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Microscopic Perspective on the Adsorption Isotherm of a Heterogeneous Surface.

ABSTRACT: Adsorption of dissolved molecules onto solid surfaces can be extremely sensitive to the atomic-scale properties of the solute and surface, causing difficulties for the design of fluidic systems in industrial, medical and technological applications. In this communication, we show that the Langmuir isotherm for adsorption of a small molecule to a realistic, heterogeneous surface can be predicted from atomic structures of the molecule and surface through molecular dynamics (MD) simulations. We highlight the method by studying the adsorption of dimethyl-methylphosphonate (DMMP) to amorphous silica substrates and show that subtle differences in the atomic-scale surface properties can have drastic effects on the Langmuir isotherm. The sensitivity of the method presented is sufficient to permit the optimization of fluidic devices and to determine fundamental design rules for controlling adsorption at the nanoscale.

SUBMITTER: Carr R

PROVIDER: S-EPMC3353733 | biostudies-literature | 2011 Jul

REPOSITORIES: biostudies-literature

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Project description:Environment-friendly composite hydrogel beads based on carboxymethyl cellulose (CMC), alginate (Alg) and graphene oxide (GO) were synthesized by an ionotropic gelation technique and studied as an efficient adsorbent for methylene blue (MB). The chemical structure and surface morphology of the prepared hydrogel beads were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential thermal analysis (DTA) and point of zero charge (pHpzc). A hybrid response surface methodology integrated Box-Behnken design (RSM-BBD) was successfully developed to model, simulate, and optimize the biosorption process. The synergistic effects between three critical independent variables including adsorbent dose (0.3-0.7 g), pH of the MB solution (6.5-9.5) and initial MB concentration (15-45 mg L-1) on the MB adsorption capacity (mg g-1) and removal efficiency (%) were statistically studied and optimized. The performance of the RSM-BBD method was found to be very impressive and efficient. Results proved that the adsorption process follows a polynomial quadratic model since high regression parameters were obtained (R 2-value = 99.8% and adjusted R 2-value = 99.3%). Analysis of variance (ANOVA) further confirms the validity of the suggested model. The optimal conditions for 96.22 ± 2.96% MB removal were predicted to be 0.6 g of CMC-Alg/GO hydrogel beads, MB concentration of 15 mg L-1 and pH of 9.5 within 120 min. The adsorption equilibrium is better described by the Freundlich isotherm, indicating that physisorption is the rate controlling mechanism. The MB adsorption process was thermodynamically spontaneous and endothermic. A reusability study revealed that the prepared adsorbent is readily reusable. The adsorbent still maintains its ability to adsorb MB for up to four cycles. Results reported in this study demonstrated that CMC-Alg/GO hydrogel beads are an effective, promising and recyclable adsorbent for the removal of MB from aqueous solutions.

Project description:For more than a century, monolayer adsorptions in which adsorbate molecules and adsorbing sites behave ideally have been successfully described by Langmuir's adsorption isotherm. For example, the amount of adsorbed material, as a function of concentration of the material which is not adsorbed, obeys Langmuir's equation. In this paper, we argue that this relation is valid only for macroscopic systems. However, when particle numbers of adsorbate molecules and/or adsorbing sites are small, Langmuir's model fails to describe the chemical equilibrium of the system. This is because the kinetics of forming, or the probability of observing, occupied sites arises from two-body interactions, and as such, ought to include cross-correlations between particle numbers of the adsorbate and adsorbing sites. The effect of these correlations, as reflected by deviations in predicting composition when correlations are ignored, increases with decreasing particle numbers and becomes substantial when only few adsorbate molecules, or adsorbing sites, are present in the system. In addition, any change that augments the fraction of occupied sites at equilibrium (e.g., smaller volume, lower temperature, or stronger adsorption energy) further increases the discrepancy between observed properties of small systems and those predicted by Langmuir's theory. In contrast, for large systems, these cross-correlations become negligible, and therefore when expressing properties involving two-body processes, it is possible to consider independently the concentration of each component. By applying statistical mechanics concepts, we derive a general expression of the equilibrium constant for adsorption. It is also demonstrated that in ensembles in which total numbers of particles are fixed, the magnitudes of fluctuations in particle numbers alone can predict the average chemical composition of the system. Moreover, an alternative adsorption equation, predicting the average fraction of occupied sites from the value of the equilibrium constant, is proposed. All derived relations were tested against results obtained by Monte Carlo simulations.

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Microscopic Perspective on the Adsorption Isotherm of a Heterogeneous Surface.

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