Thiet Vu Thi, Daro Nathalie, Marchivie Mathieu, Mornet Stéphane, Freysz Eric, Chastanet Guillaume
University of Bordeaux, CNRS, Bordeaux-INP, ICMCB, UMR 5026, F-33600 Pessac, France.
University of Bordeaux, CNRS, UMR 5798, LOMA, F-33405 Talence Cedex, France.
Inorg Chem. 2022 Feb 14;61(6):2945-2953. doi: 10.1021/acs.inorgchem.1c03826. Epub 2022 Feb 4.
In this paper, we report the chemical strategy followed to obtain, in a direct way, nanoparticles of the RbMn[Fe(CN)]·HO (RbMnFe) Prussian blue analogue with the aim of keeping the switching ability of this compound at the nanoscale. The switching properties come from a reversible electron transfer between the iron and manganese ions and depends on the rubidium content in the structure that has to be higher than 0.6. Despite the multifunctionality of this family of compounds and its interest in various applications, no systematic studies were performed to obtain well-defined nanoparticles. This paper relates to such an investigation. To draw relationship between size reduction, composition, and switching properties, a special attention was brought to the determination of the composition through elemental analysis and structure refinement of powder X-ray diffraction patterns together with infrared spectroscopy and elemental analysis. Several chemical parameters were explored to control both the size reduction and the composition following a direct synthetic approach. The results show that the smaller the particles, the lower the rubidium content. This observation might prevent the observation of switching properties on very small particles. Despite this antagonist effect, we achieved switchable particles of around 200 nm without any use of surfactant. Moreover, the size reduction is associated with the observation of the electron transfer down to 52% of rubidium in the nanoparticles against 64% in microparticles. This work is of particular interest in processing such nanoparticles into devices.
在本文中，我们报告了为直接获得RbMn[Fe(CN)]·HO（RbMnFe）普鲁士蓝类似物的纳米颗粒所采用的化学策略，目的是在纳米尺度上保持该化合物的开关能力。开关特性源于铁离子和锰离子之间的可逆电子转移，并且取决于结构中铷的含量，该含量必须高于0.6。尽管这类化合物具有多功能性且在各种应用中备受关注，但尚未进行系统研究以获得明确的纳米颗粒。本文涉及这样一项研究。为了建立尺寸减小、组成和开关特性之间的关系，我们特别关注通过元素分析、粉末X射线衍射图谱的结构精修以及红外光谱和元素分析来确定组成。我们探索了几个化学参数，以遵循直接合成方法来控制尺寸减小和组成。结果表明，颗粒越小，铷含量越低。这一观察结果可能会妨碍在非常小的颗粒上观察到开关特性。尽管存在这种拮抗作用，但我们在未使用任何表面活性剂的情况下获得了约200 nm的可切换颗粒。此外，尺寸减小伴随着电子转移的观察，纳米颗粒中铷的电子转移降至52%，而微粒中为64%。这项工作对于将此类纳米颗粒加工成器件具有特别的意义。
