Molecular Insights into Hierarchical Zn ²⁺ Hydration States Driving Energy-Efficient Cellulose Dissolution

Developing efficient and sustainable solvents for cellulose dissolution at ambient conditions is pivotal for advancing green chemistry and reducing reliance on petroleum-derived materials. Although ZnCl 2 -based solvents, such as the typical ZnCl 2 /H 2 O systems, demonstrate remarkable room-temperature dissolution capabilities, their molecular-level mechanisms remain poorly understood. Traditional experimental approaches face limitations in resolving dynamic interactions and thermodynamic drivers, hindering solvent optimization. Herein, molecular dynamics (MD) simulations elucidate the mechanistic synergy of hydrated Zn 2+ ions, Cl – ions, and H 2 O molecules in disrupting cellulose’s hydrogen-bonding network and hydrophobic interactions. Results reveal that [Zn(H 2 O) 3 ] 2+ hydrate preferentially penetrates cellulose chains via O3 hydroxyl sites, forming O(cellulose)···HO(H 2 O) hydrogen bonds, while [Zn(H 2 O) 4 ] 2+ hydrates stabilize dispersed chains. Cl – ions reduce hydrophobicity by interacting with C–H groups, complementing Zn 2+ -driven hydrogen bond cleavage. Thermodynamically, entropy compensation from released H 2 O molecules and Cl – ions offsets Zn 2+ ions adsorption, yielding a minimal entropy change (−498.00 J/mol/K). Enthalpy (−40.63 kJ/mol) dominates the favorable Gibbs free energy (−177.56 kJ/mol), underscoring the system’s efficiency. This work provides atomistic insights into solvent-cellulose interactions, guiding the design of eco-friendly, energy-efficient cellulose solvents aligned with sustainable development goals.