Faculty Publications
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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 Redox-Active Vanadium-Based Polyoxometalate as an Active Element in Resistive Switching Based Nonvolatile Molecular Memory(Wiley-VCH Verlag info@wiley-vch.de, 2020) Sterin, N.S.; Basu, N.; Cahay, M.; Satyanarayan, M.N.; Mal, S.S.; Das, P.P.Resistive switching (RS)-based random access memory has been envisaged as a viable alternative to existing memory technology due to its nonvolatility, high switching speed, high endurance/retention, and considerably low operating voltage. Herein, a new uniform, repetitive, and stable RS phenomenon is demonstrated based on very low-cost two-terminal metal–insulator–metal stack fabricated using a highly redox-active vanadium-based polyoxometalate (POM) molecular clusters, [V10O28]6?—belonging to polyoxovanadate (POV) family. The RS is observed to be unipolar and nonvolatile in nature, and occur at a fairly low operating bias voltage (less than 2 V), making it suitable for low-power operations. The switching event is attributed to the cycling between formation and rupture of tiny conductive nanofilaments formed due to trapping and detrapping of positively charged ionized oxygen vacancy sites present in the active switching layer of [V10O28]6?. POMs, in their rich abundance, are highly stable early transition-metal oxide nanosized clusters, capable of storing as well as releasing a large number of electrons. In addition, they can undergo fast and reversible redox reactions (both in solid and liquid electrolyte media) in “stepwise” manner—a property that makes them a promising candidate for ultrafast and multi-level nonvolatile molecular memory for high-density data storage. Preliminary investigations on the POV-based memory cells result in device resistance ratio ?25, endurance for more than 200 cycles, and stable retention time around 2200 s, in fully open air condition. © 2020 Wiley-VCH GmbHItem Growth of Very Large MoS2Single Crystals Using Out-Diffusion Transport and Their Use in Field Effect Transistors(Institute of Electrical and Electronics Engineers Inc., 2021) Pandey, S.K.; Izquierdo, N.; Campbell, S.Monolayer molybdenum disulfide (MoS2) is an attractive 2D material with a wide range of potential applications in the field of electronics and optoelectronics. To obtain the best performance, it is very necessary to grow large area single crystals of MoS2 (single domain) to avoid the effects of grain boundaries, but is exceptionally challenging to do this. Here, we report a novel method which we call out-diffusion vapor transport to grow large area single crystal monolayer MoS2 using an otherwise conventional chemical vapor deposition system. In this method, microchannels were created on the boat to significantly limit the region where MoOx vapor can react with S vapor to form crystals. This growth method resulted in triangular monolayer MoS2 single crystals up to ?640 ?m on a side grown on an oxidized silicon substrate, the largest crystals reported to date. Most of these crystals were multilayer at the center. This common feature has been identified in the literature as partially reduced transition metal oxide nucleates a second layer. We also achieved fully monolayer MoS2 single crystals up to ?450 ?m on a side, the largest demonstrated without the MoOx. Fabricated field effect transistors (FET) using MoS2 monolayer crystal as the active layer demonstrate a conventional n-type behavior, room-temperature mobility up to 45.5 cm2 V-1 s-1 and a maximum ON-Current (ION)/OFF-current (IOFF) ratio of 1.8 × 107. Raman and Photoluminescence results indicate that the as-grown large area monolayer crystals have high crystalline quality and uniformity with minimal defects, a finding that is consistent with the high electron mobility. This research work provides a superior technique to grow large-area high-quality single-crystal monolayer MoS2 without resorting to exotic equipment or techniques. © 2002-2012 IEEE.Item Boosting overall electrochemical water splitting via rare earth doped cupric oxide nanoparticles obtained by co-precipitation technique(Elsevier Ltd, 2022) Rodney, J.D.; Deepapriya, S.; Jerome das, S.J.; Robinson, M.C.; Perumal, S.; Sadhana, S.; Periyasamy, P.; Jung, H.; Justin Raj, C.J.The development of electrocatalyst based on nonprecious metals has been a persistent issue as electrochemical water splitting requires electrocatalyst with advanced activity and stability. Further, the electrocatalyst must require low overpotential above the standard potential (>1.23 V) of water splitting to produce hydrogen. This study presents the facile co-precipitation derived rare earth dysprosium (Dy) doped cupric oxide nanoparticles (Cu1−xDyxO) as a non-noble transition metal oxide nanoparticle. The 3 % Dy doped CuO (3 % Dy/CuO) and 1 % Dy doped CuO (1 % Dy/CuO) electrocatalysts showed excellent Oxygen Evolution Reaction (OER) at 1.55 V vs RHE and Hydrogen Evolution Reaction (HER) at − 0.036 V vs RHE in aqueous 1 M KOH aqueous electrolyte to attain the benchmark current density (10 mA cm−2). The stability of the driven electrocatalyst in a bi-functional electrocatalytic setup was monitored for 24 h and was found to be exhibiting a cell voltage of about 2.1 V at 30 mA cm−2 constant current density. Further, the retention capability of the electrode was observed to be 99 % with a very minimal loss. This study hugely suggests the promising consequence of doping rare earth onto a non-precious metal oxide-based electrocatalyst, making it a highly effective bifunctional material for water splitting. © 2022 Elsevier B.V.Item High-Potential Aqueous Asymmetric Supercapacitor Based on 2D Molybdenum Disulfide and Vanadium Pentoxide Electrodes(American Chemical Society, 2024) Pullanchiyodan, A.; Haridasan, G.T.; Sreeram, P.; Das, A.; T M Balakrishnan, N.; Prasanth, P.; Hegde, A.A wide-operating-voltage asymmetric supercapacitor (ASC) based on an aqueous electrolyte has great promise in the current energy storage technologies by providing better energy density, power density, safety, cost effectiveness, and long cycle life. Herein, the fabrication of an ASC using a 2D transition metal dichalcogenide (molybdenum disulfide (2D MoS2)) and a transition metal oxide (vanadium pentoxide, V2O5) as the negative and positive electrode, respectively, was demonstrated. The electrochemical and galvanostatic charge-discharge analysis of both positive (V2O5) and negative electrodes (2D MoS2) was carried out in a three-electrode setup. The results show stable operating potentials of −0.9 and 1.0 V for MoS2 and V2O5 electrodes, respectively. By combining these positive and negative electrodes in a 1 M sodium sulfate (Na2SO4) aqueous electrolyte, the developed ASC reveals a wide operating potential (2.0 V). The electrochemical analysis of the ASC in a stable operating potential of 1.4 V gives an areal capacitance and energy density of 30 mF/cm2 and 8.2 μWh/cm2, respectively, at a scan rate of 1 mV s-1. The performance of the ASC was analyzed for 5000 continuous charge-discharge cycles at a higher current of 3.5 mA. After 5000 cycles, the ASC exhibits more than 80% capacitance retention with a specific capacitance of 0.85 mF/cm2 © 2024 American Chemical Society.Item Influence of V2O5 addition as a dopant and dispersed content in barium borophosphate glass on structural and optical properties(Elsevier Ltd, 2024) Rashmi, I.; Ingle, A.; Raghuvanshi, V.; Shashikala, H.D.; Nagaraja, H.S.The Barium Borophosphate glass system with molar compositions 40P2O5– 25B2O3-(35-x) BaO-xV2O5 and 40P2O5–25B2O3–35BaO-xV2O5 (x = 0,1,3,5 mol%) was synthesized using melt-quenching method. A comprehensive investigation of the structural and optical properties was conducted to compare the effects of V2O5 as a dopant and as an addition to the glass matrix. The physical parameters were assessed through the measurement of density. The influence of V2O5 introduction on vibrational modes was studied through Fourier-transform infrared (FTIR) and Raman spectroscopy. The UV–visible absorbance analysis unveiled the existence of multiple valence states of vanadium (V3+, V4+ and V5+). The reduction in bandgap was determined through the utilization of a Tauc plot, while the measurement of the refractive index allowed for the assessment of its variation with the composition of V2O5. Photoluminescence spectroscopy (PL) was employed to explore the presence of intrinsic defects within the glass matrix and the impact of V2O5 on the emission spectra. Furthermore, CIE chromaticity coordinates of synthesized samples were observed in both the white and blue regions, suggesting their potential application in display devices. Significantly, V2O5 glass doped with 1 mol% displayed chromaticity, characterized by CIE coordinates x = 0.288 and y = 0.386, closely matching the white region as well as the bandpass filter. The introduction of transition metal oxide dopants into borophosphate glass yielded exceptional emission properties. The ability to modify optical properties makes it more promising for these glass materials, particularly for applications like optical filters and displays. © 2024 Elsevier Ltd and Techna Group S.r.l.Item A comprehensive study uncovering physical, structural, and optical properties of Cu2O and TiO2-reinforced borosilicate glasses as optical filters(Elsevier B.V., 2024) Raghuvanshi, V.; Rashmi, I.; Ingle, A.; Shashikala, H.D.; Nagaraja, H.S.In this study, the integration of transition metal oxides (TMOs), specifically Cu2O and TiO2, into a borosilicate glass matrix (30SiO2–35B2O3–35Na2O–5CaF2-X (TMO)) was investigated for enhanced glass functionality. Glass samples with varying TMO concentrations (X = 0, 1, 2, 3, 4 mol%) were prepared using the melt-quenching technique. X-ray diffraction confirmed the amorphous nature of the synthesized samples, while FTIR analysis showed structural changes, transitioning from trigonal BO3 to BO4 tetrahedra, alongside the formation of non-bridging oxygen species due to TMO integration. UV–Vis spectroscopy demonstrated a red shift in optical absorption profiles, correlating with a reduction in the indirect band gap as TMO content increased. Photoluminescence studies showed distinct behaviors, with Cu2O suppressing emission peaks and TiO2 exhibiting intriguing blue and green emissions, diminishing at higher concentrations. It was attributed that Cu2O had a larger impact on altering the glass network than TiO2. These findings contribute to understanding the properties of Cu2O and TiO2-containing borosilicate glasses, suggesting tailored optical properties for potential applications as bandpass filter and UV blocker. © 2024 Elsevier B.V.Item Influence of low concentrations of vanadium and titanium ions on the structural and optical properties of borophosphate glasses(Elsevier B.V., 2025) Rashmi, I.; Raghuvanshi, V.; Ingle, A.; Shashikala, H.D.; Nagaraja, H.S.A series of P2O5–B2O3–BaO glass system containing various V2O5 and TiO2 content (from 0.25 to 0.75 mol%) were synthesized using the melt-quenching method to examine their structural, EPR, and optical characteristics. EPR analysis confirmed VO2+ hyperfine splitting and the presence of Ti3+ ions in a tetragonally compressed octahedral structure. The local structures of VO2+ and Ti3+ centers were explored through spin Hamiltonian parameters (g??e) and optical transition energies. UV–visible spectroscopy revealed multiple oxidation states of vanadium (V3+, VO2+ and V5+) and titanium (Ti3+, Ti4+), which significantly influenced the optical characteristics. Photoluminescence (PL) studies indicated the presence of oxygen vacancies and intrinsic defects in the glass matrix, with [VO4]3- groups and Ti3+ ions significantly enhancing emission properties. The enhanced luminescence was observed for glasses with 0.75 mol% TiO2 and 0.75 mol% V2O5. Notably, the 0.75 mol% V2O5-doped glass, exhibited CIE chromaticity coordinates (x = 0.26, y = 0.31), closely aligning with standard white light. The tunability of optical properties through transition metal oxide doping highlights the potential of these glasses for advanced photonic applications, including optical filters and display technologies. © 2025 Elsevier B.V.