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Creators/Authors contains: "Phakatkar, Abhijit_H"

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  1. Abstract The nucleation and growth of nanoparticles are critical processes determining the size, shape, and properties of resulting nanoparticles. However, understanding the complex mechanisms guiding the formation and growth of colloidal multielement alloy nanoparticles remains incomplete due to the involvement of multiple elements with different properties. This study investigates in situ colloidal synthesis of multielement alloys using transmission electron microscopy (TEM) in a liquid cell. Two different pathways for nanoparticle formation in a solution containing Au, Pt, Ir, Cu, and Ni elements, resulting in two distinct sets of particles are observed. One set exhibits high Au and Cu content, ranging from 10 to 30 nm, while the other set is multi‐elemental, with Pt, Cu, Ir, and Ni, all less than 4 nm. The findings suggest that, besides element miscibility, metal ion characteristics, particularly reduction rates, and valence numbers, significantly impact particle composition during early formation stages. Density functional theory (DFT) simulations confirm differences in nanoparticle composition and surface properties collectively influence the unique growth behaviors in each nanoparticle set. This study illuminates mechanisms underlying the formation and growth of multielement nanoparticles by emphasizing factors responsible for chemical separation and effects of interplay between composition, surface energies, and element miscibility on final nanoparticles size and structure. 
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  2. Abstract Calcium oxalate (CaOx) is the major phase in kidney stones and the primary calcium storage medium in plants. CaOx can form crystals with different lattice types, water contents, and crystal structures. However, the conditions and mechanisms leading to nucleation of particular CaOx crystals are unclear. Here, liquid‐cell transmission electron microscopy and atomistic molecular dynamics simulations are used to study in situ CaOx nucleation at different conditions. The observations reveal that rhombohedral CaOx monohydrate (COM) can nucleate via a classical pathway, while square COM can nucleate via a non‐classical multiphase pathway. Citrate, a kidney stone inhibitor, increases the solubility of calcium by forming calcium‐citrate complexes and blocks oxalate ions from approaching calcium. The presence of multiple hydrated ionic species draws additional water molecules into nucleating CaOx dihydrate crystals. These findings reveal that by controlling the nucleation pathways one can determine the macroscale crystal structure, hydration state, and morphology of CaOx. 
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  3. Abstract Despite significant interest toward solid‐state electrolytes owing to their superior safety in comparison to liquid‐based electrolytes, sluggish ion diffusion and high interfacial resistance limit their application in durable and high‐power density batteries. Here, a novel quasi‐solid Li+ion conductive nanocomposite polymer electrolyte containing black phosphorous (BP) nanosheets is reported. The developed electrolyte is successfully cycled against Li metal (over 550 h cycling) at 1 mA cm−2at room temperature. The cycling overpotential is dropped by 75% in comparison to BP‐free polymer composite electrolyte indicating lower interfacial resistance at the electrode/electrolyte interfaces. Molecular dynamics simulations reveal that the coordination number of Li+ions around (trifluoromethanesulfonyl)imide (TFSI) pairs and ethylene‐oxide chains decreases at the Li metal/electrolyte interface, which facilitates the Li+transport through the polymer host. Density functional theory calculations confirm that the adsorption of the LiTFSI molecules at the BP surface leads to the weakening of N and Li atomic bonding and enhances the dissociation of Li+ions. This work offers a new potential mechanism to tune the bulk and interfacial ionic conductivity of solid‐state electrolytes that may lead to a new generation of lithium polymer batteries with high ionic conduction kinetics and stable long‐life cycling. 
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