Electrodeposition of nanostructured CoNi thin films and their anomalous infrared properties

Abstract

Different composition, thickness and structure of CoNi thin films supported on glassy carbon were prepared by electrochemical codeposition. Potential step method was applied to prepare CoNi thin films with different composition which was controlled by varying the concentration ratio of Co2+/Ni2+ (x:y) in the deposition solution, thus this type of CoNi thin film was defined as CoNi(x:y). Nevertheless, CoNi thin films with different thickness and structure (denoted as CoNi(n)) were synthesized in a fixed Co2+/Ni2+ solution under cyclic voltammetric conditions by varying the cyclic numbers (n) within a defined potential range. AES and EDS analysis revealed that the atomic ratio of Co/Ni in the film (including both outer and inner layer) was in good accordance with the initial Co2+/Ni2+ ratio. XRD investigation indicated that the CoNi(20:0) and CoNi(15:5) thin films were hexagonal closed-packed (hcp) structure, however, the CoNi(10:10), CoNi(5:15) and CoNi(0:20) thin films were face centered cubic (fcc) structure. SEM studies demonstrated that the CoNi(x:y) thin films were uniformly composed of irregular nanoparticles. In the case of CoNi(n), with n increasing, the structure of nanoparticles inside the CoNi thin films underwent a transition from imperfectly spherical particles to multiform particles, and finally to irregular polyhedral particles, accompany with an increase of average size. In situ FTIR reflection spectroscopic studies demonstrated that the mainly chemisorbed CO species (COad) on CoNi(x:y) surfaces were transferred from linearly bonded CO (COL) to bridge bonded CO (COB) as a function of the content of Ni and the crystal phase structure of CoNi thin films. CoNi(x:y) and CoNi(n) thin films all exhibited anomalous IR properties, corresponding respectively to abnormal IR effects (AIREs), Fano-like IR effects and surface-enhanced IR absorption effects. AIREs characterized mostly with inversion of IR band was found on CoNi(x:y), CoNi(4), CoNi(8) thin films which were dominated by irregular or imperfectly spherical particles. Fano-like IR bands with positive-going peak on the lower wavenumbers side were observed in cases of CO adsorbed on CoNi thin films composed mainly of multiform nanoparticles, typically on CoNi(25) thin film. IR features were finally changed into surface-enhanced IR absorption as CO adsorbed on the CoNi(50) thin film, i.e., the CoNi thin film was dominated by smooth irregular polyhedral particles.