Faculty Publications
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Item Some new observations on the structural and phase evolution of nickel titanate nanofibers(Elsevier Ltd, 2017) Kumar, B.S.; Shanmugharaj, A.M.; Kalpathy, S.K.; Anandhan, S.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). © 2017 Elsevier Ltd and Techna Group S.r.l.Item Ceria-samarium binary metal oxides: A comparative approach towards structural properties and soot oxidation activity(Elsevier B.V., 2018) Anjana, A.P.; Geethu, J.; P, M.R.; Prasad Dasari, H.P.; Lee, J.-H.; Harshini, H.; Bhaskar Babu, G.U.Binary metal oxides of CeO2-Sm2O3 (CSx, x varies from 10 to 90 mol%) along with pure CeO2 and Sm2O3 were synthesised successfully by the EDTA-Citrate method. From XRD, Raman spectroscopy and UV–vis DRS results, the whole composition of metal oxides exist in three phases: (fluorite phase (F) (CS10-CS30), bi-phase (fluorite (F) + cubic (C)) (CS30-CS90) and cubic phase (C) (Sm2O3)). For CSx samples, the calculated band gap energy values obtained from the UV–vis DRS results were in between 3.0–5.1 eV and fluorite phase samples (CS10–CS30) displayed lower band gap energy values (3.04–3.07 eV) than compared to the samples in other phases. Similarly, from XPS analysis, fluorite phase samples (CS10–CS30) showed higher surface oxygen vacancy concentration than compared to samples in other phases. Catalytic activity for soot oxidation is carried out on CSx samples, and the T50 temperature is in between 480–540 °C. Fluorite phase samples (CS10 CS30) showed higher surface area, lower degree of agglomeration, lower band gap energy, higher oxygen vacancy concentration and better catalytic activity for soot oxidation. Among all the CSx samples, CS10 sample displayed highest surface area (38 m2/g), lowest degree of agglomeration (0.36), lowest band gap energy (3.04 eV), highest oxygen vacancy concentration (64%) and highest soot oxidation activity (T50 = 480 °C). The order of the soot oxidation activity of CSx samples followed the same trend of band gap energy values. © 2018 Elsevier B.V.Item Pyrolysis-controlled synthesis and magnetic properties of sol–gel electrospun nickel cobaltite nanostructures(Springer New York LLC barbara.b.bertram@gsk.com, 2018) Kumar, B.S.; Dhanasekhar, C.; Adyam, A.; Kalpathy, S.K.; Anandhan, S.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.]. © 2018, Springer Science+Business Media, LLC, part of Springer Nature.Item Low-temperature sonochemical synthesis of high dielectric Lanthanum doped Cerium oxide nanopowder(Elsevier Ltd, 2018) Kishor Kumar, M.J.; Kalathi, J.T.Lanthanum (La) doped Cerium Oxide (CeO2) nanopowder was synthesized at a relatively lower temperature (70°C), without calcination in a simple, faster, and efficient way through sonochemical method. X-ray diffraction (XRD) results confirmed the formation of a cubic fluorite structure of nanocrystalline CeO2 and lattice deformation due to La-doping in CeO2. TEM analysis revealed that the size of La-doped CeO2 particles is in the range of 20?50 nm. In addition, selective area electron diffraction (SAED) and high-resolution TEM (HRTEM) analyses portrayed the nano-crystallinity, lattice fringe pattern, and d-spacing details of La-doped CeO2 powder. Lanthanum doping in CeO2 was further confirmed by a shift in Raman band towards the lower frequency (from 464 cm?1 to 457cm?1) along with peak intensity increase. Photoluminescence (PL) emission spectra showed that emission intensity of the La-doped CeO2 at 510 nm is increased due to oxygen vacancy mediated charge transfer. All these results confirm the successful doping of La in CeO2. The La-doped CeO2 powder possesses a high dielectric constant (?r) of 106 and a low dielectric loss (tan ?) of < 0.4 % at 1 kHz. The La-doped CeO2 finds potential applications on developing devices in the field of a thin film capacitor, transistors, and solid oxide fuel cells. © 2018 Elsevier B.V.Item Praseodymium doped ceria as electrolyte material for IT-SOFC applications(Elsevier Ltd, 2018) Shajahan, I.; Ahn, J.; Nair, P.; Medisetti, S.; Patil, S.; Niveditha, V.; Uday Bhaskar Babu, G.; Prasad Dasari, H.P.; Lee, J.-H.Praseodymium-doped ceria (PDC, Ce0.9Pr0.1O2) electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been successfully synthesised by EDTA-citrate method. From X-Ray diffraction (XRD), fluorite structure along with a crystallite size of 5.4 nm is obtained for PDC nanopowder calcined at 350 °C/24 h. Raman spectroscopy confirmed the structure, presence of oxygen vacancies with the manifestation of the main peak at 457 cm?1 and with a secondary peak at 550 cm?1. From Transmission Electron Microscopy (TEM) analysis, the average particle size is around 7–10 nm and selected area electron diffraction (SAED) patterns further confirmed the fluorite structure of PDC nanopowder. The PDC nanopowder displayed a BET surface area of 65 m2/g with a primary particle size of ?13 nm (calculated from BET surface area). Dilatometer studies revealed a multi-step shrinkage behaviour with the multiple peaks at 522, 1171 and 1461 °C which may be originated due to the presence of multiple size hard agglomerates. The PDC electrolyte pellet sintered at 1500 °C displayed an ionic conductivity of 1.213E-03 S cm?1 along with an activation energy of 1.28eV. Instead of a single fluorite structure, XRD of sintered PDC pellet showed multiple structures (Fluorite structure (CeO2) and cubic structure (PrO2). © 2018 Elsevier B.V.Item Optical and mechanical studies on free standing amorphous anodic porous alumina formed in oxalic and sulphuric acid(Springer Verlag service@springer.de, 2018) Ramana Reddy, P.R.; Ajith, K.M.; Udayashankar, N.K.Anodic porous alumina (APA) membranes with a uniform pore arrangement typically serve as an ideal template for formation of different types of nanostructured materials. In the present work, APA membranes were synthesized using two-step anodization in 0.3 M of oxalic and 0.3 M of sulphuric acid under the anodization potential of 40 V and 20 V respectively, at 8 °C. Alumina nanowires (ANW) were synthesized by the chemical etching of the APA membranes using phosphoric acid solution. The optical absorbance and reflectance measurements of APA membranes were performed on a spectrometer in the wavelength range of 200–600 nm. The band-gap energy (3.7 and 4.3 eV for oxalic and sulphuric acid) of APA membranes was determined from UV–visible absorption data. The photoluminescence (PL) investigations have revealed the presence of F and F+ defect centers, which could be attributes to oxygen vacancy-related defect centers in oxalic (483 and 466 nm) and sulphuric (423 and 421 nm) alumina. The mechanical properties of amorphous APA membranes were investigated by micro- and nanoindentation techniques. The results indicate that highest hardness (7.70 GPA) and Young’s modulus (138.80 GPA) for sulphuric alumina compared with oxalic alumina. In sulphuric alumina, more number of ANW were observed compared with oxalic alumina. © 2018, Springer-Verlag GmbH Germany, part of Springer Nature.Item Effect of ionic radius on soot oxidation activity for ceria-based binary metal oxides(John Wiley and Sons Ltd vgorayska@wiley.com Southern Gate Chichester, West Sussex PO19 8SQ, 2019) Anjana, A.P.; Prasad Dasari, H.P.; Harshini, H.; Babu, G.U.B.CeO2 (C) along with binary metal oxides of Ce0.9M0.1O2-? (M = Sn, Hf, Zr, Gd, Sm, and La; CT, CH, CZ CG, CS, and CL) are synthesized using the EDTA–citrate method. Samples having an ionic radius smaller (CT, CH, and CZ) and larger (CG, CS, and CL) than Ce4+ are classified separately, and their soot oxidation activity is analyzed. The incorporation of dopant is confirmed from lattice constant variation in X-ray diffraction result. The critical descriptors for the activity are dopant nature (ionic radius and oxidation-state), single-phase solid solution, lattice strain, reactive (200) and (220) planes, Raman intensity ration (Iov/IF2g), optical bandgap, reducibility ratio, and surface oxygen vacancy. Smaller ionic radius, isovalent dopants (CH and CZ) create a defect site by lowering the optical bandgap along with improved surface oxygen vacancy concentration and thus enhanced soot oxidation activity. Aliovalent dopant with larger ionic radius shows the involvement of lattice oxygen in oxidation reaction by charge compensation mechanism. CL showed the highest activity amongst larger ionic radius samples. © 2019 Curtin University and John Wiley & Sons, Ltd.Item A comparative study on enhancer and inhibitor of glycine–nitrate combustion ZnO screen-printed sensor: detection of low concentration ammonia at room temperature(Springer, 2020) Manjunath, G.; Pothukanuri, P.; Mandal, S.We report a comparative study on enhancing and inhibiting the sensing performance of Sr-doped ZnO (Sr0.01 Zn0.99O) and RuO2-activated Sr-doped ZnO heterostructured sensors towards the low concentration (? 50 ppm) of ammonia gas at ambient. Sub-microns sized with high specific surface area, high reactive, oxygen-deficient Sr-doped ZnO particles were synthesized at low temperature (196 °C) through facile glycine–nitrate solution combustion synthesis (SCS) method. Porous, adhered screen-printed film of Sr-doped ZnO with optical bandgap (3.22 eV) was dip-coated using 0.02 M RuCl3 aqueous solution to obtain RuO2 activation. Smaller crystallite size and lesser lattice distortion obtained with Sr-doping in ZnO enhance the gas response (S = 71) towards the 50 ppm of ammonia gas at room temperature. RuO2-activated Sr-doped ZnO sensor associated with lesser oxygen vacancies and a lower concentration of chemisorbed oxygen species due to passivation layer and no-spill-over activity of RuO2, which inhibits the gas response from 71 to 3. Sr-doped ZnO-based sensor shows high selectivity towards ammonia against 50 ppm of volatile organic compound (VOCs) vapor. Expeditious sensor kinetics (response time and recovery time) in the Sr-doped ZnO sensor was observed, in which smaller crystallite size offers a shorter distance for the diffusion of oxygen vacancies (Vo). Ultra-high-sensitive and selective sensors with ease and economical fabrication offer feasibility in industries and domestic applications where detection of the less concentration ammonia vapor is crucial. © 2020, Springer Science+Business Media, LLC, part of Springer Nature.Item Room-temperature detection of ammonia and formaldehyde gases by La xBa1?xSnO3?? (x = 0 and 0.05) screen printed sensors: effect of ceria and ruthenate sensitization(Springer Science and Business Media Deutschland GmbH, 2021) Manjunath, G.; Vardhan, R.V.; Praveen, L.L.; Pothukanuri, P.; Mandal, S.In the present work, gas sensing properties of the screen printed ceria and ruthenate-sensitized BaSnO3 (BSO) with La doping heterostructure sensors towards the detection of ammonia and formaldehyde gases at room temperature were studied. Adhered, porous screen printed films with different morphologies were obtained by depositing the LaxBa1?xSnO3?? (x = 0 and 0.05) powder particles prepared by the polymerized complex method. Ceria and ruthenate sensitization for screen printed LaxBa1?xSnO3?? (x = 0.05) film was processed through dip-coating in the 0.03 M aqueous solution of CeCl3 and RuCl3, respectively. La-doped BaSnO3 (LBSO) sensor with smaller crystallites, needle-like morphology and high concentration of oxygen vacancies exhibited superior gas response of 65 and 29 towards 50 ppm of ammonia and formaldehyde gases, respectively. Superabundant sensitization of ceria and ruthenate reduced the oxygen vacancy and structural open porosity in the LBSO sensor; therefore, the ammonia gas response was decreased from 65 to 14 and 3, respectively, whereas the formaldehyde gas response was reduced to less than 1/6th times the LBSO sensor. Limit of detection of LBSO sensors was estimated to be ~ 1 and ~ 2 ppm against ammonia and formaldehyde, respectively. The presence of fluorite structured phase ceria with high oxygen atoms storage capacity facilitates the rapid oxidization of analyte gases and caused the expeditious response (75 s) and recovery (60 s) in CeOx-sensitized LBSO sensor. This study might give a new insight into the development of doped and sensitized BSO-based gas sensors operating at ambient conditions. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.Item Development of CeO2-HfO2Mixed Oxide Thin Films for High Performance Oxygen Sensors(Institute of Electrical and Electronics Engineers Inc., 2021) Ramshanker, N.; Lakshmi Ganapathi, K.L.; Varun, N.; Bhat, M.S.; Mohan, S.In this work, the authors report the fabrication and characterization of CeO2 -HfO2 mixed oxide thin film based oxygen gas sensors. The atomic concentrations of the individual elements Ce and Hf in the mixed oxide (CeO2 -HfO2) thin films were controlled and tuned using a novel method in RF sputtering to achieve better oxygen sensing characteristics. The characteristics of the sensing film were evaluated using various characterization techniques such as TEM-EDS, FESEM-EDS, XPS and XRD. The XPS and EDS data revealed that the Hf concentration increases with an increase in size as well as number of the HfO2 pellets that are placed on a 3-inch CeO2 target during sputtering. From the XRD and XPS analysis, it was found that the mixed oxide film with 10-11% Hf atomic concentration has the best sensing characteristics. The superior sensing characteristics of the CeO2 -HfO2 film can be attributed to the existence of a highly reactive plane (200) with the highest surface energy and a strongly reduced surface with oxygen vacancy formation due to the presence of Ce3+ ions and HfOx, x < 2 on the surface of the mixed oxide film. The sensor film detected the presence of oxygen gas even at low temperatures (< 400°C); however, the response time and recovery time were slightly higher. The sensor film of thickness 220 nm with Hf concentration between 10-11% showed excellent sensitivity (15), fast response and recovery times of 8 s and 10 s respectively at an operating temperature of 400°C, which are the best values reported till date for CeO2 based oxygen sensors. © 2001-2012 IEEE.