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).

Producing pure H2 and O2 to sustain the renewable energy sources with minimal environmental damage is a key objective of photo/electrochemical water-splitting research. Metallic Ni-based electrocatalysts are expensive and eco-hazardous. This has rendered the replacement or reduction of Ni content in Ni-based electrocatalysts a decisive criterion in the development of bifunctional electrocatalytic materials. In the current study, spinel/ilmenite composite nickel titanate (NTO) nanofibers were synthesised using sol-gel assisted electrospinning followed by pyrolysis at different soaking temperatures (viz., 773, 973, and 1173 K). The presence of a defective spinel NTO phase (SNTO) distributed uniformly along the nanofibers was confirmed by X-ray photoelectron and Raman spectroscopy. The electron micrographs revealed the morphological change of NTO nanofibers from a mosaic to bamboo structure with an increase in pyrolysis soaking temperature. The electrocatalytic activity of NTO nanofibers obtained at different pyrolysis soaking temperatures for alkaline water-splitting was studied. The highly defective SNTO manifests properties similar to metallic Ni and favours H2 evolution through the hydrogen evolution reaction (HER) by adsorbing more H+ ions on active sites. In contrast, the ilmenite NTO favours O2 discharge. These results are explained based on the morphology of the NTO nanofibers. The mosaic structure which has higher porosity and greater SNTO content shows excellent HER performance. In contrast, the large bamboo structured NTO nanofibers which have lesser porosity and SNTO content cage the bigger (OH)ads ions at their catalytic sites to facilitate OER performance.

Polymorph (spinel/ilmenite) composite nanofibers of nickel titanate (NTO) were prepared by a sol-gel assisted electrospinning process followed by pyrolysis using the styrene-acrylonitrile copolymer as a precursor at three different pyrolysis soaking temperatures (i.e. T= 773, 973, and 1173 K). The magnetic behavior of these composite NTO nanofibers was studied under isothermal and non-isothermal conditions in the temperature range of 20-300 K. The magnetic parameters such as coercivity (Hc), remanence (Mr), and saturation magnetisation (Ms) were found to be strongly dependent onT. The highestHcandMrwere observed for NTO nanofibers developed at 973 K, which have a mosaic structured morphology with spinel and ilmenite NTO crystallite sizes of ~39 nm and ~24 nm, respectively. On the other hand, the highestMsand switching field distribution were observed for mosaic structured NTO nanofibers having smaller crystallites (~13 nm and 24 nm for spinel and ilmenite NTO, respectively, with high inter-particle distance and high porosity) developed at 773 K, which are also rich in spinel NTO content. The correlation between the variation in magnetic behavior and structural/morphological features of NTO nanofibers is useful for NTO-based soft magnetic and multiferroic applications.

Nickel cobaltite (NCO) is a binary transition-metal oxide, which is extensively used as an electrocatalyst and magnetic material. NCO nanofibers and NCO/graphene composite exhibit high electrochemical reactivity due to the directional bridging of NCO particles. This makes NCO a promising candidate electrode material for use in supercapacitors and batteries. Besides, NCO is also a promising magnetic material due to its unique structural composition, where the cations are seated in octahedral sites surrounded by oxygen vacancies. In the present work, a simple and reliable method was discovered for tuning the morphological and structural changes of nickel cobaltite (NCO) nanoparticles, which were reshaped along the NCO nanofibers, by controlling the pyrolysis soaking time. As the pyrolysis soaking time increases, NCO transforms from inverse spinel to normal spinel; and the morphology of NCO nanoparticles changes from spherical to rod-like. These changes were validated by the hypsochromic peak shifts in Raman, and FTIR spectroscopies. The magnetic measurements reveal changes in the shape of the hysteresis loop, which are explained on the basis of structural and morphological changes in the nanostructure. The net magnetisation increases and coercivity decreases, with an increase in pyrolysis soaking time. These changes in magnetic parameters are attributed to structural changes caused by the formation of oxygen vacancies, and surface effects due to switching in morphology of the NCO nanoparticle. [Figure not available: see fulltext.].

Randomly oriented nanofibers of nickel cobaltite (NCO) were fabricated using sol-gel electrospinning followed by calcination. The precursor fibers were collected on rotating disc (RDI) and rotating drum (RDR) collectors. Variable fictitious forces produce continuous deflection at each fiber landing position on the RDI collector, which subjects the nanofibers to non-bundling. On the other hand, in the case of the RDR collector, the fictitious forces act just at the surface, and these forces merely cause slip of the fibers along the rotational axis of the RDR. This slip along with the retained Columbic charges on the surface of the fibers produces fiber bundling, which affects the morphological and structural properties of the NCO nanofibers obtained by calcining the precursor fibers. The use of the RDI collector in sol-gel electrospinning is a simple and optimal method of fabricating precursor nanofibers, which yields non-agglomerated and impurity-free inorganic nanofibers.

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.