Department Of Chemistry
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Item Synergistic photophysical and electrochemical response of Te @ PANI for energy harvesting(Springer, 2023-01-07T00:00:00) Rani, Pinki; Jewariya, Yogesh; Haldar, Krishna Kanta; Biswas, Rathindranath; Alegaonkar, Prashant S.Materials with synergistic functionality are of great importance in consumer electronics. We report on the preparation and assessments of Te @ PANI composite for energy conversion and storage application. Initially, (5�15%) Te @ PANI composites were synthesized by the facile, room temperature, time and cost-effective solid-state synthesis technique followed by characterizations using Fourier transform infra-red, UV-Visible, energy dispersive spectroscopic including X-ray diffractometry and field electron scanning microscopy. Te exfoliates polymeric segments of PANI by bonding benzenoid rings through sulphonated impurity sites which have a profound impact on symmetry molecular bond vibrations. Its analysis is presented. In photophysical application, both dark and luminescent I-V measurements have been performed that showed a linear variation with minimum photo-resistance offered by 10% composite and reaching current > 10�mA under 1.5�V biased conditions. In storage response, Te @ PANI supercapacitor devices are dominating in inductive coupling over capacitive coupling by ten times. Corresponding shunt impedance is seen to be favourably lower for 10% composition, and respective charge transfer impedance has also followed identical behaviour over other classes of samples. The quality factor of the device for 10% is found to be almost twelve times better. However, at a low scan rate (10�mV/s), the presence of Te has changed the tendency of ion migration, thereby, reducing the magnitude of ion current by about three times with an increase in Te from 5 to 15%. Thus, fabricated composite demonstrated synergistic aspects of energy. � 2023, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.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.Item Dithiophosphonate Anchored Heterometallic (Ag(I)/Fe(II)) Molecular Catalysts for Electrochemical Hydrogen Evolution Reaction(American Chemical Society, 2022-08-12T00:00:00) Jangid, Dilip Kumar; Dastider, Saptarshi G.; Biswas, Rathindranath; Khirid, Samreet; Meena, Sangeeta; Kumar, Pankaj; Sahoo, Subash C.; Verma, Ved Prakash; Makde, Ravindra D.; Kumar, Ashwani; Jangir, Ravindra; Mondal, Krishnakanta; Haldar, Krishna Kanta; Dhayal, Rajendra S.The dichalcogenide ligated molecules in catalysis to produce molecular hydrogen through electroreduction of water are rarely explored. Here, a series of heterometallic [Ag4(S2PFc(OR)4] [where Fc = Fe(?5-C5H4)(?5-C5H5), R = Me, 1; Et, 2; nPr, 3; isoAmyl, 4] clusters were synthesized and characterized by IR, absorption spectroscopy, NMR (1H, 31P), and electrospray ionization mass spectrometry. The molecular structures of 1, 2, and 3 clusters were established by single-crystal X-ray crystallographic analysis. The structural elucidation shows that each triangular face of a tetrahedral silver(I) core is capped by a ferrocenyl dithiophosphonate ligand in a trimetallic triconnective (?3 ?2, ?1) pattern. A comparative electrocatalytic hydrogen evolution reaction of 1-5 (R = iPr, 5) was studied in order to demonstrate the potential of these clusters in water splitting activity. The experimental results reveal that catalytic performance decreases with increases in the length of the carbon chain and branching within the alkoxy (-OR) group of these clusters. Catalytic durability was found effective even after 8 h of a chronoamperometric stability test along with 1500 cycles of linear sweep voltammetry performance, and only 15 mV overpotential was increased at 5 mA/cm2 current density for cluster 1. A catalytic mechanism was proposed by applying density functional theory (DFT) on clusters 1 and 2 as a representative. Here, a ?1 coordinated S-site between Ag4 core and ligand was found a reaction center. The experimental results are also in good accordance with the DFT analysis. � 2022 American Chemical Society.Item Genomic DNA-mediated formation of a porous Cu2(OH)PO4/Co3(PO4)2�8H2O rolling pin shape bifunctional electrocatalyst for water splitting reactions(Royal Society of Chemistry, 2022-01-28T00:00:00) Singh, Harjinder; Ahmed, Imtiaz; Biswas, Rathindranath; Mete, Shouvik; Halder, Krishna Kamal; Banerjee, Biplab; Haldar, Krishna KantaAmong the accessible techniques, the production of hydrogen by electrocatalytic water oxidation is the most established process, which comprises oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Here, we synthesized a genomic DNA-guided porous Cu2(OH)PO4/Co3(PO4)2�8H2O rolling pin shape composite structure in one pot. The nucleation and development of the porous rolling pin shape Cu2(OH)PO4/Co3(PO4)2�8H2O composite was controlled and stabilized by the DNA biomolecules. This porous rolling pin shape composite was explored towards electrocatalytic water oxidation for both OER and HER as a bi-functional catalyst. The as-prepared catalyst exhibited a very high OER and HER activity compared to its various counterparts in the absence of an external binder (such as Nafion). The synergistic effects between Cu and Co metals together with the porous structure of the composite greatly helped in enhancing the catalytic activity. These outcomes undoubtedly demonstrated the beneficial utilization of the genomic DNA-stabilised porous electrocatalyst for OER and HER, which has never been observed. This journal is � The Royal Society of Chemistry.Item Charge Separated One-Dimensional Hybrid Cobalt/Nickel Phosphonate Frameworks: A Facile Approach to Design Bifunctional Electrocatalyst for Oxygen Evolution and Hydrogen Evolution Reactions(American Chemical Society, 2021-09-30T00:00:00) Rom, Tanmay; Biswas, Rathindranath; Haldar, Krishna Kanta; Sarkar, Sourav; Saha, Uttam; Paul, Avijit KumarTwo new organoamine templated one-dimensional transition metal phosphonate compounds are synthesized, and their bifunctional electrocatalytic activities are examined in highly alkaline and acidic media. Compared with state-of-the-art materials, the cobalt phosphonate system is a new fabrication of sustainable and highly efficient catalysts toward electrochemical water splitting systems. � 2021 American Chemical Society. All rights reserved.