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 analysis via Quantum Theory of Atoms in Molecules (QTAIM), and molecular dynamics (MD) simulations at 300 K 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 analysis 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 MD simulations demonstrate that functionalization promotes spatial organization on nanotube surfaces, increasing contact regions and reducing molecular mobility. Systems with moderate interactions (CNT+OH x +G1 and CNT+OH x +G3) present environmentally and economically viable solutions, enabling adsorbent regeneration and reuse. The findings indicate that OH-functionalized CNTs show significant promise for glyphosate detection and capture applications in environmental monitoring and remediation, regardless of the pesticide’s ionization state.