Bera Suman, Shyamal Sanjib, Pradhan Narayan
School of Materials Sciences, Indian Association for the Cultivation of Science, Kolkata 700032, India.
J Am Chem Soc. 2021 Sep 15;143(36):14895-14906. doi: 10.1021/jacs.1c07231. Epub 2021 Sep 1.
Light emitting lead halide perovskite nanocrystals are currently emerging as the workhorse in quantum dot research. Most of these reported nanocrystals are isotropic cubes or polyhedral; but anisotropic nanostructures with controlled anisotropic directions still remain a major challenge. For orthorhombic CsPbBr, the 1D shaped nanostructures reported are linear and along either of the axial directions ⟨100⟩. In contrast, herein, spiral CsPbBr perovskite nanorods in the orthorhombic phase are reported with unusual anisotropy having (101) planes remaining perpendicular to the major axis [201]. While these nanorods are synthesized using the prelattice of orthorhombic CsCdBr with Pb(II) diffusion, the spirality is controlled by manipulation of the compositions of alkylammonium ions in the reaction system which selectively dissolve some spiral facets of the nanorods. Further, as spirality varied with facet creation and elimination, these nanorods were explored as photocatalysts for CO reduction, and the evolution of methane was also found to be dependent on the depth of the spiral nanorods. The entire study demonstrates facet manipulation of complex nanorods, and these results suggest that even if perovskites are ionic in nature, their shape could be constructed by design with proper reaction manipulation.
发光卤化铅钙钛矿纳米晶体目前正成为量子点研究中的主力军。这些已报道的纳米晶体大多是各向同性的立方体或多面体;但具有可控各向异性方向的各向异性纳米结构仍然是一个重大挑战。对于正交相的CsPbBr₃,已报道的一维形状纳米结构是线性的,且沿着任一轴向〈100〉方向。相比之下,本文报道了正交相的螺旋状CsPbBr₃钙钛矿纳米棒,其具有不寻常的各向异性,(101)面保持垂直于主轴[201]。虽然这些纳米棒是利用正交相CsCdBr₃的前晶格通过Pb(II)扩散合成的,但螺旋度是通过控制反应体系中烷基铵离子的组成来控制的,该组成选择性地溶解了纳米棒的一些螺旋面。此外,由于螺旋度随晶面的产生和消除而变化,这些纳米棒被用作光催化还原CO₂的催化剂,并且还发现甲烷的生成取决于螺旋纳米棒的深度。整个研究展示了对复杂纳米棒的晶面操控,这些结果表明,即使钙钛矿本质上是离子性的,其形状也可以通过适当的反应操控进行设计构建。