School Of Basic And Applied Sciences

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    Unraveling the Role of Orbital Interaction in the Electrochemical HER of the Trimetallic AgAuCu Nanobowl Catalyst
    (American Chemical Society, 2023-03-24T00:00:00) Biswas, Rathindranath; Dastider, Saptarshi Ghosh; Ahmed, Imtiaz; Barua, Sourabh; Mondal, Krishnakanta; Haldar, Krishna Kanta
    Unraveling the origins of the electrocatalytic activity of composite nanomaterials is crucial but inherently challenging. Here, we present a comprehensive investigation of the influence of different orbitals� interaction in the AuAgCu nanobowl model electrocatalyst during the hydrogen evolution reaction (HER). According to our theoretical study, AgAuCu exhibits a lower energy barrier than AgAu and AgCu bimetallic systems for the HER, suggesting that the trimetallic AgAuCu system interacts optimally with H*, resulting in the most efficient HER catalyst. As we delve deeper into the HER activity of AgAuCu, it was observed that the presence of Cu allows Au to adsorb the H* intermediate through the hybridization of s orbitals of hydrogen and s, dx2-y2, and dz2 orbitals of Au. Such orbital interaction was not present in the cases of AgAu and AgCu bimetallic systems, and as a result, these bimetallic systems exhibit lower HER activities. � 2023 American Chemical Society.
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    Transition Metal-based Perovskite Oxides: Emerging Electrocatalysts for Oxygen Evolution Reaction
    (John Wiley and Sons Inc, 2023-01-23T00:00:00) Deeksha; Kour, Pawanpreet; Ahmed, Imtiaz; Sunny; Sharma, Surender Kumar; Yadav, Kamlesh; Mishra, Yogendra Kumar
    Development of clean and sustainable renewable energy sources is imperative to deal with the future energy crises. Various technologies have been developed in this context, for example, water electrolysis, reversible fuel cell and metal-air batteries etc. However, the sluggish kinetics of oxygen evolution reaction (OER) occurring at the anode of these energy storage/conversion systems becomes a significant hurdle. Recently, researchers utilized noble metals as electrocatalysts to enhance their efficiency still the high cost and scarcity of these materials draw the attention of researchers towards the cost-effective Perovskite oxide nanomaterials due to their extraordinary flexibility. In this review, the importance of perovskite oxide nanomaterials as electrocatalysts for OER is discussed, followed by related reaction mechanisms and series of activity descriptors. Fundamental understanding about the instrumentation, parameters and protocols for the experimental measurements including concerned issues are also summarized. Moreover, various activation strategies adopted in recent years to enhance the electrocatalytic performance of perovskite oxides are also underlined. The article concludes with an outlook of existing challenges and future scope of these materials as electrocatalysts. The challenges and prospects discussed herein may pave the ways to rationally design the highly active and stable perovskites to outperform noble metal-based OER electrocatalysts. � 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH.
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    LaCoO3Perovskite Nanoparticles Embedded in NiCo2O4Nanoflowers as Electrocatalysts for Oxygen Evolution
    (American Chemical Society, 2022-11-08T00:00:00) Kubba, Deeksha; Ahmed, Imtiaz; Kour, Pawanpreet; Biswas, Rathindranath; Kaur, Harpreet; Yadav, Kamlesh; Haldar, Krishna Kanta
    It is essential to design high-efficiency, stable, and inexpensive electrocatalysts for the oxygen evolution reaction (OER). We fabricate a hybrid system of perovskite LaCoO3 with spinel NiCo2O4 denoted LaCoO3/NiCo2O4 via an in situ hydrothermal process. In situ incorporation of LaCoO3 nanoparticles on the NiCo2O4 nanoflower surface is confirmed by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images. Benefiting from the interface engineering, the obtained LaCoO3/NiCo2O4 hybrid nanoflowers exhibit the lowest overpotential of 353 at a current density of 10 mA/cm2 and a small Tafel slope of 59 mV/dec in alkaline media compared with pristine LaCoO3 (401 mV, 116 mV/dec) and NiCo2O4 (386 mV, 73 mV/dec). The optimized sample possesses a higher electrochemical surface of 111.45 cm2 than LaCoO3 perovskite (35.37 cm2) and NiCo2O4 spinel oxide (61.37 cm2) structures. The enhanced OER performance of the LaCoO3/NiCo2O4 composite structure is due to the accumulation of LaCoO3 nanoparticles over NiCo2O4 petals, which introduces a substantial number of electrochemically active sites for the catalysis process to promote charge and mass transport. In addition to this, LaCoO3/NiCo2O4 exhibits long-term stability over 20 h. Thus, it is believed that the excellent OER activity of the LaCoO3/NiCo2O4 composite structure is associated with strong interaction between LaCoO3 and NiCo2O4 as well as a large surface area and a unique flower structure. � 2022 American Chemical Society.
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    Bifunctional electrochemical OER and HER activity of Ta2O5 nanoparticles over Fe2O3 nanoparticles
    (Royal Society of Chemistry, 2023-08-23T00:00:00) Ahmed, Imtiaz; Burman, Vishal; Biswas, Rathindranath; Roy, Ayan; Sharma, Rohit; Haldar, Krishna Kanta
    Hydrogen production via electrocatalytic water splitting offers encouraging innovations for sustainable and clean energy production as an alternative to conventional energy sources. The improvement of extraordinarily dynamic electrocatalysts is of great interest for work on the performance of gas generation, which is firmly blocked due to the sluggish kinetics of the oxygen evolution reaction (OER). The development of highly efficient base metal catalysts for electrochemical hydrogen and oxygen evolution reactions (HER and OER) is a challenging and promising task. In the present work, a particle over particles of Fe2O3 and Ta2O5 was successfully produced by hydrothermal treatment. The prepared composite shows promising catalytic performance when used as an electrochemical catalyst for OER and HER in alkaline and acidic electrolytes with low overpotentials of 231 and 201 mV at 10 mV cm?2, small Tafel slopes of 71 and 135 mV dec?1, respectively, and good stability properties. The calculated electrochemical surface area (ECSA) for composites is five times higher than that of the original oxides. The result of the OER is significantly better than that of commercial IrO2 catalysts and offers a promising direction for the development of water-splitting catalysts. � 2023 The Royal Society of Chemistry.
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    Bio-assisted Synthesis of Au/Rh Nanostructure Electrocatalysts for Hydrogen Evolution and Methanol Oxidation Reactions: Composition Matters!
    (American Chemical Society, 2023-08-11T00:00:00) Biswas, Rathindranath; Dastider, Saptarshi Ghosh; Ahmed, Imtiaz; Biswas, Sayani; Mondal, Krishnakanta; Haldar, Krishna Kanta
    In the field of catalysis, bimetallic nanostructures have attracted much interest. Here, we discuss the effect of Au/Rh bimetallic composition-tuned nanostructure and electrocatalytic activity. A simple bio-assisted technique was used to fabricate multiple Au:Rh nanoplate ratios (25:75, 50:50, and 75:25). XRD and XPS studies show that both Au and Rh phases coexist in a bimetallic nanostructure, and electron microscopy confirms the formation of a triangle-shaped nanoplate. Au0.25Rh0.75 exhibited the maximum catalytic activity and good stability for hydrogen evolution reaction (HER) with an overpotential of 105 mV at a current density of 10 mA/cm2. On the other hand, Au0.50Rh0.50 exhibits a higher activity for methanol oxidation reaction (MOR) compared to the other compositions. Theoretical studies indicate that the electrocatalytic enhancement obtained for both HER and MOR relies on electronic modification effects of the surface, with the overall reaction energy profile being optimized due to Au/Rh d-band mixing. � 2023 American Chemical Society.
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    BiFeO3/g-C3N4/f-CNF ternary nanocomposite as an efficient photocatalyst for methylene blue dye degradation under solar light irradiation
    (Elsevier Ltd, 2023-06-21T00:00:00) Deeksha; Kour, Pawanpreet; Ahmed, Imtiaz; Haldar, Krishna Kanta; Yadav, C.S.; Sharma, Surender Kumar; Yadav, Kamlesh
    The development of Perovskite oxide photocatalysts with superior dye degradation efficiency under solar light irradiation has gained attention in recent years, owing to their extraordinary flexibility, chemical composition, and tunability. Herein, we report the facile synthesis of a novel ternary composite composed of BiFeO3 (BFO) perovskite, g-C3N4, and functionalized carbon nanofibers (f-CNF), referred to as BFO/g-C3N4/f-CNF using a simple solution method as a photocatalyst to accelerate the degradation of methylene blue dye. Detailed structural and microstructural features confirm the formation of a ternary composite composed of BFO nanoparticles and f-CNFs mounted on g-C3N4 nanosheets. The photocatalytic activity of the sample for the degradation of methylene blue dye was studied in solar light using UV�visible spectroscopy. The BFO/g-C3N4/f-CNF ternary composite displays excellent photocatalytic activity with a degradation rate of 87 % after illumination for 120 min under solar light than BFO, g-C3N4, and binary composites BFO/g-C3N4 and BFO/f-CNF. The highest rate constant (k = 0.01675 min?1) for BFO/g-C3N4/f-CNF further confirms improved photocatalytic efficiency. The red shift in the UV�visible absorption spectrum of BFO/g-C3N4/f-CNF indicates a reduced band gap (1.9 eV) compared to that of pure BFO (2.28 eV) and g-C3N4 ( 2.72 eV). A decrease in the photoluminescence intensity of the ternary composite compared to that of BFO indicates the inhibition of photoexcited electron recombination which results in the availability of more charge carriers for the photocatalytic process. The enhanced efficiency of BFO/g-C3N4/f-CNF can be explained by the synergistic effect between BFO and g-C3N4 and the incorporation of f-CNF further promotes the migration rate of electrons from BFO to g-C3N4. � 2023 Elsevier B.V.
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    Efficient MoS2/V2O5 Electrocatalyst for Enhanced Oxygen and Hydrogen Evolution Reactions
    (Springer, 2023-04-29T00:00:00) Haldar, Krishna Kanta; Ahmed, Imtiaz; Biswas, Rathindranath; Mete, Shouvik; Patil, Ranjit A.; Ma, Yuan-Ron
    Electrochemical (EC) water splitting is a promising approach for the generation of renewable hydrogen (H2) fuels and oxygen (O2) evolution. Composite structured molybdenum disulphide (MoS2)/vanadium pentoxide (V2O5) with low overpotential is a promising electrocatalyst for anodic and cathodic material for an alternative energy source. We fabricated a flower shape MoS2/V2O5 composite via a hydrothermal approach where V2O5grew on the surface of the MoS2 petals. The unique flower-type composite structure alleviates the surface expansion of electrode material. The electrochemical studies show that the composite possesses good stability with low overpotential and smaller Tafel slope compared to its constituents. It has been found that the MoS2/V2O5 composite exhibits a stable rate performance under the current density of 10�mA�cm?2 which indicates that the MoS2/V2O5 composite might be a good candidate for both oxygen and hydrogen evolution reactions.; Graphical Abstract: [Figure not available: see fulltext.] � 2023, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.
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    Cu-Metal Organic Framework Derived Multilevel Hierarchy (Cu/CuxO@NC) as a Bifunctional Electrode for High-Performance Supercapacitors and Oxygen Evolution Reaction
    (American Chemical Society, 2023-05-25T00:00:00) Abbas, Zahir; Hussain, Nissar; Ahmed, Imtiaz; Mobin, Shaikh M.
    The development of a MOFs-derived multilevel hierarchy in a single step still remains a challenging task. Herein, we have synthesized novel Cu-MOF via a slow diffusion method at ambient temperature and further utilized it as a precursor source for MOF-derived multilevel hierarchy (Cu/CuxO@NC, x = 1 and 2). This studies suggest that the organic ligands served as a source of an N-doped carbon matrix encapsulated with metal oxide nanoparticles which were confirmed by various characterization techniques; further BET analysis reveals a surface area of 178.46 m2/g. The synthesized multilevel hierarchy was utilized as an electro-active material in a supercapacitor that achieved a specific capacitance of 546.6 F g-1 at a current density of 1 A g-1 with a higher cyclic retention of 91.81% after 10 000 GCD cycles. Furthermore, the ASC device was fabricated using Cu/CuxO@NC as the positive electrode and carbon black as the negative electrode and utilized to enlighten the commercially available LED bulb. The fabricated ASC device was further employed for a two-electrode study which achieved a specific capacitance of 68 F g-1 along with a comparable energy density of 13.6 Wh kg-1. Furthermore, the electrode material was also explored for the oxygen evolution reaction (OER) in an alkaline medium with a low overpotential of 170 mV along with a Tafel slope of 95 mV dec-1 having long-term stability. The MOF-derived material has high durability, chemical stability, and efficient electrochemical performance. This work provides some new thoughts for the design and preparation of a multilevel hierarchy (Cu/CuxO@NC) via a single precursor source in a single step and explored multifunctional applications in energy storage and an energy conversion system. � 2023 American Chemical Society.
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    NiS/MoS2 Anchored Multiwall Carbon Nanotube Electrocatalyst for Hydrogen Generation and Energy Storage Applications
    (John Wiley and Sons Inc, 2023-04-05T00:00:00) Ahmed, Imtiaz; Biswas, Rathindranath; Iqbal, Muzahir; Roy, Ayan; Haldar, Krishna Kanta
    Although sulfide-based materials are known to be efficient catalysts for oxygen evolution reactions (OER), hydrogen evolution reactions (HER), and supercapacitor applications, improving the catalytic activity of sulfide materials for both electrochemical water splitting and supercapacitors remains a challenging problem. Here, an easy and one-step integrated methodology is implemented to develop NiS/MoS2 anchored multiwall carbon nanotubes (MWCNT/NiS/MoS2) catalysts that can effectively and robustly catalyze both the HER and OER. The MWCNT/NiS/MoS2 hybrid composite offers the lowest overpotential of 201 mV and 193 mV to achieve a current density of 10 mA/cm2 and ?10 mA/cm2 with a small Tafel slope of 58 mV/dec 41 mV/dec for OER and HER, respectively, in alkaline and acidic conditions. The obtained multi-walled carbon nanotubes anchored with intertwined NiS/MoS2 have a significant number of active sites and defects throughout the structure. The hybrid composite electrode delivered a specific capacitance of >371.45 F/g at 2 A/g in a two-electrode system, along with high energy density of 51.63 Wh/kg (ED) along with the power density (PD) of 953.63 W/kg, and good capacitance retention ?82% after 2000 cycles. Therefore, a tandem electron transfer mechanism between NiS and MoS2 (MoS2?NiS) is believed to have an electrical synergistic effect that promotes both HER and OER activity. This research opens a new path for the construction of multi-component, cheap electrocatalysts that are highly effective for overall water splitting and energy storage applications. � 2023 Wiley-VCH GmbH.
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    Facile Fabrication of Ni9S8/Ag2S Intertwined Structures for Oxygen and Hydrogen Evolution Reactions
    (John Wiley and Sons Inc, 2022-12-21T00:00:00) Biswas, Rathindranath; Ahmed, Imtiaz; Manna, Priyanka; Mahata, Partha; Dhayal, Rajendra S.; Singh, Amol; Lahtinen, Jouko; Haldar, Krishna Kanta
    Here, we report the fabrication of the unique intertwined Ni9S8/Ag2S composite structure with hexagonal shape from their molecular precursors by one-pot thermal decomposition. Various spectroscopic and microscopic techniques were utilized to confirm the Ni9S8/Ag2S intertwined structure. Powder X-ray Powder Diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis suggest that there is an enrichment of Ni9S8 phase in Ni9S8/Ag2S. The presence of Ag2S in Ni9S8/Ag2S improves the conductivity by reducing the interfacial energy and charge transfer resistance. When Ni9S8/Ag2S is employed as an electrocatalyst for electrochemical oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) activity, it requires a low overpotential of 152 mV for HER and 277 mV for OER to obtain the geometrical current density of 10 mA cm?2, which is definitely superior to that of its components Ni9S8 and Ag2S. This work provides a simple design route to develop an efficient and durable electrocatalyst with outstanding OER and HER performance and the present catalyst (Ni9S8/Ag2S) deserves as a potential candidate in the field of energy conversion systems. � 2022 Wiley-VCH GmbH.