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This tutorial review describes the use of variable temperature infrared spectroscopy of adsorbed species (VTIR), a recent method for studying the thermodynamics of weak solid-gas interactions. Examples show how a fundamental relationship of thermodynamics (the van't Hoff equation, used long since in several fields of physical chemistry) can describe equilibrium processes at the solid-gas interface. The VTIR method is fully exploited by measuring absorbance of an IR band, temperature and pressure over a wide temperature range: an estimation of the interaction energy is, however, possible even ignoring the equilibrium pressure. Precise thermodynamic characterization of solid-gas interactions is required in several fields: on the applied side, gas sensing, separation and storage, which involve such areas as work-place security, air pollution control and the energy sector; regarding fundamental knowledge, weak solid-gas interactions are relevant to a number of fields, including hydrogen bonding, coordination chemistry and surface phenomena in a broad sense. Infrared (IR) spectroscopy of (gas) molecules adsorbed on a solid is frequently used to characterize both, the adsorbed species and the adsorbing centres at the solid surface. The potential of the technique can be greatly enhanced by obtaining IR spectra over a temperature range, and simultaneously measuring IR absorbance, temperature and equilibrium pressure. When this is done, variable temperature infrared (VTIR) spectroscopy can be used not only for a more detailed surface characterization, but also for precise studies on the thermodynamics of solid-gas interactions. Furthermore, when weak interactions are concerned, the technique shows favourable features compared to adsorption calorimetry, or to other classical methods. The potential of the VTIR method is highlighted by reviewing recently reported studies on dihydrogen, dinitrogen and carbon monoxide adsorption on zeolites. To facilitate understanding, an outline of the basis of the method is also given, together with an appraisal of the critical points involved in its practical use.

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Imogolite-like nanotubes have been synthesised in which SiCH(3) groups have been introduced in place of the SiOH groups that naturally occur at the inner surface of imogolite, an alumino-silicate with formula (OH)(3)Al(2)O(3)SiOH, forming nanotubes with inner and outer diameter of 1.0 and 2.0 nm, respectively. The new nanotubular material, composition (OH)(3)Al(2)O(3)SiCH(3), has both larger pores and higher specific surface area than unmodified imogolite: it forms as hollow cylinders 3.0 nm wide and several microns long, with a specific surface area of ca. 800 m(2) g(-1) and intriguing surface properties, due to hydrophobic groups inside the nanotubes and hydrophilic Al(OH)Al groups at their outer surface. Adsorption of methane at 30 °C has been studied in the pressure range between 5 and 35 bar on both the new material and unmodified imogolite: it resulted that the new material adsorption capacity is about 2.5 times larger than that of imogolite, in agreement with both its larger pore volume and the presence of a methylated surface. On account of these properties and of its novelty, the studied material has several potential technical applications, e.g. in the fields of gas chromatography and gas separation.

The adsorption of carbon dioxide onto M-ZSM-5 zeolites (M = Li, Na, K, Cs) was studied by means of FTIR spectroscopy and adsorption microcalorimetry. Quantum chemical calculations, at the B3-LYP level, on the interaction of CO2 with the bare alkali-metal cations were performed to assist interpretation of the experimental results. With the likely exception of Li+, CO2 was found to undergo a two-step interaction with the metal ions. At a low equilibrium pressure linear 1:1 adducts of the type M+···OCO (M = Na+, K+, Cs+) are formed; upon increasing the CO2 equilibrium pressure, the metal cation coordinates a second CO2 molecule, forming a 2:1 adduct. Calculated (ab initio) bond lengths for the 1:1 adduct are given, as well as corresponding values of the binding energy and enthalpic term. Experimentally derived values of the main thermodynamic functions (ΔH°, ΔG°, and ΔS°) are discussed and correlated with detailed results from IR spectroscopy. The interaction cation/CO2 alone cannot account for the body of evidence, and the contribution of nearby O2- anions has to be invoked.

The development of an "artificial leaf" that collects energy in the same way as a natural one is one of the great challenges for the use of renewable energy and a sustainable development. To avoid the problem of intermittency in solar energy, it is necessary to design systems that directly capture CO(2) and convert it into liquid solar fuels that can be easily stored. However, to be advantageous over natural leaves, it is necessary that artificial leaves have a higher solar energy-to-chemical fuel conversion efficiency, directly provide fuels that can be used in power-generating devices, and finally be robust and of easy construction, for example, smart, cheap and robust. This review discusses the recent progress in this field, with particular attention to the design and development of 'artificial leaf' devices and some of their critical components. This is a very active research area with different concepts and ideas under investigation, although often the validity of the considered solutions it is still not proven or the many constrains are not fully taken into account, particularly from the perspective of system engineering, which considerably limits some of the investigated solutions. It is also shown how system design should be included, at least at a conceptual level, in the definition of the artificial leaf elements to be investigated (catalysts, electrodes, membranes, sensitizers) and that the main relevant aspects of the cell engineering (mass/charge transport, fluid dynamics, sealing, etc.) should be also considered already at the initial stage because they determine the design and the choice between different options. For this reason, attention has been given to the system-design ideas under development instead of the molecular aspects of the O(2) - or H(2) -evolution catalysts. However, some of the recent advances in these catalysts, and their use in advanced electrodes, are also reported to provide a more complete picture of the field.

The interaction between CO (either via the C or the O end) and the alkaline cations (Li+, Na+, K+, Rb+, and Cs+) has been studied by means of six ab initio methods, featuring the classical Hartree–Fock, the second order Mo/ller–Plesset treatment of electron correlation, one local density functional and two gradient-corrected methods as well as a quadratic configuration interaction inclusive of single and double substitutions with a noniterative triples contribution to the energy. Basis sets adopted for CO, Li+, Na+, and K+ and the corresponding adducts are of triple-ζ valence quality augmented with a double set of polarization functions (d on C and O; p on the cations). For Rb+ and Cs+, Hay–Wadt effective core potential basis sets have been adopted. Calculated features are the binding energy, the frequency and intensity of the CO stretch, the bending mode, the cation-carbon (or oxygen) stretch, and the equilibrium geometry. Gradient-corrected density functional methods yield results nearly as good as the most expensive correlated method based on configurations interaction. A number of correlations are established among the observables. The role of electrostatics in the interaction is analyzed both by studying the molecular electrostatic potential of CO and by replacing the cation with a proton in the same position. Binding through the C end is invariably preferred, though, with increasing size of the cation, binding through the O end become progressively less unfavored. Experimental data concerning alkaline-cation substituted zeolites are compared with computational results, and an overall agreement is observed.

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