Exploring the hydrogen interaction on Zn12O12 nanocages: A first-principles study
Por:
Paularokiadoss F., Jeyakumar T.C., Celaya C.A., Solórzano M., Belhocine Y., Gassoumi B., Ayachi S.
Publicada:
1 ene 2025
Resumen:
This study uses density functional theory (DFT) a powerful computational method, to analyze how the hydrogen molecules adsorb in the Zn12O12 nanocage, a promising material for lightweight hydrogen storage applications. The adsorption mechanism is primarily governed by the charge redistribution and polarization effect originating from Zn[sbnd]O bonds, which induce preferential binding of H2 molecules at Zn sites. Detailed electronic structure analysis, supported by Quantum Theory of Atoms in Molecules (QTAIM) and Non-covalent Interaction (NCI) calculations, reveals that these interactions are weakly physisorption yet highly stable, ensuring reversible adsorption. The compute average adsorption energy is approximately -0.04 eV per H2 molecule, indicating facile adsorption-desorption under ambient conditions. Zn12O12 nanocages demonstrate an impressive gravimetric hydrogen storage capacity exceeding 7.6 wt%, surpassing several current nanostructured materials. Furthermore, ab initio molecular dynamics (AIMD) simulations conducted at 300 K confirm the structural stability of Zn12O12 during H2 adsorption. To further enhance the tunability of Zn12O12 nanocage properties for hydrogen storage applications, alkali metal doping (Li, Na, K) was investigated by substituting a Zn atom with an alkali element. Structural optimization and stability assessments confirm that the doped nanocages preserve their geometric integrity, while molecular electrostatic potential (MEP) analysis reveals pronounced localized charge redistribution around the dopant site. Although the computed average H2 adsorption energies remain comparable to the pristine nanocage, the induction of alkali dopants generates chemically active regions that could facilitate tailored surface reactivity, enhance spillover processes, and enable applications specific functionalization. These findings provide deep insights into the H2 retention mechanisms within Zn12O12 clusters, highlighting their versatility and potential for next-generation hydrogen energy systems. © 2025 The Authors
Filiaciones:
Paularokiadoss F.:
PG & Research Department of Chemistry, St. Joseph College of Arts & Science, Tamil Nadu, Cuddalore, 607001, India
Jeyakumar T.C.:
PG & Research Department of Chemistry, The American College (Autonomous), Tamil Nadu, Madurai, 625002, India
Celaya C.A.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Carretera Tijuana-Ensenada, B.C., C.P, Ensenada, 22800, Mexico
Solórzano M.:
Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Carretera Tijuana-Ensenada, B.C., C.P, Ensenada, 22800, Mexico
Belhocine Y.:
Department of Process Engineering, Faculty of Technology, University of 20 August 1955, Skikda, 21000, Algeria
Laboratory of Catalysis, Bioprocess and Environment, Department of Process Engineering, Faculty of Technology, University of 20 August 1955, Skikda, 21000, Algeria
Gassoumi B.:
Laboratory of Advanced Materials and Interfaces (LIMA), University of Monastir, Faculty of Sciences of Monastir, Avenue of Environment, Monastir, 5000, Tunisia
Ayachi S.:
Laboratory of Physico-Chemistry of Materials (LR01ES19), Faculty of Sciences, University of Monastir, Avenue of the Environment, Monastir, 5019, Tunisia
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