Faculty Publications
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Item Effect of annealing temperature on the bifunctional electrocatalytic properties of strontium nickelate (SrNiO3) nanoparticles for efficient overall water splitting(Elsevier Ltd, 2022) J, J.; Jayalakshmi, J.; Rodney, J.D.The global trend in energy demand has paved way for clean hydrogen (H2) energy production at large scale. To address this issue, perovskite (ABX3) nanomaterials are widely researched to replace the noble metal electrocatalysts for electrochemical water splitting. In this work, the effect of annealing temperature on the structural and electrochemical properties of combustion derived strontium nickelate (SrNiO3) nanoparticles are studied. Benefitting from the unique features of perovskites, SrNiO3 nanoparticles displays excellent OER and HER activity in 1.0 M KOH with an overpotential of 259 mV and 451 mV to achieve 10 mAcm−2 respectively. SrNiO3 nanoparticles show superior HER activity when annealed at higher temperature and subtle change in OER activity. The stability of SrNiO3 nanoparticles were noteworthy as it shows no degradation even after 12 h. The overall water splitting of highly active SrNiO3 nanoparticles was carried out in a two-electrode system and the setup posted a cell voltage of 1.88 V at 10 mAcm−2 after continuous water splitting for 24 h. Thus, SrNiO3 nanoparticles may possibly serve as a potential bifunctional electrocatalyst for H2 production. © 2022 Hydrogen Energy Publications LLCItem 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 Combustion-derived BaNiO3 nanoparticles as a potential bifunctional electrocatalyst for overall water splitting(Elsevier Ltd, 2023) J, J.; Jayalakshmi, D.; Rodney, J.D.Electrochemical water electrolyser though an assuring solution for clean hydrogen production, the sluggish kinetics and high cost of existing precious metal electrocatalyst remains a barrier to its effective utilization. Herein, solution combustion route derived perovskite type barium nickelate (BaNiO3) nanoparticles were developed and studied for their bifunctional electrocatalytic properties towards overall water splitting. The unannealed BaNiO3 nanoparticles exhibited the highest OER and HER activity with overpotentials 253 mV and 427 mV respectively to attain 10 mAcm−2 in 1.0 M KOH. Using unannealed BaNiO3 as a bifunctional electrocatalyst in a two-electrode alkaline electrolyser, the cell was able to achieve the benchmark current density at a low cell voltage of 1.82 V. Impressively the setup's electrocatalytic performance improved 4.9% after continuous overall water splitting for 24 h at 30 mAcm−2. Therefore, BaNiO3 nanoparticles can be a low-cost and efficient alternative for noble metal electrocatalysts for clean H2 production. © 2022 Hydrogen Energy Publications LLCItem Significance of transition metal (Co, Ni and Zn) doping on the nano MnSe for high-performance supercapacitor electrode(Elsevier Ltd, 2024) Mascarenhas, F.J.; Rodney, J.D.; Kim, B.C.; Badekai Ramachandra, B.R.The demand for electrode materials in supercapacitors necessitates designs with exceptional performance, superior structure, and environmental sustainability, all while remaining affordable and abundantly available. This study introduces an economical hydrothermal synthesis method for producing MxMn1-xSe (M=Co / Ni / Zn) nanomaterials at varying concentrations (x = 0.0, 0.01, 0.02, and 0.03). Diverse characterization methods confirm the successful formation of nanomaterials. Among the materials studied, Co0.01Mn0.99Se nanoclusters exhibit superior performance as electrode materials for supercapacitors, delivering a specific capacitance of 421 F/g at 5 mV/s and 377 F/g at 1 A/g in a 5 M KOH solution. A two-electrode symmetric configuration was established utilizing Co0.01Mn0.99Se as the active material in a 5 M KOH electrolyte, yielding a notable specific capacitance of 73 F/g at 0.5 A/g. The maximum energy density and power density achieved are 20.44 Wh/kg and 2838 W/kg respectively. This configuration demonstrates the exceptional electrochemical performance and energy storage capabilities of Co0.01Mn0.99Se in a two-electrode system. Impressively, the symmetric cell maintains a significant 70% capacitance retention even after 5000 charge-discharge cycles. Considering these findings, the developed Co0.01Mn0.99Se emerges as a pivotal advancement, providing a robust framework for the development of cutting-edge energy conversion and storage technologies. © 2024 Elsevier B.V.Item Electrocatalytic synergies of melt-quenched Ni-Sn-Se-Te nanoalloy for direct seawater electrolysis(Elsevier B.V., 2024) Rodney, J.D.; Joshi, S.; Ray, S.; Rao, L.; Deepapriya, S.; Carva, K.; Badekai Ramachandra, B.R.; Udayashankar, N.K.; Perumal, S.; Sadhana, S.; Justin Raj, C.J.; Kim, B.C.The study focuses on the development of binary nanoalloys based on metal dichalcogenides (Sn30Se70, Ni30Te70) and quaternary nanoalloy (Ni15Sn15Se35Te35) using the melt quenching technique. The nanoalloys show extensive water splitting in fresh and real seawater. Sn30Se70-coated nickel foam achieved a benchmark current density of 349 mV for the oxygen evolution reaction (OER), while Ni15Sn15Se35Te35-coated nickel foam (NF) required only 185 mV for the hydrogen evolution reaction (HER) in 1 M KOH. The study also shows that a two-electrode system can achieve sustained total water splitting at higher current densities (1 A.cm?2). Modification with a CuSx layer over NF at the OER end facilitated faster kinetics and mitigated chlorine corrosion enabling direct seawater splitting at 1.26 V. Continuous direct splitting of seawater at 100 mA cm?2 for 120 h required only 1.88 V, showing an efficiency of 92.9 % for H2 production in real seawater. © 2024 Elsevier B.V.Item Cerium-Modulated Zinc Oxide for enhanced Photoelectrochemical Non-Enzymatic biosensing of Cholesterol: An experimental and First Principle Analysis(Elsevier B.V., 2024) Rao, L.; Rodney, J.D.; Joy, A.; Shivangi Nileshbhai, C.; James, A.; S, S.; Joyline Mascarenhas, F.; Udayashankar, N.K.; Anjukandi, P.; Chul Kim, B.; Badekai Ramachandra, B.R.Herein, we synthesized CexZn1-xO (x = 0.00, 0.01, 0.02, and 0.03) using the wet chemical method. The investigation explores photoelectrochemical (PEC) biosensors for enzyme-free detection of cholesterol, employing Ce0.03Zn0.97O (CZO3)/Nickel Foam (NF) as the active material. The investigation revealed notable enhancements in sensitivity for cholesterol detection, with a recorded activity of 2.812 mA.mM?1.cm?2, marking a twofold increase in comparison to dark mode (1.37 mA.mM?1.cm?2). The Limit of Detection (LOD) was determined to be 17 µM (light) and 28 µM (dark), while the Limit of Quantification (LOQ) was measured at 54 µM (light) and 98 µM (dark) in 0.1 M KOH solution. These findings demonstrate a linear detection range spanning from 80 µM to 2 mM. Ab-initio calculations based on Density Functional Theory (DFT) were carried out on 101 surfaces of both pristine ZnO and CZO3 to understand how the doping affected the pristine ZnO band gap. The findings indicate that CZO3 exhibits superior activity compared to pristine ZnO, underscoring its enhanced performance and potential for sensing application. The CZO3/NF photoelectrochemical (PEC) biosensor displayed notable cyclic stability, retaining 97 % of its performance over a 60-day period. This underscores its potential for reliable and enduring operation in biosensing applications. Additionally, CZO3/NF exhibited robust sensing capabilities when utilized with human serum samples, showcasing consistent performance in both dark and illuminated conditions. © 2024 Elsevier B.V.Item Sustained hydrogen production through alkaline water electrolysis using Bridgman–Stockbarger derived indium-impregnated copper chromium selenospinel(Elsevier Ltd, 2024) Jauhar, R.M.; Raji, R.; Deepapriya, S.; Raja, A.; Rao, L.; Joshi, S.; Era, P.; Badekai Ramachandra, B.R.; Udayashankar, N.K.; Vadivel, V.; Mangalaraja, R.V.; J, J.; Ghfar, A.A.; Senthilpandian, M.; Kim, B.C.; Rodney, J.D.The depletion of conventional fossil fuels necessitates the development of sustainable energy alternatives, with electrochemical water splitting for hydrogen (H2) production being a promising solution. However, large-scale hydrogen generation is hindered by the scarcity of cost-effective electrocatalysts to replace noble metals such as Pt and RuO2 in the Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER). In this study, we report the synthesis of CuCr2-xInxSe4 (x = 0, 0.2, 0.4) using a dual approach combining the Bridgman-Stockbarger method and ball milling. Among the synthesized materials, CuCr1.8In0.2Se4 demonstrates outstanding HER activity in 1.0 M KOH, achieving a potential of ?0.16 V vs. RHE at a current density of 10 mA cm?2. Moreover, the material shows remarkable durability during a three-electrode accelerated degradation test in an alkaline medium, maintaining its performance over 24 h at a constant current density of ?200 mA cm?2, with a stable potential of ?0.57 V vs. RHE. Additionally, CuCr1.8In0.2Se4 was tested in a two-electrode configuration alongside CoFe LDH, achieving a benchmark of 1.7 V for overall water splitting. It sustained a current density of 400 mA cm?2 for 24 h in an accelerated degradation test, exhibiting a minimal loss of 0.1 V after the testing period. These results highlight CuCr1.8In0.2Se4 as a promising non-noble metal catalyst for HER, demonstrating its potential to reduce reliance on noble materials for large-scale hydrogen production. © 2024 Hydrogen Energy Publications LLC