According to the European Commission, in 2016 the residential sector represented 25.4% of the final energy consumption. Heating and cooling in EU households account for 69.1% of the total energy consumption. The fraction of 84% for heating and cooling is still generated from fossil fuels, and only 16% is generated from renewable energy. To decrease carbon dioxide emissions of fossil fuel consumption, it is crucial to find alternatives to supply the heating and cooling demand. Alternatives such as adsorption-based heat pumps and desiccant cooling systems are receiving much attention because of their moderate energy consumption. These systems are based on the energetic exchange during the adsorption/desorption of working fluids. In this work, we combined experiments and simulations to evaluate the viability of several zeolites and MOFs with water for cooling systems applications. We combined the study of adsorption mechanisms and the dynamics of water inside the pores of the structures, thereby obtaining an overall understanding of the working pair. We found that the Al content in FAU-topology zeolites is a key factor for an efficient process. We also identify ZJNU-30 metal–organic framework as a suitable candidate for cooling applications because of its outstanding water capacity, cooling capacity, and coefficient of performance.@en

The separation and purification of light hydrocarbons is challenging in the industry. Recently, a ZJNU-30 metal-organic framework (MOF) has been found to have the potential for adsorption-based separation of olefins and diolefins with four carbon atoms [H. M. Liu et al. Chem. - Eur. J. 2016, 22, 14988-14997]. Our study corroborates this finding but reveals Fe-MOF-74 as a more efficient candidate for the separation because of the open metal sites. We performed adsorption-based separation, transient breakthrough curves, and density functional theory calculations. This combination of techniques provides an extensive understanding of the studied system. Using this MOF, we propose a separation scheme to obtain a high-purity product.

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The effect of confinement on the equilibrium reactive system containing nitrogen dioxide and dinitrogen tetroxide is studied by molecular simulation and the reactive Monte Carlo (RxMC) approach. The bulk-phase reaction was successfully reproduced and five all-silica zeolites (i.e. FAU, FER, MFI, MOR, and TON) with different topologies were selected to study their adoption behavior. Dinitrogen tetroxide showed a stronger affinity than nitrogen dioxide in all the zeolites due to size effects, but exclusive adsorption sites in MOR allowed the adsorption of nitrogen dioxide with no competition at these sites. From the study of the adsorption isotherms and isobars of the reacting mixture, confinement enhanced the formation of dimers over the full range of pressure and temperature, finding the largest deviations from bulk fractions at low temperature and high pressure. The channel size and shape of the zeolite have a noticeable influence on the dinitrogen tetroxide formation, being more important in MFI, closely followed by TON and MOR, and finally FER and FAU. Preferential adsorption sites in MOR lead to an unusually strong selective adsorption towards nitrogen dioxide, demonstrating that the topological structure has a crucial influence on the composition of the mixture and must be carefully considered in systems containing nitrogen dioxide.

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We present a molecular simulation study on the most suitable zeolite topologies for hydrogen adsorption and storage. We combine saturation capacities, pore size distributions, preferential adsorption sites, and curves of heat of adsorption of hydrogen as a function of temperature (we call them heats of adsorption (HoA)-curve) to identify the optimal zeolites for storage and release of hydrogen. Then, we analyze the relation between the shape of the HoA-curve and the topology of the materials. We also evaluate the influence of incorporating Feynman-Hibbs effect on the adsorption behavior. We can establish different shapes on the HoA-curve depending on the uniformity or not of the pores of the zeolites. Parabola-like curves are observed in structures with one or similarly sized pores, whereas deviations from the parabola are found at low temperature for structures combining large and small pores. The Feynman-Hibbs quantum correction reduces the adsorption capacity of the materials affecting not only the saturation capacity but also the shape of the isotherms. From our results, the zeolites studied in this work can be considered potential candidates for the storage and release of hydrogen.

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An increase in demand for energy efficient processes for the separation of saturated and unsaturated light hydrocarbons mixtures drives the need of noncryogenic processes. The adsorptive separation using Metal-Organic Frameworks with coordinatively unsaturated metal sites may provide a cost-effective alternative due to the strong binding of the metal cation with the unsaturated hydrocarbons. Since experiments on adsorption equilibrium of gas mixtures are challenging, we propose classical force field based simulations to analyse the ability of MOF-74 with different metal substitutions for the separation of C2 and C3 olefin/paraffin binary mixtures. We parametrized the force field by fitting to available experimental single-component adsorption isotherms of ethane, ethene, propane, and propene in M–MOF-74 (M=Co, Fe, Mn, and Ni). The force field was validated for a variety of temperatures ranged from 273 K to 353 K. We then conducted Monte Carlo simulations in the Grand-Canonical ensemble to elucidate the adsorption mechanisms of the saturated/unsaturated hydrocarbon mixtures, at 318 K and 353 K. We computed the adsorption isotherms, and from these the adsorption selectivity, and addressed the variations of MOF properties with different metal cations. Fe-based MOF-74 appears the best option for both ethane/ethene and propane/propene separation applications. This finding partly agrees with previous work based on the Ideal Adsorbed Solution Theory.@en

Computing bubble-points of multicomponent mixtures using Monte Carlo simulations is a non-trivial task. A new method is used to compute gas compositions from a known temperature, bubble-point pressure, and liquid composition. Monte Carlo simulations are used to calculate the bubble-points of carbon dioxide (CO2) and methane (CH4) mixtures in the ionic liquids (ILs) 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [bmim][Tf2N] and 1-ethyl-3-methylimidazolium diethylphosphate [emim][dep]. The Continuous Fractional Component Monte Carlo (CFCMC) method in the osmotic ensemble has been used to compute the solubility of CO2/CH4 gas mixtures at different temperatures (T), pressures (P), and gas compositions (yi). The effect of T, P, and yi on the real CO2/CH4 selectivity (i.e., the selectivity of CO2 in the presence of CH4) is investigated. The real selectivity will differ from the ideal selectivity, which is defined as the ratio of the Henry's constants, if the solubility of CO2 is influenced by the presence of CH4. The computed real selectivities are compared with the experimentally obtained real and ideal selectivities. The real CO2/CH4 selectivity decreases with increasing temperature and pressure, while the gas phase composition has a minor effect. The real selectivity is approximately identical to the ideal selectivity for relatively low pressures and low solute concentrations in the liquid phase. The real selectivity deviates from the ideal selectivity as the solute concentration in the liquid phase increases.@en

Monte Carlo simulations are used to calculate the solubility of natural gas components in ionic liquids (ILs) and Selexol, which is a mixture of poly(ethylene glycol) dimethyl ethers. The solubility of the pure gases carbon dioxide (CO₂), methane (CH₄), ethane (C₂H₆), and sulfur dioxide (SO₂) in the ILs 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C_nmim][Tf₂N], n = 4, 6), 1-ethyl-3-methylimidazolium diethylphosphate ([emim][dep]), and Selexol (CH₃O[CH₂CH₂O]_nCH₃, n = 4, 6) have been computed at 313.15 K and several pressures. The gas solubility trend observed in the experiments and simulations is: SO₂ > CO₂ > C₂H₆ > CH₄. Overall, the Monte Carlo simulation results are in quantitative agreement with existing experimental data. Molecular simulation is an excellent tool to predict gas solubilities in solvents and may be used as a screening tool to navigate through the large number of theoretically possible ILs.

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