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 Polyoxovanadate inhibition of: Escherichia coli growth shows a reverse correlation with Ca2+-ATPase inhibition(Royal Society of Chemistry, 2019) Marques-Da-Silva, D.; Fraqueza, G.; Lagoa, R.; Anandan Vannathan, A.A.; Mal, S.S.; Aureliano, M.Recently, a global analysis of the structure-activity-relationship of a series of polyoxometalates (POMs) revealed that the most active POMs were ascribed to be polyoxovanadates (POVs), especially decavanadate (V10), which was very active against certain bacteria (Bijelic et al., Chem. Commun., 2018). The present study explores this observation and compares the effects of three POVs namely MnV11, MnV13 and V10 against Escherichia coli growth. It was observed that MnV11 presents the lowest growth inhibition (GI50) value for Escherichia coli followed by the MnV13 compound, being about 2 times lower than that of V10; respectively, the values obtained were 0.21, 0.27 and 0.58 mM. All three compounds were more effective than vanadate alone (GI50 = 1.1 mM) and also than decaniobate, Nb10 (GI50 > 10 mM), an isostructural POM of V10. However, the POVs exhibiting the highest antibacterial activity (MnV11) were shown to have the lowest Ca2+-ATPase inhibitor capacity (IC50 = 58 ?M) whereas decavanadate, which was also very active against this membranar ATPase (IC50 = 15 ?M), was less active against bacterial growth, suggesting that POV inhibition of ion pumps might not be associated with the inhibition of Escherichia coli growth. This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.Item Improved electrochemical performance of graphene oxide supported vanadomanganate (IV) nanohybrid electrode material for supercapacitors(Elsevier Ltd, 2020) Kumari, S.; Maity, S.; Anandan Vannathan, A.A.; Shee, D.; Das, P.P.; Mal, S.S.Graphene oxide (GO)-supported polyoxometalates (POMs) have been considered as promising electrode materials for energy storage applications due to their ability to undergo fast and reversible redox reactions. Herein, vanadomanganate-GO composites (K7MnIVV13O38.18H2O-GO with 2:1 and 4:1 ratio) were investigated for use as potential electrode materials in supercapacitors (SCs). The K7MnIVV13O38.18H2O (MnV13) was synthesized and anchored on GO through electron transfer interaction and electrostatic interaction to make the composite electrodes for the present study. All synthesized electrode materials were fully characterized by various techniques, e.g., Fourier Transform Infrared (FTIR) Spectroscopy, Powder X-ray Diffraction (XRD), Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS) and High Resolution-Transmission Electron Microscopy (HR-TEM). The electrochemical properties of MnV13/GO composites with different MnV13/GO ratios were investigated by two-electrode cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) in different electrolytes. The MnV13/GO composite of ratio 2:1 in 1 M LiCl electrolyte and that of ratio 4:1 in 1 M Na2SO4 electrolyte showed significant specific capacitance values of 269.15 F/g and 387.02 F/g, respectively and energy density of 37.38 Wh/kg and 53.75 Wh/kg, respectively for a scan rate of 5 mV/s. Interestingly, the 1:1 (MnV13/GO) composite in 1 M Na2SO4 and 1 M LiCl electrolytes showed very low specific capacitance values as the deposition of MnV13 on GO was not sufficient, as indicated by FTIR and SEM. Thus, it is evident that the specific capacitance value of these composite materials depends on the amount of MnV13 deposited on GO and these composite materials exhibit the potential to improve the performance of GO-based SCs. © 2019Item In situ vanadophosphomolybdate impregnated into conducting polypyrrole for supercapacitor(Elsevier Ltd, 2020) Anandan Vannathan, A.A.; Maity, S.; Kella, T.; Shee, D.; Das, P.P.; Mal, S.S.The fast modernization and advancement in lifestyle increase the consumption of power daily due to all innovative technologies, e.g., hybrid vehicles, solar cells, smart power grid, communication devices, artificial hearts, etc. Conducting organic polymer-based energy storage devices had attracted much attention due to the conductive nature for a long time. However, its application has been restricted because of swelling and shrinking capability during the charge and discharge cycle. The combination of redox-active inorganic metal oxides, such as polyoxometalates (multi-metal oxide cluster) with conduction polymers, could enhance the material's stability due to its fast multi-electron redox property. Here, we report the two polypyrroles combined vanadophosphomolybdates, namely PPy-H4[PVMo11O40] and PPy-H5[PV2Mo10O40] nanohybrid electrode materials. The PPy-H5[PV2Mo10O40] electrode material behaves as pseudocapacitance and can deliver an excellent capacitance of 561.1 F/g in 0.1 M H2SO4 electrolyte solution at a 0.2 A/g current density, indicating capacitive composite material. The electrochemical impedance spectroscopy (EIS) reveals that PPy-H5[PV2Mo10O40] is more capacitive than PPy-H4[PVMo11O40] and PPy with equivalent series resistance (ESR) of 5.74 ?. The cell capacitance of PPy-H5[PV2Mo10O40] and PPy-H4[PVMo11O40] are found to be 5.38 and 9.15 mF, stipulating in small SC cell application. Likewise, the PPy-H5[PV2Mo10O40] nanohybrid electrode shows better responsive behavior with a relaxation time of 0.16 ms. Furthermore, the PPy-H5[PV2Mo10O40] electrode exhibits outstanding cycle stability, retaining ~95% of its capacitance after 4500 cycles as compare to PPy-H4[PVMo11O40] (~91%) electrode. © 2020Item Enhanced Power Density of Graphene Oxide–Phosphotetradecavanadate Nanohybrid for Supercapacitor Electrode(Springer, 2021) Maity, S.; Anandan Vannathan, A.A.; Kumar, K.; Das, P.P.; Mal, S.S.Successful exploration of supercapacitor (SC) material to integrate with high energy and high power density storage device still remains a daunting challenge. Conducting carbon nanostructures have been primarily used for this purpose; however, most of their surface area remains unutilized throughout the storage process. Herein, a new type of hybrid material has been reported by effectively using active sides of carbon nanostructures. Insertion of faradaic-type polyoxometalates (POMs), namely phosphotetradecavanadate (Na7[H2PV14O42], hereafter described as PV14), into the graphene oxide (GO) matrix creates a novel hybrid material for SC applications. Owing to the formation of nanohybrid, it can store charges both electrostatically and electrochemically. PV14/GO composite’s electrochemical behavior in different electrolyte (acidic/neutral) solutions shows different types of characteristics. The PV14/GO composite as a working electrode exhibits a high galvanostatic capacitance of 139 F/g while maintaining at a power density of 97.94 W/kg in 0.25 M H2SO4 electrolyte. The specific energy density was also found out to be around 56.58 Wh/kg at a 5 mV/s scan rate for the same electrolyte. Furthermore, in 1 M Na2SO4 solution, PV14/GO composite demonstrates a specific capacitance of 85.4 F/g at a scan rate of 5 mV/s. The equivalent series resistance for the device was found to be approximately 0.51 ? with a circuit resistance of 3.881 ?, using electrochemical impedance spectroscopy. The cell capacitance, employing the Nyquist plot, was calculated to be around 2.78 mF. © 2021, ASM International.Item One-Pot Synthesis of Polyoxometalate Decorated Polyindole for Energy Storage Supercapacitors(American Chemical Society, 2021) Anandan Vannathan, A.A.; Kella, T.; Shee, D.; Mal, S.S.The demand for energy storage supercapacitor devices has increased interest in completing all innovative technologies and renewable energy requirements. Here, we report a simple method of two polyoxomolybdate (H4[PVMo11O40] and H5[PV2Mo10O40]) doped polyindole (PIn) composites for electrochemical supercapacitors. The interactions between polyoxomolybdates and PIn were measured by Fourier transform infrared spectroscopy (FTIR), and powder XRD, and stability was measured by thermogravimetry. The field emission scanning microscopy (FESEM) was employed to investigate the morphology of the materials. The electrochemical measurements show that the PIn/PV2Mo10 electrode exhibits a higher capacitance of 198.09 F/g with an energy density of 10.19 Wh/kg and a power density of 198.54 W/kg at 0.2 A/g current density than the PIn/PVMo11 electrode. Both electrodes show a pseudocapacitance behavior due to the doping of redox-active polyoxomolybdates on the PIn surface and enhance the electrochemical properties. The electrodes' capacitive nature was measured by electrochemical impedance spectroscopy (EIS), which shows that the PIn/PVMo11 electrode has a resistive nature within the electrode-electrode interface. Moreover, the PIn/PV2Mo10 electrode offers remarkable cycle stability, retaining ?84% of its capacitance after 10,000 cycles (?83% for the PIn/PVMo11 electrode). The higher specific capacitance, faster charge/discharge rates, and higher cycle stability make them promising electrodes in supercapacitors. ©Item Imidazolium cation linkers of polyoxomolybdate-polypyrrole nanocomposite electrode-based energy storage supercapacitors(Elsevier Ltd, 2022) Muhammed Anees, P.K.; Anandan Vannathan, A.A.; Abhijith, M.B.; Kella, T.; Shee, D.; Mal, S.S.The electrochemical properties of a new hybrid electrode, liquid-polyoxometalate-polypyrrole (BMIM-PVMo11-PPy) have been studied. The H4[PVMo11O40] (PVMo11) was combined with 1-Butyl-3-methyl-imidazolium (BMIM) ionic liquid and then doped on the polypyrrole (PPy) surface. In order to investigate the interaction between the BMIM, PVMo11, and PPy compound was characterized using various analytical techniques, such as Infrared spectroscopy, thermal stability analysis, powder X-ray diffraction, multinuclear NMR (1H and 13C), FESEM, EDX, and surface adsorption studies. The electrochemical performance of the BMIM-PVMo11-PPy composite material has been tested in an aqueous 0.25 M H2SO4 electrolytic solution. The BMIM-PVMo11-PPy composite exhibits the highest specific capacitance of 527.39 F g−1 at a current density of 1 A g−1, along with remarkable specific energy and power of 51.07 Wh kg−1 and 1078.96 W kg−1, respectively. The BMIM-PVMo11-PPy composite was observed to light up red and blue color LED bulbs for 66 and 16 s, respectively, with 84 mg of sample coated on carbon cloth, suggesting an incredible specific power of that material. © 2021 Elsevier B.V.Item Investigations of redox-active polyoxomolybdate embedded polyaniline-based electrode material for energy application(Springer Science and Business Media Deutschland GmbH, 2022) Anandan Vannathan, A.A.; Kella, T.; Shee, D.; Mal, S.S.Higher capacitance supercapacitors have received considerable attention, including their massive power density, high stability, and long cycle life. On the other hand, polymers have been known for their energy storage device application because of the pseudocapacitance behavior resulting from the extended conjugation over the polymer backbone. Here, we report a simple chemical bath deposition method for the synthesis of two polyoxometalates (H4[PVMo11O40] and H5[PV2Mo10O40]) impregnated polyaniline (PAni) composite (PVMo11@PAni and PV2Mo10@PAni) for electrochemical supercapacitors. Various analytical methods characterized the electrode materials, e.g., Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) method, and the morphological features of those electrodes were acquired by field emission scanning microscopy (FESEM). The exceptionally high average capacitance of 1371 F g−1 was obtained for the composite PVMo11@PAni electrode at a 3 A g−1 current density and 1 V potential window with an energy density of 137.5 W h kg−1. The PVMo11@PAni composite electrode showed almost 4.3 times the higher energy density than pure PAni and 2.3 times higher than PV2Mo10@PAni. In contrast, PV2Mo10@PAni composite showed 1.9 times more energy density than pure PAni composite electrode. Interestingly, high average capacitance, charge–discharge rates, and high energy density with high-level power delivery make them promising electrode candidates for supercapacitors. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.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 High-performance electrochemical supercapacitors based on polyoxometalate integrated into polyaniline and activated carbon nanohybrid(Springer Science and Business Media Deutschland GmbH, 2023) Anandan Vannathan, A.A.; Kella, T.; Shee, D.; Mal, S.S.Polyaniline (PANI) and carbonaceous materials and metallic compounds have played a significant role in energy storage and conversion devices. PANI has demonstrated tremendous potential in the supercapacitor industry due to its high specific capacitance, high flexibility, and economical price. The CPs damage the hierarchical structure during the charging and discharging process and start swelling. Thus, incorporating polyoxometalates (POMs) into the conducting polymer matrix increases the stability of the electrode material. Here, we have demonstrated a comparative study of two newly synthesized composite materials consisting of K5H2[PV4W8O40] ·11H2O, (PV4W8) POM incorporated into two different supports, such as pseudocapacitive polyaniline (PANI) and EDLC activated carbon (AC) matrix. It was observed that the PANI-PV4W8 composite exhibited excellent capacitance nature at 0.5 M H2SO4 electrolyte solution than AC-PV4W8. The PANI-PV4W8 composite demonstrated the specific capacitance of 584 F g−1 at 0.8 A g−1. The composite also exhibited energy and power density of 81Wh kg−1 and 1598 W kg−1, respectively. Besides, the composite shows 93.13% capacity retention after 4500 cycles by cyclic voltammetry measurement at a 500 mV s−1 scan rate. Furthermore, the AC-PV4W8 showed a specific capacitance of 62 F g−1 at the current density of 0.6 A g−1. Interestingly, The PANI-PV4W8 composite could glow up the red and yellow LED bulb for more than a minute, suggesting a promising electrode material for practical supercapacitor purposes. © 2023, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.