Browsing by Author "Haldar, Krishna Kanta"

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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 Kanta
Attractive 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.
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.
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.
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.
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 Kumar
Two 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.
Core-Size-Dependent Catalytic Properties of Bimetallic Au/Ag Core− Shell Nanoparticles
(ACS Publications, 2017) Haldar, Krishna Kanta; Kundu, Simanta; Patra, Amitava
Bimetallic core−shell nanoparticles have recently emerged as a new class of functional materials because of their potential applications in catalysis, surface enhanced Raman scattering (SERS) substrate and photonics etc. Here, we have synthesized Au/Ag bimetallic core−shell nanoparticles with varying the core diameter. The red-shifting of the both plasmonic peaks of Ag and Au confirms the core−shell structure of the nanoparticles. Transmission electron microscopy (TEM) analysis, line scan EDS measurement and UV−vis study confirm the formation of core−shell nanoparticles. We have examined the catalytic activity of these core−shell nanostructures in the reaction between 4- nitrophenol (4-NP) and NaBH4 to form 4-aminophenol (4-AP) and the efficiency of the catalytic reaction is found to be increased with increasing the core size of Au/Ag core−shell nanocrystals. The catalytic efficiency varies from 41.8 to 96.5% with varying core size from 10 to 100 nm of Au/Ag core−shell nanoparticles, and the Au100/Ag bimetallic core−shell nanoparticle is found to be 12-fold more active than that of the pure Au nanoparticles with 100 nm diameter. Thus, the catalytic properties of the metal nanoparticles are significantly enhanced because of the Au/Ag core−shell structure, and the rate is dependent on the size of the core of the nanoparticles.
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 Kanta
Transition-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.
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.
DNA Origami Directed Au Nanostar Dimers for Single-Molecule Surface-Enhanced Raman Scattering
(American Chemical Society, 2017) Tanwar, Swati; Haldar, Krishna Kanta; Sen, Tapasi; Tanwar, S.; Haldar, K.K.; Sen, T.
We demonstrate the synthesis of Au nanostar dimers with tunable interparticle gap and controlled stoichiometry assembled on DNA origami. Au nanostars with uniform and sharp tips were immobilized on rectangular DNA origami dimerized structures to create nanoantennas containing monomeric and dimeric Au nanostars. Single Texas red (TR) dye was specifically attached in the junction of the dimerized origami to act as a Raman reporter molecule. The SERS enhancement factors of single TR dye molecules located in the conjunction region in dimer structures having interparticle gaps of 7 and 13 nm are 2 ? 1010 and 8 ? 109, respectively, which are strong enough for single analyte detection. The highly enhanced electromagnetic field generated by the plasmon coupling between sharp tips and cores of two Au nanostars in the wide conjunction region allows the accommodation and specific detection of large biomolecules. Such DNA-directed assembled nanoantennas with controlled interparticle separation distance and stoichiometry, and well-defined geometry, can be used as excellent substrates in single-molecule SERS spectroscopy and will have potential applications as a reproducible platform in single-molecule sensing. ? 2017 American Chemical Society.
DNA Origami-Templated Bimetallic Core-Shell Nanostructures for Enhanced Oxygen Evolution Reaction
(American Chemical Society, 2022-04-15T00:00:00) Kaur, Gagandeep; Biswas, Rathindranath; Haldar, Krishna Kanta; Sen, Tapasi
Hydrogen generation through electrocatalytic water splitting offers promising technology for sustainable and clean energy production as an alternative to conventional energy sources. The development of highly active electrocatalysts is of immense interest for improving the efficiency of gas evolution, which is strongly hindered due to the sluggish kinetics of oxygen evolution reaction (OER). Herein, we present the design of Ag-coated Au nanostar (core-shell-type Au@Ag nanostar) monomer structures assembled on rectangular DNA origami and study their electrocatalytic activities through OER, which remains unexplored. Our designed DNA origami-templated bimetallic nanostar catalyst showed excellent OER activity and high stability without using any external binder and exhibited a current density of 10 mA cm-2at a low overpotential of 266 mV, which was smaller than those of ss-DNA-functionalized Au@Ag nanostars and DNA origami-templated pure Au nanostars. Our results reveal that DNA origami-assembled core-shell Au@Ag nanostars show better electrocatalytic performance as compared to pure-core Au nanostars immobilized on DNA origami, owing to the presence of a highly conductive Ag layer. Such controlled assembly of bimetallic nanostructures on a DNA origami template can provide additional electrochemical surface area and a higher density of active sites resulting in enhanced electrocatalysis. � 2022 American Chemical Society. All rights reserved.
Does Water Play a Crucial Role in the Growth of ZnO Nanoclusters in ZnO/Cu Catalyst?
(American Chemical Society, 2023-05-04T00:00:00) Dastider, Saptarshi Ghosh; Panigrahi, Abhishek Ramachandra; Banerjee, Arup; Haldar, Krishna Kanta; Fortunelli, Alessandro; Mondal, Krishnakanta
The catalytically active configuration of ZnO/Cu in the commercial ZnO/Cu/Al2O3 catalyst for methanol synthesis from CO2 is still not clear. In this study, we employ density functional theory based methods to shed light on the structure and stoichiometry of ZnO clusters both free in the gas phase and also deposited on the Cu(111) surface under methanol synthesis conditions. Specifically, we investigate the structural evolution of ZnO clusters in the presence of hydrogen and water. We find that the stability of ZnO clusters increases with the concentration of water until the ratio of Zn and OH in the clusters reaches 1:2, with a morphological transition from planar to 3D configurations for clusters containing more than 4 Zn atoms. These clusters exhibit weak interaction with CO2, and water is predicted to block the active center. The Cu(111) surface plays an important role in enhancing the adsorption of CO2 on the ZnO/Cu(111) systems. We infer that ZnO nanostructures covered with OH species may be the morphology of the ZnO during the methanol synthesis from the hydrogenation of CO2 on the industrial catalyst. � 2023 American Chemical Society.
Dumbbell-Shaped Ternary Transition-Metal (Cu, Ni, Co) Phosphate Bundles: A Promising Catalyst for the Oxygen Evolution Reaction
(American Chemical Society, 2022-01-27T00:00:00) Singh, Harjinder; Biswas, Rathindranath; Ahmed, Imtiaz; Thakur, Pooja; Kundu, Avinava; Panigrahi, Abhishek Ramachandra; Banerjee, Biplab; Halder, Krishna Kamal; Lahtinen, Jouko; Mondal, Krishnakanta; Haldar, Krishna Kanta
Development of economical and high-performance electrocatalysts for the oxygen evolution reaction (OER) is of tremendous interest for future applications as sustainable energy materials. Here, a unique member of efficient OER electrocatalysts has been developed based upon structurally versatile dumbbell-shaped ternary transition-metal (Cu, Ni, Co) phosphates with a three-dimensional (3D) (Cu2(OH)(PO4)/Ni3(PO4)2�8H2O/Co3(PO4)2�8H2O) (CNCP) structure. This structure is prepared using a simple aqueous stepwise addition of metal ion source approach. Various structural investigations demonstrate highly crystalline nature of the composite structure. Apart from the unique structural aspect, it is important that the CNCP composite structure has proved to be an excellent electrocatalyst for OER performance in comparison with its binary or constituent phosphate under alkaline and neutral conditions. Notably, the CNCP electrocatalyst displays a much lower overpotential of 224 mV at a current density of 10 mA cm-2 and a lower Tafel slope of 53 mV dec-1 with high stability in alkaline medium. In addition, X-ray photoelectron spectroscopy analysis suggested that the activity and long-term durability for the OER of the ternary 3D metal phosphate are due to the presence of electrochemically dynamic constituents such as Ni and Co and their resulting synergistic effects, which was further supported by theoretical studies. Theoretical calculations also reveal that the incredible OER execution was ascribed to the electron redistribution set off in the presence of Ni and Cu and the most favorable interaction between the *OOH intermediate and the active sites of CNCP. This work may attract the attention of researchers to construct efficient 3D ternary metal phosphate catalysts for various applications in the field of electrochemistry. � 2022 American Chemical Society.
Effect of oxygen vacancies, lattice distortions and secondary phase on the structural, optical, dielectric and ferroelectric properties in Cd-doped Bi2Ti2O7 nanoparticles
(Elsevier Ltd, 2021-04-27T00:00:00) Anu; Yadav, Kamlesh; Gaur, Anurag; Haldar, Krishna Kanta
(Bi1-xCdx)2Ti2O7 (x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10 and 0.12) nanoparticles are synthesised using the co-precipitation method. The prepared samples show pyrochlore phase formation except for x = 0.02 and 0.08, where Bi4Ti3O12 appears as a secondary phase. The crystallite size and unit cell volume decrease while the strain and dislocation density increase with an increase in Cd-doping. The vibrational bands corresponding to Cd?O and C[dbnd]O are red-shifted, while the H[sbnd]O[sbnd]H bending band is blue-shifted with increasing Cd-doping. The band gap energy for x = 0.00 is found to be 1.78 eV. It increases with an increase in �x� up to 0.06 and then decreases with a further increase in �x� except for x = 0.02 and x = 0.08. The impedance data show non-Debye type relaxation. The pyrochlore phase is found to be non-ferroelectric. However, the samples with x = 0.02 and x = 0.08 having the secondary phase (Bi4Ti3O12) are ferroelectric. � 2021 Elsevier Ltd
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.
Europium Molybdate/Molybdenum Disulfide Nanostructures with Efficient Electrocatalytic Activity for the Hydrogen Evolution Reaction
(American Chemical Society, 2023-04-26T00:00:00) Ghosh, Debarati; Ghosal Chowdhury, Monojit; Biswas, Rathindranath; Haldar, Krishna Kanta; Patra, Amitava
The design of hybrid nanostructures of molybdenum disulfide (MoS2) has been extensively explored as potent electrocatalysts for hydrogen generation reactions. Here, we report the in situ synthesis of a nanocomposite containing europium molybdate [Eu2(MoO4)3] and molybdenum disulfide (MoS2) for an enhanced electrochemical hydrogen evolution reaction (HER). The characteristic X-ray diffraction (XRD) peaks of both 2H-MoS2 and ?-Eu2(MoO4)3 confirm the formation of the nanocomposite. The nanoflower (NF) architecture of MoS2 coupled with flakes of europium molybdate is observed in the transmission electron microscopy (TEM) and scanning electron microscopy (SEM) images, which lead to an enhanced surface area of the nanocomposite. Raman and X-ray photoelectron spectroscopy (XPS) studies reveal a variation in the layer thickness of MoS2 and a significant interfacial electronic interaction between Eu2(MoO4)3 and MoS2. As evident from the small onset potential of ?0.05 V vs reversible hydrogen electrode (RHE) and a lower overpotential value of 186 mV (at a current density of 10 mA/cm2), the nanocomposite outperforms pristine MoS2 nanoflowers in terms of electrocatalytic HER. The charge-transfer resistance of the nanocomposite (80.02 ?) is significantly low compared to pristine MoS2 (158.37 ?), thus confirming the enhanced interfacial charge transfer. The Tafel slope value of the nanocomposite (189 mV/dec) is notably less than that of pristine MoS2 (313 mV/dec), indicating the enhanced HER activity of the nanocomposite. The fabrication of lanthanide-containing MoS2 nanocomposites appears to be promising for an efficient electrocatalytic activity for the hydrogen evolution reaction. � 2023 American Chemical Society
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.
Ferrocene decorated homoleptic silver(I) clusters: Synthesis, structure, and their electrochemical behaviour
(Elsevier B.V., 2021-06-07T00:00:00) Khirid, Samreet; Jangid, Dilip Kumar; Biswas, Rathindranath; Meena, Sangeeta; Sahoo, Subash C.; Verma, Ved Prakash; Nandi, Chandan; Haldar, Krishna Kanta; Dhayal, Rajendra S.
Silver(I) ferrocenyl dithiophosphonato [Ag{S2P(OiPr)Fc}]n I, [Fc = Fe(?5-C5H4)(?5-C5H4)] 1D polymer was yielded via a ligand exchange reaction between silver nanocluster [Ag21(S2P(OiPr2)12)]PF6 and monoanionic [S2P(OiPr)Fc]� ligand. As per molecular stoichiometry of 1, a direct reaction between [Ag(CH3CN)4]PF6 and [S2P(OiPr)Fc]? was performed in methanol solvent and surprisingly, generate a tetrahedral Ag4{S2P(OiPr)Fc}4 2 cluster instead of 1. Both (1 and 2) clusters are the novel example of homoleptic Ag(I) complexes supported by ferrocenyl dithiophosphonates. Molecular structure of these clusters was unequivocally established by single crystal X-ray crystallographic analyses and supported by the ESI-MS, and 1H and 31P NMR spectroscopy. Structural elucidations reveal that compound 1 has subsequently Ag2S2 square plane and Ag2S4P2 twisted boat units to build a long chain 1D polymer. The cluster 2 exhibits with a tetrahedral Ag(I) core framed by four [S2P(OiPr)Fc]? ligands. interstingly, the [S2P(OiPr)Fc]? ligand display a trimetallic triconnective (?3; �1, �2) bonding pattern in both molecules. The electrochemical behaviours of both compounds (1 and 2) were studied by using cyclic voltammetry, which shows a single wave for all the peripheral ferrocenes and implies negligible electrostatic factor between all ferrocene moieties. � 2021
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 Kanta
Among 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.
Graphitic Carbon Nitride Composites with MoO3-Decorated Co3O4Nanorods as Catalysts for Oxygen and Hydrogen Evolution
(American Chemical Society, 2021-10-22T00:00:00) Ahmed, Imtiaz; Biswas, Rathindranath; Patil, Ranjit A.; Halder, Krishna Kamal; Singh, Harjinder; Banerjee, Biplab; Kumar, Bhupender; Ma, Yuan-Ron; Haldar, Krishna Kanta
We have prepared a graphitic carbon nitride (g-C3N4) composite with MoO3-decorated Co3O4 nanorods (Co3O4/MoO3/g-C3N4) via the hydrothermal approach, and this hybrid material acts as a highly active and durable electrocatalyst for water splitting reactions. This material could fundamentally influence the catalytic processes and performance of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The OER and HER activities of Co3O4-/MoO3-based nanorods are enhanced by blending with conducting support, for example, graphitic carbon nitrides (g-C3N4). The X-ray diffraction pattern and the attenuated total reflectance-Fourier transform infrared data revealed that the as-synthesized nanorods are highly crystalline in nature and are attached to the g-C3N4 support. Transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy studies also affirm the successful heterointerface formation between Co3O4/MoO3 nanorods and g-C3N4. This Co3O4/MoO3/g-C3N4 rod-shaped catalyst is highly stable in comparison to its individual constituent and generates a current density of 10 mA cm-2 at a low overpotential of 206 mV for OER and 125 mV for HER in alkaline and acidic media, respectively. This work could pave the way for developing Co3O4/MoO3/g-C3N4 composite materials as electrocatalysts for overall water splitting reactions. � 2021 American Chemical Society. All rights reserved.
Green Approach for the Fabrication of Au/ZnO Nanoflowers: A Catalytic Aspect
(American Chemical Society, 2021-03-19T00:00:00) Biswas, Rathindranath; Banerjee, Biplab; Saha, Monochura; Ahmed, Imtiaz; Mete, Shouvik; Patil, Ranjit A.; Ma, Yuan-Ron; Haldar, Krishna Kanta
An easy, environmentally benign, and biomimetic approach employing Azadirachta indica (neem) leaf extract as a reducing as well as capping agent was used for the fabrication of gold (Au)/zinc oxide (ZnO) hybrid nanoflowers in one pot without utilizing any hazardous chemicals. The different phytoconstituents, for example, nimbolide, azadirachtin, ascorbate, etc., present in A. indica (neem) leaf extract synergistically reduce gold(III) ions to gold(0), which later on acts as an active surface for the growth of zinc oxide (ZnO) via thermal decomposition of sodium zincate [Na2Zn(OH)4]. The development of Au/ZnO hybrid nanoflowers was observed by estimating the absorption maxima at various time intervals in the wake of adding a Au precursor to the aqueous extract. X-ray diffraction (XRD) studies and X-ray photoelectron spectroscopy (XPS) investigation unambiguously confirm the formation of highly crystalline Au/ZnO composed of Au(0) and ZnO. The as-synthesized Au/ZnO hybrid nanoflowers were analyzed utilizing different spectroscopic and microscopic techniques. The transmission electron microscopy (TEM) images clearly show that the synthesized hybrid Au/ZnO nanoflowers are monodisperse and uniform. The fabricated Au/ZnO nanoflowers were used as a catalyst for the efficient reduction of various aromatic nitro compounds to corresponding amino compounds with excellent yield (76-94%) in the presence of reducing agent sodium borohydride. The superior catalytic properties were credited to the extraordinary nanoflower morphology and the synergistic impact of the typified Au nanoparticles. � 2021 American Chemical Society.