Physics-guided thermodynamic screening of H₂ adsorption on alkaline-earth-modified anatase TiO₂ nanoparticles with LLM-assisted interpretation.
4 affiliations
- 1Department of Electrical and Computer Engineering, Texas A&M University at Qatar Doha Qatar [email protected].
- 2Department of Prosthetics and Orthotics, Ankara University Ankara Türkiye.
- 3Department of Electrical and Computer Engineering, Texas A&M University College Station TX USA.
- 4College of Science and Engineering, Hamad Bin Khalifa University Doha Qatar [email protected].
Abstract
Understanding how surface modification tunes H₂ adsorption on oxide nanomaterials is important for designing reversible hydrogen-interaction platforms under near-ambient conditions. Here, we examine single-H₂ adsorption on a fixed, idealized ∼1.8 nm anatase-derived TiO₂ nanoparticle reference model, both pristine and surface-modified with alkaline-earth (AE) species (Be, Mg, Ca, Sr, Ba, and Ra), using GATOR, a physics-guided DFTB-based screening framework with LLM-assisted interpretation. Within this framework, the deterministic thermodynamic screening sequence defines the classification, whereas the constrained language model serves only as an interpretive layer rather than as a predictor of adsorption physics. The workflow combines DFTB-derived adsorption energetics, adsorption-mode analysis, finite-temperature thermodynamic descriptors, Langmuir-type coverage estimates, rule-based thermodynamic screening, and post-hoc consistency checks to evaluate local H₂ uptake-release behavior. Electronic adsorption energies are mapped onto finite-temperature descriptors at 298 K, including finite-temperature-corrected adsorption enthalpy surrogates, standard-state free-energy estimates, desorption midpoint temperatures, and pressure-dependent fractional coverages. Across the series, Be-TiO₂ and Ra-TiO₂ occupy excessive-binding/heating-needed regimes, whereas Ca-, Sr-, and Ba-modified TiO₂ remain weak-binding and under-loaded near ambient pressure. Pristine TiO₂ and Mg-modified TiO₂ represent the most balanced strong-binding cases, but both lie above the practical desorption window under the entropy-consistent thermodynamic treatment. Frontier-orbital and conceptual-DFT descriptors change only modestly upon H₂ adsorption, indicating that the observed trends are governed mainly by local adsorption geometry and finite-temperature adsorption thermodynamics rather than by substantial global electronic-structure reorganization. Within the DFTB-based screening framework, pristine TiO₂ and Mg-TiO₂ occupy the most balanced region of the representative adsorption landscape. Higher-level PBE-D3(BJ) calculations support attractive local H₂ interactions for both representative motifs, but they do not reproduce the small DFTB energetic preference for Mg-TiO₂ and place the local Mg-H₂ minimum at a longer separation. Accordingly, the pristine/Mg ordering should be regarded as method-sensitive, and no method-independent energetic preference between these two systems is assigned.
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BibTeX
@article{kurban2026physicsguided,
title = {{Physics-guided thermodynamic screening of H₂ adsorption on alkaline-earth-modified anatase TiO₂ nanoparticles with LLM-assisted interpretation.}},
author = {Mustafa Kurban and Can Polat and Erchin Serpedin and Hasan Kurban},
journal = {RSC advances},
year = {2026},
month = oct,
doi = {10.1039/d6ra04252j},
url = {https://europepmc.org/article/MED/42852144},
note = {CC BY},
}
RIS
TY - JOUR
TI - Physics-guided thermodynamic screening of H₂ adsorption on alkaline-earth-modified anatase TiO₂ nanoparticles with LLM-assisted interpretation.
AU - Mustafa Kurban
AU - Can Polat
AU - Erchin Serpedin
AU - Hasan Kurban
PY - 2026
DA - 2026/10/07
JO - RSC advances
DO - 10.1039/d6ra04252j
UR - https://europepmc.org/article/MED/42852144
AB - Understanding how surface modification tunes H₂ adsorption on oxide nanomaterials is important for designing reversible hydrogen-interaction platforms under near-ambient conditions. Here, we examine single-H₂ adsorption on a fixed, idealized ∼1.8 nm anatase-derived TiO₂ nanoparticle reference model, both pristine and surface-modified with alkaline-earth (AE) species (Be, Mg, Ca, Sr, Ba, and Ra), using GATOR, a physics-guided DFTB-based screening framework with LLM-assisted interpretation. Within this framework, the deterministic thermodynamic screening sequence defines the classification, whereas the constrained language model serves only as an interpretive layer rather than as a predictor of adsorption physics. The workflow combines DFTB-derived adsorption energetics, adsorption-mode analysis, finite-temperature thermodynamic descriptors, Langmuir-type coverage estimates, rule-based thermodynamic screening, and post-hoc consistency checks to evaluate local H₂ uptake-release behavior. Electronic adsorption energies are mapped onto finite-temperature descriptors at 298 K, including finite-temperature-corrected adsorption enthalpy surrogates, standard-state free-energy estimates, desorption midpoint temperatures, and pressure-dependent fractional coverages. Across the series, Be-TiO₂ and Ra-TiO₂ occupy excessive-binding/heating-needed regimes, whereas Ca-, Sr-, and Ba-modified TiO₂ remain weak-binding and under-loaded near ambient pressure. Pristine TiO₂ and Mg-modified TiO₂ represent the most balanced strong-binding cases, but both lie above the practical desorption window under the entropy-consistent thermodynamic treatment. Frontier-orbital and conceptual-DFT descriptors change only modestly upon H₂ adsorption, indicating that the observed trends are governed mainly by local adsorption geometry and finite-temperature adsorption thermodynamics rather than by substantial global electronic-structure reorganization. Within the DFTB-based screening framework, pristine TiO₂ and Mg-TiO₂ occupy the most balanced region of the representative adsorption landscape. Higher-level PBE-D3(BJ) calculations support attractive local H₂ interactions for both representative motifs, but they do not reproduce the small DFTB energetic preference for Mg-TiO₂ and place the local Mg-H₂ minimum at a longer separation. Accordingly, the pristine/Mg ordering should be regarded as method-sensitive, and no method-independent energetic preference between these two systems is assigned.
SN - 2046-2069
ER -