Enhancing electrocatalytic activity in metallic thin films through surface segregation of carbon

• Published in: Physical chemistry chemical physics : PCCP 2024-01, Vol.26 (3), p.2355-2362
• Main Authors: Kousar, Ayesha, Quliyeva, Ulviyya, Pande, Ishan, Sainio, Jani, Julin, Jaakko, Sajavaara, Timo, Karttunen, Antti J, Laurila, Tomi
• Format: Article
• Language: English
• Subjects: Adhesion; Annealing; Ascorbic acid; Carbon; Chromium; Diffusion barriers; Diffusion layers; Dopamine; Elastic analysis; Electrochemical analysis; Electrons; Flight operations; Graphene; Graphite; Microstructure; Nanomaterials; Oxidation; Photoelectrons; Quantum chemistry; Raman spectroscopy; Solubility; Thin films; Titanium; X ray photoelectron spectroscopy
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d3cp04316a

Thin layers of commonly used adhesion metals i.e. , Cr and Ti were annealed to investigate and estimate their impact on the electrochemical properties of the carbon nanomaterials grown on top of them. The microstructure, surface chemistry, and electrochemical activities of these materials were evaluated and compared with those of as-deposited thin films. The results from X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, grazing incidence X-ray diffraction (GIXRD), time-of-flight elastic recoil detection analysis (TOF-ERDA), and conductive atomic force microscopy (C-AFM) indicated the formation of a catalytic graphite layer on Cr following annealing, while no such layer was formed on Ti. This is attributed to the formation of the Cr 2 O 3 layer on annealed Cr, which acts as a barrier to carbon diffusion into the underlying Cr. Conversely, Ti exhibits a high solubility for both carbon and oxygen, preventing the formation of the graphite layer. Cyclic voltammetry results showed that annealed Cr electrodes are electrochemically active towards both dopamine (DA) and ascorbic acid (AA) while no electrochemical activity is exhibited by annealed Ti. Quantum chemical calculations suggested that the presence of carbon as graphene or an amorphous form is critical for the oxidation reaction of probes. These results are significant for comprehending how the distinct solubilities of typical interstitial solutes influence the microstructure of adhesion metal layers and consequently yield diverse electrochemical properties. Annealing commonly used adhesion layers deposited on the Si substrate (Ti/Si or Cr/Si) leads to catalytic graphite layer formation on the thin Cr layer, resulting in its electrochemical reactivity for dopamine and ascorbic acid, in contrast to Ti.