Sreeram K Kalpathy

Nickel cobaltite (NCO) nanofibers were synthesized using poly(styrene-co-acrylonitrile) (SAN) as the polymeric binder through sol–gel assisted electrospinning. Defect-free precursor nanofiber mats were pyrolyzed at 773 K at three different pyrolysis soaking times t = 2, 4, and 6 h. The SAN present in the precursor nanofibers caused morphological changes in the NCO nanofibers during their thermochemical degradation. Consequently, fractal aggregates of NCO nanoparticles were formed along the length of the nanofibers. X-ray photoelectron spectroscopy (XPS) revealed both + 2 and + 3 oxidation states for Ni and Co, with spinel crystal defects due to oxygen rich atmosphere. XPS, high-resolution transmission microscopy, and optical analysis showed graphene-like structures embedded within the NCO nanofibers. With increase in pyrolysis soaking time, the morphology of the NCO particles markedly changed from spherical to rod-like. We propose a mechanism for the morphological change of NCO nanoparticles on the basis of crystallite splitting accompanied by particle splitting and reordering.

In this study, we report for the first time the synthesis of nickel titanate (NTO) nanofibers containing a mixture of ilmenite and spinel phases of NTO, at an atypical low temperature. Precursor nanofibers produced by sol-gel electrospinning were calcined at three different temperatures to produce the NTO nanofibers. Thermal analysis along with X-ray photoelectron spectroscopy confirmed the formation of non-crystalline stable phases of TiN and Ti-O-N that restrained the formation of ilmenite NTO, and the Ni-rich environment pushed the Ti atoms to tetrahedral sites to form a defective spinel structure. The crystallite size of spinel NTO was observed to increase as a function of the calcination temperature above 700 °C, as the activation energy for coalescence and growth of spinel NTO was favorable. NTO nanofibers obtained above the calcination temperature of 700 °C exhibited new band gap energy around 2.5 eV in Tauc plot. Oxygen vacancies in these ceramic nanofibers decreased as the calcination temperature was increased. A hypsochromic shift of 20 nm in the photoluminescence spectra suggested that the material had a Ni2+ rich NTO (spinel).

Nickel cobaltite (NCO) attains the apex of Sabatier-type volcano plot for electrochemical reaction compared to simple oxides due to synergetic effect of mixed transition metal cations. The combination of high surface area, aspect ratio, and porosity of electrospun NCO nanofibers (NCO-NF) enhance their electrocatalytic performance by improved electron mobility and more active sites. In the present study, NCO-NF fabricated using poly (styrene-co-acrylonitrile) (SAN) as a sacrificial polymer, were embellished with graphene nanoclusters (GNC), which augment the electrocatalytic performance of the NCO-NF. The in situ formed GNC along the NCO-NF are result of the interaction between the polar functional groups of the polymer, and the cations of precursor salts during the calcination of precursor nanofibers. The GNC/NCO-NF with least crystallite size and high aspect ratio having porous NCO nanoparticles and in situ grown GNC were developed using sol-gel electrospinning process assisted by calcination of precursor nanofibers. This simple, eco-friendly, and economical synthesis route with unique structure chemistry of SAN to form GNC and the presence of dual cations (Ni and Co) provides enhanced performance and multifunctionality to GNC/NCO-NF electrodes for electrocatalytic applications, such as biosensors and water-splitting. In the present study, the modified electrodes (GNC/NCO-NF/graphite electrode) exhibited excellent non-enzymatic glucose detection over a wide range of concentration with a lower limit of 1.2 μM and sensitivity of 1827.5 μA mM−1 mg−1 in 0.1 M NaOH. Further, the modified electrodes were also tuned for H2O2 detection to aid enzymatic glucose sensing. When examined for bifunctional water-splitting in 1 M NaOH, the electrode reached an onset potential of −0.537 V and 0.735 V against reversible hydrogen reference electrode and a Tafel slope of 37.6 mV·dec−1 and 67.0 mV·dec−1 for hydrogen and oxygen evolution reactions, respectively. The results prove that GNC/NCO-NF are promising candidates as multifunctional electrocatalyst.