RESUMO
Organic additives are widely used in the deposition baths of metals and alloys thanks to their special function which affects the growth and the building of the crystal. This study investigates the effect of glycerol on Ni deposition onto carbon felt (CF) and its effect on the catalytic activity towards glycerol electrooxidation. The impact of glycerol on the morphology, distribution, and particle size of the electrodeposited Ni is disclosed using a scanning electron microscope (SEM). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) techniques were used to probe the possible changes of the electrodeposited Ni oxide phases. Electrochemical measurements show that the as-synthesized Ni0.05@CF electrocatalyst prepared in the presence of 50 mM glycerol has a marked activity towards glycerol electrooxidation, as confirmed by the impressive increase of the oxidation current by about 1.6 times concurrently with a favorable negative shift of its onset potential. Moreover, the charge transfer resistance (R ct) is much reduced from 140 to 87 ohm. The addition of glycerol to the deposition bath is believed to retard the growth of the formed Ni deposits while enhancing the nucleation rate and thus increases the particle density and, consequently, the distribution of deposited Ni over the entire CF is improved along with increasing the surface concentration and surface-active sites. This assumption is supported by density functional theory (DFT) calculations.
RESUMO
Herein, 3D-Carbon Felt (CF) are decorated with nickel-copper (Ni-Cu@CF) bimetallic nanostructures through either sequential or co-electrodeposition tactics. Their catalytic activity towards glycerol electrooxidation is investigated by employing cyclic voltammetry (CV) and linear sweep voltammetry LSV. The morphology and composition of the various Ni-Cu@CF are investigated using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) together with various electrochemical measurements (e.g., CV, chronoamperometry, LSV). The co-deposition of Ni-Cu shows a dendritic-like structure with higher electrocatalytic activity towards glycerol electrooxidation compared to the monometallic counterparts. Interestingly, the best electrode (NiCu@CF Ni particles as the top layer) prepared by sequential electrodeposition shows 1.6-fold higher glycerol oxidation activity, manifested in oxidation current, compared to Ni-coated CF due to Ni particles covering the surface of dendritic copper uniformly. Thus, the surface concentration of Ni is increased and at the same time a synergistic effect occurs between Ni and Cu by the simple addition of Cu which reinforces the surface concentration of Ni from 3.4 × 10-8 to 1.1 × 10-7 mol cm-2.
RESUMO
Nowadays, the glucose electro-oxidation reaction (GOR) is considered one of the most important solutions for environmental pollution. The GOR is the anodic reaction in direct glucose fuel cells and hybrid water electrolysis. In this study, the GOR is boosted using a carbon support modified with Ni(OH)2 as a non-precious catalyst. The carbon support, with in situ generated graphene nanosheets having a large surface area, grooves, and surface functional groups, is prepared via a simple electrochemical treatment of the carbon rods of an exhausted zinc-carbon battery. Ni(OH)2 is electrodeposited on the surface of the functionalized exfoliated graphite rod (FEGR) via the dynamic hydrogen bubbling technique (DHBT) and tested for GOR. The thus-prepared Ni(OH)2/FEGR electrode is characterized by SEM, mapping EDX, HR-TEM, XRD, and XPS characterization tools. Ni(OH)2/FEGR displays an onset potential of 1.23 V vs. the reversible hydrogen electrode (RHE) and attains high current densities at lower potentials. Additionally, Ni(OH)2/FEGR showed prolonged stability toward GOR by supporting a constant current over a long electrolysis time. The enhanced catalytic performance is attributed to the superb ionic and electronic conductivity of the catalyst. Importantly, ionic conductivity increased, due to (i) a large surface area of in situ generated graphene layers, (ii) enhanced distribution of active material during deposition using DHBT, and (iii) increased hydrophilicity of the underlying substrate. Therefore, the Ni(OH)2/FEGR electrode can be used efficiently for GOR as a low-cost catalyst, achieving low onset potential and high current densities at low potentials.