Molecular selective adsorption processes at the solid surface of biopolymers in mixed solvent systems are poorly understood due to manifold interactions. However, the ability to achieve adsorptive fractionation of liquid mixtures is posited to relate to the role of specific solid-liquid interactions at the adsorbent interface. The hydration of solid biopolymers (amylose, amylopectin, cellulose) in binary aqueous systems is partly governed by the relative solvent binding affinities with the biopolymer surface sites, in accordance with the role of textural and surface chemical properties. While molecular models that account for the surface area and solvent effects provide reliable estimates of hydration energy and binding affinity parameters, spectroscopic and thermal methods offer a facile alternative experimental approach to account for detailed aspects of solvation phenomena at biopolymer interfaces that involve solid-liquid adsorption. In this report, thermal and spectroscopic methods were used to understand the interaction of starch- and cellulose-based materials in water-ethanol (W-E) binary mixtures. Batch adsorption studies in binary W-E mixtures reveal the selective solvent uptake properties by the biomaterials, in agreement with their solvent swelling in pure water or ethanol. The nature, stability of the bound water, and the thermodynamic properties of the biopolymers in variable hydration states were probed via differential scanning calorimetry and Raman spectroscopy. The trends in biopolymer-solvent interactions are corroborated by dye adsorption and scanning electron microscopy, indicating that biopolymer adsorption properties in W-E mixtures strongly depend on the surface area, pore structure, and accessibility of the polar surface groups of the biopolymer systems, in agreement with the solvent-selective uptake results reported herein.

The adsorption-desorption behavior of flax fibers (FFs) is reported in this paper. FFs are a potential desiccant material for air-to-air energy wheels, which transfer heat and moisture in building heating, ventilation, and air conditioning (HVAC) systems. The raw FFs sample was subjected to physical modification, followed by complementary material characterization to understand the relationship between its structure and its moisture uptake performance. The surface and textural properties of the modified FFs were determined by gas adsorption (N2, H2O) and gravimetric liquid water swelling studies and further supported by spectroscopic (infrared and scanning electron microscopy) results. A FF-coated small-scale energy exchanger was used to determine the moisture transfer (or latent effectiveness; εl) using single-step and cyclic testing. The FF-coated exchanger had εl values of ∼10 and 40% greater compared to similar exchangers coated with starch particles (SPs) and silica gel (SG) reported in a previous study. The enhanced surface and textural properties, along with the complex compositional structure of FFs and its greater propensity to swell in water, account for the improved performance over SPs. Thus, FFs offer an alternative low-cost, environment-friendly, and sustainable biodesiccant for air-to-air energy wheel applications in buildings. The current study contributes to an improved understanding of the structure-function relationship of biodesiccants for such energy wheel applications.

Graphene oxide (GO) was cross-linked with chitosan to yield a composite (GO-LCTS) with variable morphology, enhanced surface area, and notably high methylene blue (MB) adsorption capacity. The materials were structurally characterized using thermogravimetric analysis and spectroscopic methods (X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectroscopy, and 13C solid-state NMR) to support that cross-linking occurs between the amine groups of chitosan and the -COOH groups of GO. Equilibrium swelling studies provide support for the enhanced structural stability of GO-cross-linked materials over the synthetic precursors. Scanning electron microscopy studies reveal the enhanced surface area and variable morphology of the cross-linked GO materials, along with equilibrium and kinetic uptake results with MB dye in aqueous media, revealing greater uptake of GO-LCTS composites over pristine GO. The monolayer uptake capacity (Q m; mg g-1) with MB reveals twofold variation for Q m, where GO-LCTS (402.6 mg g-1) > GO (286.9 mg g-1). The kinetic uptake profiles of MB follow a pseudo-second-order trend, where the GO composite shows more rapid uptake over GO. This study reveals that the sorption properties of GO are markedly improved upon formation of a GO-chitosan composite. The facile cross-linking strategy of GO reveals that its physicochemical properties are tunable and versatile for a wider field of application for contaminant removal, especially over multiple adsorption-desorption cycles when compared against pristine GO in its highly dispersed nanoparticle form.