Faculty Publications
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Item Polyoxovanadate-activated carbon-based hybrid materials for high-performance electrochemical capacitors(Institute of Physics, 2022) Anandan Vannathan, A.A.; Chandewar, P.R.; Shee, D.; Mal, S.S.Two different polyoxovanadates derivatives K5MnIVV11O33.10 H2O (MnV11) and K7MnIVV13O38.18 H2O (MnV13), have been studied to evluate their electrochemical performance. These polyoxovanadates were deposited on activated carbon (AC) to prepare AC-MnV11 and AC-MnV13 composites. The electrochemical performance of the AC- MnV11 electrode exhibits the remarkable specific capacitance of 479.73 F g-1 at a current density of 0.4 A g-1, along with incredible specific power and energy of 960 W kg-1. Likewise, the AC-MnV13 exhibits a specific capacitance of 357.33 F g-1 at the same current density of 0.4 A g-1 with a specific energy of 71.46 Wh kg-1. Interestingly, the AC- MnV11 could light up the red and yellow color LED bulbs for a duration of 80 and 60 seconds, respectively, indicating a considerable specific power of the material. The AC-MnV13 electrode shows significantly less lighting up the 65 and 30 seconds period with red and yellow LED bulbs. © The Electrochemical SocietyItem Photocatalytic degradation of ciprofloxacin & norfloxacin and disinfection studies under solar light using boron & cerium doped TiO2 catalysts synthesized by green EDTA-citrate method(Elsevier B.V., 2021) Manjunatha, M.; Chandewar, P.R.; Mahalingam, H.The presence of antibiotic residues in water bodies is an emerging global concern due to its potential development of antimicrobial resistance. Hence, it is essential to develop photocatalysts that not only degrade the antibiotics but can also simultaneously disinfect. Four different boron and cerium doped TiO2 photocatalysts, synthesized by the EDTA-citrate method, are studied for the degradation of two common fluoroquinolone-based antibiotics: ciprofloxacin (CIP) and norfloxacin (NOR) under sunlight. The catalysts are characterized by SEM, TEM, Raman spectroscopy, XPS, DRS, BET surface area and particle size analyzer. At optimized conditions, the synthesized catalysts showed 90–93% degradation for both CIP and NOR. The effects of catalyst loading and initial concentration are studied, and the reaction is found to be pseudo-first-order. The degradation is analyzed by COD reduction and LC–MS, and the by-products of degradation determined. The recycle studies showed that the catalysts are stable up to three consecutive runs. The scavenging experiments indicated e? and OH? as the dominant species responsible for the photocatalytic activity. The disinfection studies using these catalysts under solar light gave 95–99.99% efficiency for E.coli confirming that they are very efficient and can be further exploited for large scale treatment. © 2020 Elsevier B.V.Item Polyoxomolybdate-Polypyrrole-Graphene Oxide Nanohybrid Electrode for High-Power Symmetric Supercapacitors(American Chemical Society, 2021) Maity, S.; Je, M.; Biradar, B.R.; Chandewar, P.R.; Shee, D.; Das, P.P.; Mal, S.Supercapacitors have emerged as one of the most promising candidates for high-performance, safe, clean, and economical routes to store and release of nonfossil energy. Designing hybrid materials by integrating double-layer and pseudocapacitive materials is crucial to achieving high-power and high-energy storage devices simultaneously. Herein, we synthesized a polyoxomolybdate-polypyrrole-graphene oxide nanohybrid via a one-pot reaction. The inclusion of polypyrrole enables a uniform distribution of the polyoxomolybdate clusters; it also confines the restacking of graphene oxide nanosheets. The structural and morphological analysis to unveil the nanohybrid architecture implies excellent interfacial contact, enabling fast redox reaction of polyanions, and a quick transfer of charge to the interfaces. Electrochemical characteristics tested under a two-electrode system exhibit the highest capacitance of 354 F g-1 with significantly high specific energy and power of 49.16 Wh kg-1 and 999.86 W kg-1, respectively. In addition, the cell possesses a high-rate capability and long cycle life by maintaining 96% of its capacitance over 5000 sweeping cycles. The highest specific power of ?10 »000 W kg-1 was computed with Coulombic efficiency of 92.30% at 5 A g-1 current density. Electrochemical impedance spectroscopy additionally reveals enhanced redox charge transfer due to double hybridization. Furthermore, it also demonstrates the impedance and capacitive behavior of supercapacitor cells over a definite frequency regime. ©Item Asymmetric polyoxometalate-polypyrrole composite electrode material for electrochemical energy storage supercapacitors(Elsevier B.V., 2022) Anandan Vannathan, A.; Chandewar, P.R.; Shee, D.; Mal, S.Nowadays, metal-oxides impregnated conducting polymers as electrode materials are attracted much attention due to their higher stability. Here, the metal-oxide cluster, polyoxometalate (K5H2[PV4W8O40]·11H2O, PV4W8), was introduced into the polypyrrole (PPy) matrix to overcome the polymers stability issues, and thus, the resulting novel PV4W8/PPy (symmetric) composite electrode has been reported. XPS confirmed the presence of all atoms on the polymer backbone with respective oxidation states. Nevertheless, doping of PV4W8 on the conductive PPy matrix's surface can affectively improve the ion's transfer. Finally, the asymmetric PV4W8-PPy/PPy composite exhibits a prodigious specific capacitance of 291 F g−1, larger than the PPy (90.01 F g−1) and PV4W8 (39.03 F g−1) at 0.4 A g−1 current density. The PV4W8-PPy/PPy (asymmetric) electrode showed excellent cycle stability. However, a symmetric supercapacitor device based on PV4W8/PPy composite possesses a specific capacitance of 195.27 F g−1 and an energy density of 8.94 Wh kg−1 at the same current density as PV4W8-PPy/PPy (asymmetric) electrode with remarkable cycle stability. © 2021 Elsevier B.V.Item Exploring the Synergy of B, Ce Dopants in Codoped Titanium Dioxide Multifunctional Photocatalysts for Antibiotic Degradation and Microbial Disinfection Under Solar Light(John Wiley and Sons Inc, 2022) Manjunatha, M.; Chandewar, P.R.; Mahalingam, H.An eco-friendly, controllable citrate-EDTA complexing sol–gel method is employed to systematically synthesize a series of BxCe1−xTiO2 (x = 0.9, 0.8, 0.7 at%) codoped photocatalysts. The degradation of ciprofloxacin (CIP) and norfloxacin (NOR) antibiotics, as well as Escherichia coli disinfection under sunlight, is assessed using these synthesized codoped photocatalysts. After physicochemical characterization of the synthesized catalysts for particle size, surface area, morphology, crystal structure, surface chemistry, bandgap energy values, and recombination, it is evident that the codoping has improved the visible light absorption, reduced the recombination, and promoted higher crystallinity as well as anatase phase content. The codoped catalysts also demonstrate an enhanced photocatalytic activity under solar light with regard to the degradation of the chosen antibiotics when compared to the performance of the monodoped counterparts or the latest generation catalysts from the literature. The highest degradation performance (≈98%) is shown by B0.8Ce0.2TiO2 in the case of CIP and B0.9Ce0.1TiO2 in the case of NOR. Also, in the case of microbial disinfection, these codoped catalysts are much better (by a factor of ≈10) than that of the monodoped catalysts. © 2021 Wiley-VCH GmbH.Item Vanadomanganate as a synergistic component in high-performance symmetric supercapacitor(Elsevier Ltd, 2022) Maity, S.; Anandan Vannathan, A.A.; Chandewar, P.R.; Shee, D.; Das, P.P.; Mal, S.S.Supercapacitor devices fabricated from capacitive and battery-type hybrid electrodes have been projected as a promising energy storage system because of their ability to produce high specific power and energy simultaneously. In this work, we have demonstrated a facile method of impregnation of faradaic type manganese (III) polyoxovanadate, [MnV14O40]−6 on the high surface area substrate of activated carbon (AC) as well as graphene oxide (GO). Materials and electrochemical characterizations data confirm the successful incorporation of capacitive and faradaic type manganese (III) polyoxovanadate into the nanohybrid electrode material. Furthermore, the synergic effect between the carbonaceous nanostructures (AC/GO) and redox-active oxometalate (MnV14) provides a better pathway for ion transport to the interface resulting in enhancement of the conductivity, diffusion ability of the nanohybrid. Moreover, the battery-type MnV14 clusters disperse in the micro/mesopores of AC, whereas the oxygen-containing functional groups in GO act as active sites for anchoring of MnV14 clusters. Thus, the surface modification with MnV14 clusters enhances the specific capacitance of nanohybrid with remarkable electrical and mechanical stability. The AC/MnV14 nanohybrid exhibits an enhanced specific capacitance of 547 F g−1 with specific energy and power of 76 Wh kg−1 and 1600 W kg−1, respectively, at 0.8 A g−1 current density. Additionally, GO/MnV14 shows a specific capacitance of 330 F g−1 with improved specific energy and power of 30 Wh kg−1 and 1276 W kg−1, respectively, at the same current density. Moreover, both the nanohybrids possess excellent cycle stability by retaining 92% (AC/MnV14) and 90.6% (GO/MnV14) of initial capacitance even after 5000 sweeping cycles. © 2021 Elsevier B.V.Item Polyoxovanadate-Activated Carbon-Based Hybrid Materials for High-Performance Electrochemical Capacitors(Institute of Physics, 2022) Anandan Vannathan, A.; Chandewar, P.R.; Shee, D.; Mal, S.S.Two different polyoxovanadates derivatives, K5MnIVV11O32.10 H2O (MnV11) and K7MnIVV13O38.18 H2O (MnV13), have been studied to evaluate their electrochemical performance. These polyoxovanadates were deposited on activated carbon (AC) to prepare AC-MnV11 and AC-MnV13 composites. The electrochemical performance of the AC-MnV11 electrode exhibits the remarkable specific capacitance of 479.73 F g-1 at a current density of 0.6 A g-1, along with incredible specific power and energy of 960 W kg-1. Likewise, the AC-MnV13 exhibits a specific capacitance of 357.33 F g-1 at the current density of 0.6 A g-1 with a specific energy of 71.46 Wh kg-1. Interestingly, the AC-MnV11 could light up the red and yellow color LED bulbs for a duration of 80 and 60 s, respectively, indicating a considerable specific power of the material. The AC-MnV13 electrode shows significantly less lighting up during the 65 and 30 s period with red and yellow LED bulbs. © 2022 The Electrochemical Society ("ECS"). Published on behalf of ECS by IOP Publishing Limited.Item Phosphomolybdic acid embedded into biomass-derived biochar carbon electrode for supercapacitor applications(Elsevier B.V., 2023) J.e, M.; Chandewar, P.R.; Shee, D.; Mal, S.S.In high-performance, clean, safe, and cost-effective ways, supercapacitors are among the most promising ways to store and release nonfossil energy. In recent years, renewable biomass-derived activated carbon has been explored as a potential option for electrode material. It restricts their specific capacitance despite being environment-friendly and possessing intrinsic mechanical strength. In order to overcome this limitation and preserve all other properties, we are infusing polyoxometalate into the activated carbon; this increases specific capacitance with its fast reversible redox behaviour and preserves the carbon's characteristics. Beside suffusing phosphomolybdic acid (PMA) into biomass waste material, such as orange peel-derived activated carbon (OPAC), a new hybrid material (OPAC-PMA) was developed. The nanohybrid design was revealed by structural and morphological research, which showed high interfacial contact, allowing polyanions to redox rapidly. The novel hybrid electrode material (OPAC-PMA) has a capacitance value of 66% higher than the bare OPAC electrode. A further study showed that OPAC-PMA composite showed 88.23% cycle stability in 0.5 M H2SO4 electrolyte at 6 A g−1 for 4000 cycles. © 2023 Elsevier B.V.Item Waste dry cell derived photo-reduced graphene oxide and polyoxometalate composite for solid-state supercapacitor applications(Royal Society of Chemistry, 2023) Maity, S.; Biradar, B.R.; Srivastava, S.; Chandewar, P.R.; Shee, D.; Das, P.; Mal, S.S.In the modern era, realizing highly efficient supercapacitors (SCs) derived through green routes is paramount to reducing environmental impact. This study demonstrates ways to recycle and reuse used waste dry cell anodes to synthesize nanohybrid electrodes for SCs. Instead of contributing to landfill and the emission of toxic gas to the environment, dry cells are collected and converted into a resource for improved SC cells. The high performance of the electrode was achieved by exploiting battery-type polyoxometalate (POM) clusters infused on a reduced graphene oxide (rGO) surface. Polyoxometalate (K5[α-SiMo2VW9O40]) assisted in the precise bottom-up reduction of graphene oxide (GO) under UV irradiation at room temperature to produce vanadosilicate embedded photo-reduced graphene oxide (prGO-Mo2VW9O40). Additionally, a chemical reduction route for GO (crGO) was trialed to relate to the prGO, followed by the integration of a faradaic monolayer (crGO-Mo2VW9O40). Both composite frameworks exhibit unique hierarchical heterostructures that offer synergic effects between the dual components. As a result, the hybrid material's ion transport kinetics and electrical conductivity enhance the critical electrochemical process at the electrode's interface. The simple co-participation method delivers a remarkable specific capacity (capacitance) of 405 mA h g−1 (1622 F g−1) and 117 mA h g−1 (470 F g−1) for prGO-Mo2VW9O40 and crGO-Mo2VW9O40 nanocomposites alongside high capacitance retentions of 94.5% and 82%, respectively, at a current density of 0.3 A g−1. Furthermore, the asymmetric electrochromic supercapacitor crGO//crGO-Mo2VW9O40 was designed, manifesting a broad operating potential (1.2 V). Finally, the asymmetric electrode material resulted in an enhanced specific capacity, energy, and power of 276.8 C g−1, 46.16 W h kg−1, and 1195 W kg−1, respectively, at a current density of 0.5 A g−1. The electrode materials were tested in the operating of a DC motor. © 2023 The Royal Society of Chemistry.Item High areal capacitance polyoxotungstate-reduced graphene oxide-based supercapacitors(Elsevier B.V., 2023) Biradar, B.R.; Maity, S.; Chandewar, P.R.; Shee, D.; Das, P.P.; Mal, S.S.The modern lifestyle has driven the advent of high-power electronic gadgets to need high-efficiency energy storage devices. Towards that goal, reduced graphene oxide (rGO) mediated polyoxometalates (POMs) based electrode materials are increasingly showing promising performance for building efficient energy storage devices primarily due to their redox properties. In this report, the silicotungstate [K5[SiVW11O40]. nH2O (SiVW11) embedded rGO nanocomposites as electrode materials in supercapacitor applications were synthesized via chemical and hydrothermal methods. The synthesized nanocomposites were characterized by various techniques, such as Fourier-Transform-Infrared (FTIR) Spectroscopy, Powder X-ray Diffraction (XRD) and Energy Dispersive X-ray Spectroscopy (EDS), Thermogravimetric Analysis (TGA), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) measurement. The nanocomposite's electrochemical properties were examined by adopting a two-electrode setup with cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) in a 0.5 M H2SO4 electrolyte medium. The hydrothermally reduced graphene oxide (HrGO) nanocomposite exhibited a noticeable surge in areal capacitance of 377.4 mF/cm2 at a current density of 1.5 mA/cm2. The resulting composite had 52.4 µWh/cm2 and 1500 µW/cm2 as energy and power density, respectively at 1.5 mA/cm2 current density. In addition, the capacitance retention is over 81% after 5000 cycles at a current density of 9 mA/cm2. The highest specific power of 5000 µW/cm2 was obtained at 5 mA/cm2 current density. On the other hand, chemically reduced graphene (CrGO) nanocomposite showed an areal capacitance of 277.2 mF/cm2 at the same current density. As a result, the SiVW11 clusters coupled with the rGO increase the areal capacitance of nanocomposites with exceptional electrical and mechanical stability. From an application standpoint, both composites were employed successfully for running a DC motor in a series cell connection. © 2023 Elsevier B.V.