Faculty Publications
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Item Polyoxometalate-based materials for the effluent treatment of removing heavy metals in the water pollutants: mini review(Springer Science and Business Media Deutschland GmbH, 2023) Madhusree, J.E.; Mal, S.S.Water contamination is a big concern nowadays due to increased human activity and the quick expansion of modern industry and agriculture. In our current environment, heavy metal pollution has become a primary concern. Treatment of heavy metals is especially significant, because these metals absorb into biological cells and can lead to severe illness and disorders. Several studies have been conducted over the last several years to remove heavy metals from wastewater using various strategies and materials. Among those strategies, complexation's reaction and the electrochemical sensor are attractive because of their excellent metal selectivity, cost-effectiveness, short analytical time, and high removal efficiency. Polyoxometalates (POMs) are a group of metal–oxygen cluster compounds with extremely electronegative and oxo-enriched surfaces and variable structure and size. POMs have drawn much interest in removing toxins from wastewater due to their electrical and physical characteristics. The removal of heavy metals from wastewater is covered in this review using POM and POM-based MOF nanocomposites in various treatment methods like complexation and electrochemical sensor, which have the advantages of high removal efficiency, excellent metal selectivity, in-expansive, and rapid analytical times. © 2023, King Abdulaziz City for Science and Technology.Item Electrocatalysis by crown-type polyoxometalates multi-substituted by transition metal ions; Comparative study(Elsevier Ltd, 2015) Naseer, R.; Mal, S.S.; Kortz, U.; Armstrong, G.; Laffir, F.; Dickinson, C.; Vagin, M.; McCormac, T.Abstract The difference in electrochemical properties of three crown-type polyoxometalates multi-substituted by Fe3+, Ni2+ or Co2+ ions and their precursor has been rationalized with respect to their electrocatalytic performances studied in solution and in the immobilized state within the layer-by-layer film formed with a positively charged pentaerythritol-based Ru(II)-metallodendrimer. The film assembly was monitored with electrochemical methods and characterized by surface analysis techniques. An influence of the terminal layer on the electrode reaction and on film porosity has been observed. The electrocatalytic performance of the compounds on nitrite reduction was assessed in solution and in the immobilized state. © 2015 Elsevier Ltd.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 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 Activated carbon- supported Vanado-nickelate (IV) based hybrid materials for energy application(Elsevier Ltd, 2021) Maity, S.; BM, N.; Kella, T.; Shee, D.; Das, P.P.; Mal, S.S.The rapid development of supercapacitor (SC) technology leads to increased demand for nanofabrication of novel and effective electroactive hybrid materials for next-generation energy storage devices. Herein, nickel tetradecavanadate, K2H5[NiV14O40](NiV14), is doped into porous activated carbon (AC), for the first time, in different wt.% in order to investigate the homogeneous loading of the inorganic metal-oxide component on the AC matrix. The resulting complex, AC-NiV14, is found to have possessed an enhanced electrochemical characteristic (for both symmetric and asymmetric SC cell), which operates at a significantly higher potential of 1.2 V. The combination of the double-layer capacitance (EDLC) and the redox-active polyoxometalate cluster leads to an intrinsic increase in specific capacitance (capacity) (from 45.3 Fg?1 (54.4 Cg?1) for AC to 316 Fg?1 (379.2 Cg?1) for 15 wt.% AC-NiV14 at a current density of 1 Ag?1). It was also observed that there is an increase of 20% in the operating voltage compared to conventional AC supercapacitors with acidic aqueous electrolytes. Firstly, symmetric supercapacitor's electrochemical performances of various wt.% of NiV14 composition were studied in acidic aqueous electrolyte (0.5 M H2SO4) solution. We observed that the 15 wt.% of AC-NiV14 hybrid electrode showed remarkable specific energy value (~63.2 Wh kg?1) compared with pristine AC and NiV14 electrodes, separately. Besides, the asymmetric layout (AC//AC-NiV14) increased the potential window up to 1.5 V and enhanced the specific energy and power values (90.1 Whkg?1 and 2400 Wkg?1, respectively), with 98% coulombic efficiency. Meanwhile, the AC-NiV14//NiV14 asymmetric cell possesses a specific capacitance (capacity) of 375 Fg?1 (450 Cg?1) with a maximum power of 3140 Wkg?1 at the high current density of 2 Ag?1. © 2021 Elsevier LtdItem 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 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.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.