arXiv subjects

H. T. Silva

Publications and source records attributed to H. T. Silva.

3 recordsLinked to original sources

arXiv2026

From Electronic Structure to Environmental Remediation: Adsorption of Ionized Glyphosate on COOH-Modified Carbon Nanotube

Glyphosate is a widely used herbicide whose persistence and toxicity in aquatic and terrestrial environments demand efficient removal strategies. Here we employ GFN2 xTB calculations with implicit ALPB aqueous solvation and automated docking to investigate the adsorption of all five pH dependent ionized forms of glyphosate (G1-G5) on (10,0) single walled carbon nanotubes covalently functionalized with carboxyl groups at 0-25% coverage. Adsorption energies reveal a clear charge dependent trend: the dianionic (G4) and trianionic (G5) species exhibit the most negative binding energies over the entire functionalization range, while the protonated and neutral forms (G1, G2) bind weakly, approaching reversible adsorption at high COOH contents. The deprotonated form G5 strengthens from -2.17 eV on pristine CNT to about -5.7 eV at 10% and 25% functionalization, with a local minimum near 15-20% COOH due to steric and electrostatic crowding of adjacent groups. Decomposition of the solvation free energy shows dominant electrostatic stabilization complemented by increasingly favorable hydrogen bond contributions as carboxyl density grows. All complexes display very small HOMO-LUMO gaps (0.02-0.22 eV), indicating high electronic sensitivity to adsorption and functionalization. Overall, CNT+COOH systems can operate in both strong capture and regenerable regimes depending on glyphosate ionization state, offering a tunable platform for pH responsive remediation.

cond-mat.mtrl-sci↗

arXiv2025

pH-Responsive Glyphosate Adsorption on Hydroxylated Carbon Nanotubes: From Electronic Structure to Molecular Dynamics

This computational study investigates glyphosate adsorption mechanisms on hydroxyl-functionalized carbon nanotubes (CNTs) as an alternative approach for environmental remediation. Single-walled CNTs with (10,0) zigzag chirality were functionalized with hydroxyl groups at concentrations of 5-25% and evaluated for interactions with glyphosate in five different ionization states (G1-G5) corresponding to pH-dependent protonation. Using semi-empirical tight-binding methods implemented in xTB software, molecular geometry optimization, electronic property calculations, topological analyses via Quantum Theory of Atoms in Molecules (QTAIM), and molecular dynamics simulations at 300K were performed. Results demonstrate that functionalization significantly enhances adsorption capacity, with binding energies becoming increasingly negative at higher OH concentrations and with more deprotonated glyphosate forms (G4 and G5). Electronic coupling analyses reveal optimized charge reactivity and transport in systems with 20-25% OH functionalization. Topological characterization identified 477 bond critical points, confirming donor-acceptor interactions with strong covalent contributions, particularly in highly functionalized systems. Radial distribution function profiles from molecular dynamics simulations demonstrate that functionalization promotes spatial organization on nanotube surfaces, increasing contact regions and reducing molecular mobility. Systems with moderate interactions (CNT+OHx+G1 and CNT+OHx+G3) present environmentally and economically viable solutions, enabling adsorbent regeneration and reuse. The findings indicate that OH-functionalized carbon nanotubes show significant promise for glyphosate detection and capture applications in environmental monitoring and remediation, regardless of the pesticide's ionization state.

cond-mat.mtrl-sci↗

arXiv2025

Computational study of interactions between ionized glyphosate and carbon nanotube: An alternative for mitigating environmental contamination

The extensive use of glyphosate in agriculture has raised environmental concerns due to its adverse effects on plants, animals, microorganisms, and humans. This study investigates the interactions between ionized glyphosate and single-walled carbon nanotubes (CNT) using computational simulations through semi-empirical tight-binding methods (GFN2-xTB) implemented in the xTB software. The analysis focused on different glyphosate ionization states corresponding to various pH levels: G1 (pH < 2), G2 (pH ~ 2-3), G3 (pH ~ 4-6), G4 (pH ~ 7-10), and G5 (pH > 10.6). Results revealed that glyphosate in G1, G3, G4, and G5 forms exhibited stronger interactions with CNT, demonstrating higher adsorption energies and greater electronic coupling. The neutral state (G2) showed lower affinity, indicating that molecular protonation significantly influences adsorption. Topological analysis and molecular dynamics confirmed the presence of covalent, non-covalent, and partially covalent interactions, while the CNT+G5 system demonstrated moderate interactions suitable for material recycling. These findings suggest that carbon nanotubes, with their extraordinary properties such as nanocapillarity, porosity, and extensive surface area, show promise for environmental monitoring and remediation of glyphosate contamination.

cond-mat.mtrl-sci↗