Chemistry - Research Publications
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Item 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 KantaHydrogen 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.Item 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 KantaIn 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.Item 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, KamleshThe 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.Item 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-RonElectrochemical (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.Item 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.Item 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 KantaAlthough 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.Item 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 KantaHere, 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.Item Access to carbon nanofiber composite hydrated cobalt phosphate nanostructure as an efficient catalyst for the hydrogen evolution reaction(Frontiers Media S.A., 2023-02-23T00:00:00) Ahmed, Imtiaz; Biswas, Rathindranath; Sharma, Rohit; Burman, Vishal; Haldar, Krishna KantaAttractive technology for producing sustainable hydrogen with water electrolyzers was foreseen as one of the most promising ways to meet the increasing demands of renewable resources and electricity storage. Mainly used for the efficient generation of H2, water electrolysis involving hydrogen evolution reactions (HERs) depends on efficient and affordable electrocatalysts. Hydrogen is an effective fuel that can be produced by splitting water. Hence, the search for highly efficient HER catalysts is a major challenge as efficient hydrogen evolution catalysts are sought to replace catalysts such as platinum. Here, we describe a low-cost and highly effective electrocatalyst for the proper incorporation of the HER electrocatalyst with low overpotential, effective charge transfer kinetics, low Tafel slope, and good durability. By using a simple hydrothermal approach to produce Co3(PO4)2.8H2O/CNF, it is possible to attach Co3(PO4)2.8H2O to the surface of carbon nanofibers (CNFs), which also exhibit remarkable HER activity at an overpotential of 133�mV and produce a current density of 10�mA/cm2 and a 48�mV/decade for the Tafel slope. Large electrochemical surface areas and easy charge transfer from Co3(PO4)2.8H2O to the electrode through conductive Co3(PO4)2.8H2O/CNF composites are the reasons for the improved performance of Co3(PO4)2.8H2O/CNF. Copyright � 2023 Ahmed, Biswas, Sharma, Burman and Haldar.Item Coupling Nonstoichiometric Zn0.76Co0.24S with NiCo2S4Composite Nanoflowers for Efficient Synergistic Electrocatalytic Oxygen and Hydrogen Evolution Reactions(American Chemical Society, 2022-12-15T00:00:00) Biswas, Rathindranath; Thakur, Pooja; Ahmed, Imtiaz; Rom, Tanmay; Ali, Mir Sahidul; Patil, Ranjit A.; Kumar, Bhupender; Som, Shubham; Chopra, Deepak; Paul, Avijit Kumar; Ma, Yuan-Ron; Haldar, Krishna KantaTransition-metal sulfide-based composite nanomaterials have garnered extensive interest not only for their unique morphological architectures but also for exploring as a noble-metal-free cost-effective, durable, and highly stable catalyst for electrochemical water splitting. In this work, we synthesized in situ nonstoichiometric Zn0.76Co0.24S with NiCo2S4binary composite flowers (Zn0.76Co0.24S/NiCo2S4) in one step by thermal decomposition of Zn2[PDTC]4and Ni[PDTC]2complexes by a solvothermal process in a nonaqueous medium from their molecular precursor, and their potential application in electrochemical oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) was investigated. Field-emission scanning electron microscopy and transmission electron microscopy analyses revealed the flower-shaped morphology of as-synthesized Zn0.76Co0.24S/NiCo2S4. Again, the structural and chemical compositions were confirmed through powder X-ray diffraction and X-ray photoelectron spectroscopy studies, respectively. The as-obtained 3D flower-type Zn0.76Co0.24S/NiCo2S4nanostructure was further subject to electrochemical OER and HER in alkaline and acidic media, respectively. Zn0.76Co0.24S/NiCo2S4showed low overpotential values of 248 mV (Tafel slope, 85 mV dec-1) and 141 mV (Tafel slope, 79 mV dec-1) for OER and HER activities, respectively, due to the synergistic effects of Zn0.76Co0.24S and NiCo2S4. Several long-term stability tests also affirmed that the Zn0.76Co0.24S/NiCo2S4composite nanostructure is a highly stable and efficient electrocatalyst toward OER and HER activities as compared to the recently reported superior bifunctional electrocatalysts as well as state-of-the-art materials. � 2023 American Chemical Society. All rights reserved.Item Green synthesis of hybrid papain/Ni3(PO4)2 rods electrocatalyst for enhanced oxygen evolution reaction(Royal Society of Chemistry, 2022-10-21T00:00:00) Ahmed, Imtiaz; Biswas, Rathindranath; Singh, Harjinder; Patil, Ranjit A.; Varshney, Rohit; Patra, Debabrata; Ma, Yuan-Ron; Haldar, Krishna KantaHydrogen production using electrocatalytic water splitting provides encouraging innovations for enduring and clean energy generation as an option in contrast to traditional energy sources. Improvement in exceptionally dynamic electrocatalysts is of tremendous interest for work on the proficiency of gas generation, which has been emphatically blocked because of the sluggish kinetics of the oxygen evolution reaction (OER). We have synthesized a noble rod-shaped papain/Ni3(PO4)2 catalyst, which was further explored for electrocatalytic OER activity. An environmentally benign approach was applied to prepare binary papain/Ni3(PO4)2 in the presence of papain obtained from green papaya fruit. The yield of Ni3(PO4)2 rod structures could be controlled by varying the amount of papain extract during reaction conditions. The morphology and structural properties of the biogenic papain/Ni3(PO4)2 electrocatalyst were investigated with various microscopic and spectroscopic techniques, for example, FE-SEM, XRD, XPS, and FTIR. To show how such a papain/Ni3(PO4)2 hybrid structure could deliver more remarkable electrocatalytic OER activity, we inspected the correlation between catalytic demonstrations of the papain/Ni3(PO4)2 catalyst and its constituents, and the role of papain on its own was studied during the OER process. A biosynthesised papain/Ni3(PO4)2 catalyst exhibits excellent electrochemical OER performance with the smallest overpotentials of 217 mV, 319 mV and 431 mV in alkaline, neutral and acidic conditions, respectively, at 10 mA cm?2 current density. Transport of ions and electrons is also assisted by the long peptide backbone present in papain, which plays an important role in boosting OER activity. Our results reveal that papain/Ni3(PO4)2 shows better electrocatalytic OER execution along with cyclic stability compared to its different counterparts, owing to synergism-assisted enhancement by several amino acids from papain with metal ions in Ni3(PO4)2 � 2022 The Royal Society of Chemistry.