RESUMO
A prominent role of water in aqueous-phase heterogeneous catalysis is to modify free energies; however, intuition about how is based largely on pure metal surfaces or even homogeneous solutions. Using multiscale modeling with explicit liquid water molecules, we show that the influence of water on the free energies of adsorbates at metal/support interfaces is different than that on pure metal surfaces. We specifically compute free energies of solvation for methanol and its constituents on a Pt/Al2O3 catalyst and compare the results to analogous values calculated on a pure Pt catalyst. We find that the more hydrophilic Pt/Al2O3 interface leads to smaller (more positive) free energies of solvation due to an increased entropy penalty resulting from the additional work necessary to disrupt the interfacial water structure and accommodate the interfacial species. The results will be of interest in other fields, including adsorption and proteins.
RESUMO
Liquid water and electric fields play significant roles in phenomena occurring at catalytic and electrocatalytic interfaces; however, how their interplay influences interfacial energetics remains uncertain. Electric fields control the orientations of water molecules, which we hypothesized would influence the solvation thermodynamics of surface species. To explore this hypothesis, we used multiscale simulations involving density functional theory and classical molecular dynamics. We computed the energies and entropies of solvation of surface species on Pt(111), specifically, adsorbed CH3OH, COH, and CO, which are intermediates in the pathway of methanol oxidation, in the presence of electric fields spanning -0.5 to +0.5 V Å-1. We found that both the energy and entropy of solvation depend on the strength and direction of the field, with the entropy of solvation being significantly impacted. Both the energy and entropy dependence on the field can be ascribed to water molecule orientations. Specifically, more positive fields orient water molecules so that they can more effectively hydrogen bond with surface species, which strengthens the energies of solvation. However, at more negative fields, competition with the surface species causes interfacial water molecules to reorient, which leads to disorder in the water structure and hence increased entropy.
RESUMO
A mathematical model was developed for the simulation of a parallel plate ammonia electrolyzer to convert ammonia in wastewater to nitrogen and hydrogen under basic conditions. The model consists of fundamental transport equations, the ammonia oxidation kinetics at the anode, and the hydrogen evolution kinetics at the cathode of the electrochemical reactor. The model shows both qualitative and quantitative agreement with experimental measurements at ammonia concentrations found within wastewater (200-1200 mg L(-1)). The optimum electrolyzer performance is dependent on both the applied voltage and the inlet concentrations. Maximum conversion of ammonia to nitrogen at the rates of 0.569 and 0.766 mg L(-1) min(-1) are achieved at low (0.01 M NH4Cl and 0.1 M KOH) and high (0.07 M NH4Cl and 0.15 M KOH) inlet concentrations, respectively. At high and low concentrations, an initial increase in the cell voltage will cause an increase in the system response - current density generated and ammonia converted. These system responses will approach a peak value before they start to decrease due to surface blockage and/or depletion of solvated species at the electrode surface. Furthermore, the model predicts that by increasing the reactant and electrolyte concentrations at a certain voltage, the peak current density will plateau, showing an asymptotic response.
