Thermally stable cellulose nanospheres prepared from office waste paper by complete removal of hydrolyzed sulfate groups.

Cellulose nanocrystals are commonly obtained by acid hydrolysis, particularly with H2SO4. However, a small amount of deposited sulfate-groups contributes to the degradation of their thermal stability. This study prepared thermally-stable and sulfate-group-free cellulose nanospheres (CNSs) from office waste paper by H2SO4 hydrolysis followed by solvolytic desulfation. The optimal desulfation conditions (i.e., 5 wt% MeOH, reaction temperature of 90 °C, a reaction time of 20 min, 0.5 mM pyridine) were preliminarily found from a one-factor-at-a-time experiment and validated by the results of a central composite design. The optimal desulfation conditions promoted environmental sustainability with less pyridine and MeOH and comparably shorter reaction time. The desulfated CNSs had a significant thermal stability enhancement from 186 to 340 °C. Comprehensive characterization of the morphology, chemical composition, and thermal behavior of the desulfated CNSs reconfirmed the complete removal of sulfate groups without harmful pyridine residues, demonstrating the potential use of the thermally stable CNSs.

Mechano-chemical stability and water effect on gas selectivity in mixed-metal zeolitic imidazolate frameworks: a systematic investigation from van der Waals corrected density functional theory.

A series of Zn/Cu Zeolitic Imidazolate Frameworks (ZIFs) ZIF-202, -203, and -204 are systematically investigated by Density Functional Theory (DFT) with and without van der Waals (vdW) corrections. The elastic constants for non-solvent structures indicate that ZIF-202 and -204 are mechanically stable while ZIF-203 is unstable, which arises from the stiffness along the x-axis under a uniaxial strain in the PBE-D3 method. By considering the presence of solvents in ZIF-203, a structural phase transformation from a monoclinic to a triclinic structure is found which could be explained by the Jahn-Teller distortion. From the chemical bonding point of view, it is found that vdW interactions and hybridization between d-orbitals (copper) and p-orbitals (imidazolate) are the main-driving forces in stabilizing ZIF-202 and -204, respectively. The electronic structure calculations predict the presence of two optical transitions in the visible region in agreement with the experimental observation for ZIF-204 both without and with water. The DFT simulations reveal that CO2 molecules prefer to locate near imidazolate and water in dry and hydrated ZIF-204, respectively. The analysis of Canonical Monte Carlo (GCMC) simulations reveals that Coulomb interaction between CO2 and H2O molecules is mainly responsible for the enhanced CO2 uptake and selectivity under humid conditions compared to dry ones.