arXiv subjects

Manju Kumari

Publications and source records attributed to Manju Kumari.

3 recordsLinked to original sources

arXiv2026

Distribution of Relaxation Times analysis of evolution of Oxygen Reduction Pathways for ionic conductor infiltration on MIEC cathode

Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices; however, the sluggish cathodic oxygen reduction reaction (ORR) remains a major limitation for intermediate-temperature operation. ORR subprocesses can be modified by infiltrating ionic Sm0.2Ce0.8O2-delta (SDC) on mixed ionic electronic SrFe0.9Ti0.1O3-delta (STF). However, the processes are indistinguishable in most cases and poorly understood using conventional equivalent circuits. Distribution of Relaxation Times (DRT) analysis distinguishes these processes to identify the dynamics with temperature and surface reconstruction. Such analysis is being reported, revealing the connection between increase of active sites, temperature, and polarization resistance (RP). SDC infiltration preferentially accelerates oxygen surface exchange and activation processes over the relatively high frequency charge transfer process related to cathode surface at elevated temperatures for the infiltrated cells. RP was reduced substantially with the systematic redistribution of each process to as low as 0.04 ohm.cm2 at 800 degC. This work underlines the deconvolution of the processes using DRT as a tool, and SDC infiltrated STF as a model cathode system to provide a mechanistic insight of understanding ORR kinetics and design a rationale for developing high-performance SOFC air electrodes

cond-mat.mtrl-sci↗

arXiv2025

Increased Covalence and V-center mediated Dark Fenton-Like Reactions in V-doped TiO2: Mechanisms of Enhanced Charge-Transfer

Tuning the valence state and electronic structure of catalytically active sites is crucial for improving Fenton and Fenton-like reactions, which rely on the efficient activation of the H2O2 molecule. Pure TiO2, however, has inadequate activity towards the H2O2 activation and is often constrained by the intrinsic electronic limitations of pristine TiO2. Herein, a rational approach has been demonstrated to improve the Fenton-like catalytic performance of TiO2 through multivalent vanadium (V) doping. A comprehensive characterization using X-Ray Diffraction (XRD), Raman spectroscopy, UV-Vis spectroscopy, X-Ray photoelectron spectroscopy (XPS), Electron paramagnetic resonance (EPR), and Density functional theory (DFT) reveals that V incorporation substantially alters the electronic structure of TiO2. The DFT results, supported by experimental data, indicate that V doping enhances Ti-O covalence and introduces mid-gap states, resulting in a reduced band gap and improved charge transfer. XPS confirms the coexistence of multiple oxidation states of V, which serve as active centres for activating H2O2 and generating OH radicals. As a result, V-doped TiO2 exhibits significantly enhanced dark-catalytic activity in degrading the organic dye Rhodamine B (RhB). Overall, this study provides fundamental insights into multivalent-cation-induced valence state and electronic structure modulation in TiO2, offering a promising strategy for designing high-performance catalysts via defect engineering for sustainable environmental remediation.

cond-mat.mtrl-sci↗

arXiv2025

Correlation of the role of Li-doping in control of O-vacancies and Li interstitial formations in NiO with electrochemical properties

Aliovalent doping in an oxide material introduces modifications in the valence state of the host cation and often leads to tailoring the oxygen content in the lattice. Moreover, if the dopant cation is larger than the host cation, the lattice strain and disorder may be affected. Such changes are expected to modify the electronic clouds and lead to different ligand fields, which in turn should modify the bond lengths, and therefore phonons, electronic properties, transport properties, and charge storage properties. To understand such correlations an example is being investigated in this study by doping a larger Li+ ion in a NiO lattice. The effect on structure, phonons, electronic properties, and charge storage properties are investigated and correlated in a first-of-its-kind report. The charge storage properties are observed to improve with Li+ doping until 3% substitution and thereafter decrease due to the generation of Li+ interstitial in a 6% incorporated sample. The connection of oxygen vacancies and Ni3+ formation with Li+ incorporation is the backbone of this report.

cond-mat.mtrl-sci↗