion and phase conversion process particularly. Furthermore, this self-coupled polymorphic structure exhibits significantly enhanced photoelectrochemical properties compared with the individual CuS nanocrystals and CuS nanoplates, originating from the unique heterointerfaces constructed by intrinsic band alignment and the enhanced contact between high conductivity hexagonal planes and the working electrode revealed by density functional theory (DFT) calculations. So we anticipate this emerging interfacial charge separation could provide useful hints for applications in optoelectronic devices or photocatalysis.
由于不同组件之间的电子耦合效应，异质纳米结构引起了人们的广泛关注。尽管纳米结构的制造取得了巨大的进步，但通过形成异质结将独立的多晶型体结合仍然具有挑战性，但也很吸引人，例如铜硫化物 (CuS)，它具有不同的能带隙和晶体结构，具有不同的化学计量比。本文首次报道了通过简便的一锅化学转化方法自耦合的 CuS 多晶型体 (CuS-CuS)。史无前例的是，锰前体在诱导和指导这种哑铃状结构的形成中起着至关重要的作用，该结构将 1D 的 CuS 与 2D 的 CuS 结合在一起。在转化过程中，Mn 离子特别介导 Cu 离子的扩散和相转换过程。此外，与单独的 CuS 纳米晶和 CuS 纳米板相比，这种自耦合多晶型结构表现出显著增强的光电化学性能，这源于由固有能带排列和通过密度泛函理论 (DFT) 计算揭示的高导电性六方平面与工作电极之间增强的接触构建的独特异质界面。因此，我们预计这种新兴的界面电荷分离可能为在光电设备或光催化中的应用提供有用的启示。
