Institute for Composites Science Innovation, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
Department of Medical Oncology, The first affiliated Hospital, Zhejiang University School of Medicine, Hangzhou, 310003, China.
Small. 2022 Nov;18(44):e2203229. doi: 10.1002/smll.202203229. Epub 2022 Sep 1.
The assembly of biomolecules and ions (e.g., biomineralization process) generates many intricate structures in nature. However, human beings' control over the assembly processes of ions is in its infant stage compared with nature. Here, it is reported that the intermediate valence metal ions in the electrolyte can influence the growth speed of certain crystal facets and in turn adjust the shape of the electrodeposits created by anodic electrodeposition. This is because the intermediate valence metal ions (e.g., Pb , Mn , etc.) can be oxidized by the electrochemically oxidized high valence ions (e.g., Ag and Ag ). Therefore, the concentration of the electrochemically oxidized high valence ions can be controlled by the intermediate valence ions, affecting the growth kinetics of the electrodeposits. Taking the anodic electrodeposition of Ag O NO as an example, the role of intermediate valence ions in tailoring the shape of the Ag O NO electrodeposits is demonstrated. Moreover, the growth location of the second-order structure can be controlled by the intermediate valence metal ions. Additionally, the designed complex microarchitectures starting from certain crystal facets to form hollow nanoframes can be selectively etched. The control capability over the electrochemical assembly process of metal ions is significantly strengthened by introducing intermediate valence ions into the electrolyte.
生物分子和离子的组装（例如，生物矿化过程）在自然界中产生了许多复杂的结构。然而，与自然界相比，人类对离子组装过程的控制还处于起步阶段。在这里，据报道，电解液中的中间价态金属离子可以影响某些晶面的生长速度，从而调节阳极电沉积所生成的沉积物的形状。这是因为中间价态金属离子（例如 Pb、Mn 等）可以被电化学氧化的高价态离子（例如 Ag 和 Ag ）氧化。因此，电化学氧化的高价态离子的浓度可以通过中间价态离子来控制，从而影响沉积物的生长动力学。以 Ag O NO 的阳极电沉积为例，证明了中间价态离子在调整 Ag O NO 沉积物形状方面的作用。此外，可以通过中间价态金属离子来控制二级结构的生长位置。此外，还可以选择性地刻蚀从某些晶面开始形成的空心纳米框架等设计的复杂微结构。通过在电解液中引入中间价态离子，可以显著增强对金属离子电化学组装过程的控制能力。
