Parameterization of COSMO-RS model for ionic liquids

The adjustable parameters in the popular conductor-like screening model for real solvents(COSMO-RS)within the Amsterdam density functional(ADF)framework have been re-optimized to fit for the systems containing ionic liquids(ILs).To get the optimal values of misfit energy constant a^0,hydrogen bond coefficient c_(hb)and effective contact surface area of a segment a_(eff),2283 activity coefficient data points at infinite dilution and 1433 CO_2 solubility data points exhaustively collected from references were used as training set.The average relative deviations(ARDs)of activity coefficients at infinite dilution and CO_2 solubility between experimental data and predicted values are 32.22%and17.61%,respectively,both of which are significantly lower than the original COSMO-RS versions.Predictions for other activity coefficients of solutes in ILs,solubility data of CO_2 in pure ILs and the binary mixtures of ILs at either high or low temperatures,and vapor–liquid equilibrium(VLE)for binary systems involving ILs have also been performed to demonstrate the validity of the parameterization of COSMO-RS model for ILs.The results showed that the predicted results by COSMO-RS model with the new optimized parameters are in much better agreement with experimental data than those by the original versions over a wide temperature and pressure range.The COSMO-RS model for ILs presented in this work improves the prediction accuracy of thermodynamic properties for the systems containing ILs,which is always highly desirable for general chemical engineers.

Long-range Pt-Ni dual sites boost hydrogen evolution through optimizing the adsorption configuration

Elaborated design of catalytic systems with a specifically tailored site distance to match the intermediates could substantially improve reaction kinetics and boost catalytic activity under unfavorable reaction conditions.Considering the lower energy barriers of water splitting upon the synergy of dual sites,constructing synergistic Pt-M(M:transition metal)dual sites is an effective way to boost Pt with highly catalytic hydrogen evolution reaction(HER)performance.An unconventional“Ni(OH)_(2)-coated high-index Pt facets”was constructed to obtain long-range Pt-Ni dual sites,in which Ni composition as a water dissociation synergistic site can protect Pt from electrolyte corrosion and ensure efficient proton donation to Pt sites.The obtained long-range Pt-Ni dual sites present 3.84 mA·cm^(-1) of current density,which is 7.5 times specific activity higher than that of commercial Pt/C towards alkaline HER.The enhanced HER performance is attributed to synergistic catalysis on Pt-Ni dual sites accompanied by unconventional electron coupling.This work illustrates a new strategy to construct the long-range dual sites by unconventional strategy for fundamental electrocatalytic study of alkaline HER.