电沉积钴和镍六氰合铁酸盐：结构与形貌的见解

中文摘要 AI 辅助

普鲁士蓝（PB）及其类似物（PBAs）因其可调的氧化还原化学性质和开放框架结构，在电化学应用中具有重要价值。本研究通过恒电位电沉积法合成了含铁（FeHCF）、钴（CoHCF）和镍（NiHCF）的六氰合铁酸盐（HCF）。循环伏安法揭示了不同的氧化还原行为。形貌表征（SEM、EDX）显示FeHCF和CoHCF呈现均匀的金字塔形薄膜生长。相比之下，NiHCF由于残余应力，呈现出带有顶部立方簇的裂纹薄膜。尽管如此，所有样品均发现均匀的元素分布。结构表征（TEM和XRD）确认所有薄膜具有立方晶格晶体结构，且由于原子半径减小，从Fe到Co再到Ni晶格发生系统性收缩。拉曼和XPS数据揭示了向Fe2+主导氧化态的转变，以及K+和水占据PBAs框架对CN键合的影响。这些发现阐明了金属取代和沉积参数如何调节PBA薄膜的结构和电化学性质，为设计定制电极提供了一条战略途径。

英文摘要

Prussian blue (PB) and its analogues (PBAs) are interesting materials for electrochemical applications due to their tunable redox chemistry and open framework structure. In this study, hexacyanoferrates (HCF) containing iron (FeHCF), cobalt (CoHCF) and nickel (NiHCF) were synthesized via potentiostatic electrodeposition. Cyclic voltammetry revealed distinct redox behaviors. Morphological characterization (SEM, EDX) demonstrated uniform, pyramidal film growth for FeHCF and CoHCF. Otherwise, NiHCF presented a cracked film with cubic clusters on top due to residual stress. Despite this, homogeneous element distribution was found for all samples. Structural characterization (TEM and XRD) confirmed a cubic lattice crystal structure for all films, with systematic lattice contraction from Fe to Co to Ni due to decreasing atomic radius. Raman and XPS data revealed a shift toward Fe2+ dominant oxidation states and modifications in CN bonding with the influence of K+ and water occupancy in the PBAs framework. These findings illustrate how metal substitution and deposition parameters can tune the structural and electrochemical properties of PBA films, presenting a strategic route to design tailored electrodes.

发表机构

• Faculty of Physical Engineering/Computer Sciences, University of Applied Sciences Zwickau（茨维考应用科学大学物理工程/计算机科学学院）
• Leibniz Institute for Solid State and Materials Research Dresden（德累斯顿 Leibniz 固体与材料研究所）
• Institute of Solid State and Materials Physics, TU Dresden（德累斯顿工业大学固体与材料物理研究所）

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