Binary-Ternary Bi2S3-AgBiS2 Rod-to-Rod Transformation via Anisotropic Partial Cation Exchange Reaction
Binary-Ternary Bi2S3-AgBiS2 Rod-to-Rod Transformation via Anisotropic Partial Cation Exchange Reaction
复制标题
通过各向异性部分阳离子交换反应进行二元-三元 Bi2S3-AgBiS2 棒对棒转化
DOI：
10.1021/acs.inorgchem.9b01917
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发表时间：
2019-10-07
影响因子：
4.6
通讯作者：
Wang, Dan
中科院分区：
文献类型：
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作者：
Wang, Junli;Li, Linjie;Wang, Dan
基于部分阳离子交换反应的纳米级化学转化被认为是设计和可调制备三元或多元金属硫化物化合物的一种成分增加、形状保持的手段。在这里，我们提出了一种新的材料对，Bi2S3-AgBiS2，详细描述了通过部分阳离子交换实现的二元-三元化学转化及其反应热力学和动力学。预制的Bi2S3纳米棒既是反应物又是母体模板，其中Bi3+与Ag+阳离子的部分交换是在富银的扩散控制下进行的，导致了能量有利的AgBiS2的形成。与硫亚晶格重排有关的NR形状保持是由于母体Bi2S3 NRS具有合适的直径厚度(约12 nm)和迅速建立了平衡相AgBiS2，这一点得到了X射线衍射和伪二元Ag2S-Bi2S3相图的支持。有趣的是，具有轴向分段异质结构的AgBiS2-Bi2S3-AgBiS2中间体的发现揭示了真实的NR到NR的转化轨迹以及Bi2S3 NRS末端和中间的形状诱导交换反应各向异性。此外，合成的AgBiS2纳米材料具有接近0.86 eV的测量带隙，由于其令人印象深刻的可见光-近红外吸收和光电导，显示出潜在的光电子应用。
Nanoscale chemical transformations based on partial cation exchange reactions are known as a component-increased, shape-maintaining means for the design and tunable preparation of ternary or multinary metal chalcogenide compounds. Herein, we present a new material couple, Bi2S3-AgBiS2, to detail the binary-ternary chemical transformation via partial cation exchange and its reaction thermodynamics and kinetics. The preformed Bi2S3 nanorods (NRs) act as both the reactant and the parent template, within which the partial exchange of Bi3+ with Ag+ cations proceeds under a silver-rich, diffusion-controlled regime, leading to formation of energetically favorable AgBiS2. The NR shape preservation involving sulfur sublattice rearrangement is due to the proper diameter thickness (similar to 12 nm) of parent Bi2S3 NRs and the rapid establishment of equilibrium-phase AgBiS2, as supported by X-ray diffraction measurements and the pseudobinary Ag2S-Bi2S3 phase diagram. Interestingly, the finding of a AgBiS2-Bi2S3-AgBiS2 intermediate with axially segmented heterostructures reveals the real NR-to-NR conversion trajectory and the shape-induced exchange reaction anisotropy at the ends and middle of Bi2S3 NRs. Additionally, the resultant AgBiS2 NRs with a measured band gap of similar to 0.86 eV exhibit potential for photoelectronic applications because of their impressive visible-near-infrared absorption and photoconductivity.