A rapid microwave-assisted synthesis of a sodium-cadmium metal-organic framework having improved performance as a CO2 adsorbent for CCS.

We report on a facile and rapid microwave-assisted method for preparing a sodium-cadmium metal-organic framework (having coordinatively unsaturated sodium ions) that considerably shortens the conventional synthesis time from 5 days to 1 hour. The obtained (Na,Cd)-MOF showed an excellent volumetric CO2 adsorption capacity (5.2 mmol cm(-3) at 298 K and 1 bar) and better CO2 adsorption properties than those shown by the same metal-organic framework when synthesized following a more conventional procedure. Moreover, the newly prepared material was found to display high selectivity for adsorption of carbon dioxide over nitrogen, and good regenerability and stability during repeated CO2 adsorption-desorption cycles, which are the required properties for any adsorbent intended for carbon dioxide capture and sequestration (CSS) from the post-combustion flue gas of fossil fuelled power stations.

Variable-temperature IR spectroscopic and theoretical studies on CO2 adsorbed in zeolite K-FER.

Adsorption of CO(2) in K-FER zeolite is investigated by a combination of variable-temperature IR spectroscopy and periodic DFT calculations augmented for description of dispersion interactions. Calculated adsorption enthalpies for CO(2) adsorption complexes on single extra-framework K(+) sites and on dual-cation sites where CO(2) interacts simultaneously with two extra-framework K(+) cations (-40 and -44 kJ mol(-1), respectively) are in excellent agreement with experimental values. The analysis of effects on the frequency of the asymmetric CO(2) stretching mode ν(3) shows that polarization of CO(2) by the K(+) cation leads to an increase in ν(3), while the interaction of CO(2) with the zeolite framework leads to a decrease in ν(3). In the case of K-FER, the latter effect is slightly larger than the former, and thus a small redshift in ν(3) results (-3 cm(-1) with respect to free CO(2)). For adsorption complexes on dual K(+) sites, where CO(2) interacts with one K(+) cation on each end of the molecule, the polarization of CO(2) molecules on both sides results in a blueshift of ν(3). The origin of the redshift in ν(3) when CO(2) is adsorbed in purely siliceous FER is also investigated computationally. Calculations show that the dispersion interaction does not affect the vibrational frequency of adsorbed CO(2).

Variable-temperature infrared spectroscopy studies on the thermodynamics of CO adsorption on the zeolite Ca-Y.

Variable temperature FT-IR spectroscopy (in the range of 298-380 K) is used to study the thermodynamics of formation of Ca(2+)...CO carbonyl species upon CO adsorption on the faujasite-type zeolite Ca-Y, and also the (temperature-dependent) isomerization equilibrium between carbonyl and isocarbonyl (Ca(2+)...OC) species. The standard enthalpy and entropy changes involved in formation of the monocarbonyl species resulted to be DeltaH(0)=-50.3 (+/-0.5) kJ mol(-1) and DeltaS(0)=-186 (+/-5) J mol(-1) K(-1), respectively. Isomerization of the (C-bonded) Ca(2+)...CO carbonyl to yield the (O-bonded) Ca(2+)...OC isocarbonyl involves an enthalpy change DeltaH(iso)(0)=+11.4 (+/-1.0) kJ mol(-1). These results are compared with previously reported data for the CO/Sr-Y system; and also, a brief analysis of enthalpy-entropy correlation for CO adsorption on zeolites and metal oxides is given.

Materials for hydrogen storage: current research trends and perspectives.

Storage and transport of hydrogen constitutes a key enabling technology for the advent of a hydrogen-based energy transition. Main research trends on hydrogen storage materials, including metal hydrides, porous adsorbents and hydrogen clathrates, are reviewed with a focus on recent developments and an appraisal of the challenges ahead. .