Raman Spectroscopy of Redox Activity in Cathodically Electrodeposited Nickel Hexacyanoferrate Thin Films

Abstract

The intercalation of cations into electrodeposited nickel hexacyanoferrate (NiHCF) depends on the stoichiometry and oxidation state of the material. To better understand this material's performance as a cation separation matrix, the oxidation state needs to be measured independently from the stoichiometry, regardless of the particular intercalated cation. Reported is the use of Raman spectroscopy to quantify the absolute oxidation state of NiHCF thin films. Raman spectroscopy probes NiHCF's cyanide bonds, which are sensitive to the oxidation state of the matrix. The oxidation state is controlled via potentiostatic experiments in electrolytes containing Na⁺, K⁺, and Cs⁺ (NO₃⁻ is the common anion). Principal component analysis (PCA) on the Raman spectra shows that more than 90% of the spectral variance is captured by one principal component, with a score value shown to be directly related to the oxidation state of the film. A universal, predictive regression model was developed using these score values as the dependent variables and Raman spectra as the independent variables. The results were confirmed with electrochemistry and energy dispersive X-ray spectroscopy.