In this review we describe 30 years of research on the surface properties of magnesium oxide, considered as the model prototype oxide of cubic structure. The surface properties of single crystals, thin films and powdered samples (sintered at progressive higher temperatures) are considered and compared, with the aim of demonstrating that the gap between "believed perfect" single crystal surfaces, typical of "pure" Surface Science, and high surface area samples, typical of Catalysis Science, can be progressively reduced. The surface features considered in this review are the structural (morphological), optical, absorptive and reactive properties. As the carbon monoxide molecule is able to probe the surface properties of both anions and cations, it can give a complete information of the surface structure of MgO samples. For this reason the adsorption and spectroscopy of this molecule is preferentially considered in this review. Particular emphasis is given in reviewing results obtained by high resolution transmission microscopy and in situ IR spectroscopy of adsorbed species (in both reflection and transmission modes), but also UV-Vis diffuse reflectance, photoluminescence, TDS, EPR, electron based techniques are mentioned. Reviewed experimental results are also commented in view of the important theoretical literature available on this topic and are complemented by new transmission IR data concerning CO adsorbed, down to 60 K, on powdered MgO samples with increasing surface area. These innovative experiments allow us to perform, on powdered samples, the adsorption experiments typical of single crystals (or films) Surface Science, with an increase of the S/N of the vibrational features higher than two order of magnitude. As far the new results (never published before) are concerned, we report IR spectra of CO dosed at 60 K on polycrystalline MgO samples with different surface area obtained by Mg(OH)(2) decomposition and progressive sintering at high temperature. The samples morphology of each sintering stage has been controlled by high resolution TEM. The decomposition of the hydroxide to oxide is shown to occur with partial retention of the long range order, with formation of layers of compenetrated cubes oriented according to the original brucite planes. The CO adsorption experiments have been carried out using a new apparatus developed ad hoc to perform in situ mid-IR experiments, in transmission mode, on an activated (up to 1100 K) powdered samples in the desired atmosphere at any defined temperature in the 300-20 K interval. The influence of the surface area on the IR features characterizing the MgO/CO system at 60 K have been investigated by increasing the sintering treatment of the native Mg(OH)(2) and by preparing a low area MgO smoke sample, obtained by Mg combustion. New results have been compared with literature data obtained on powdered MgO at higher temperature and on MgO single crystals and thin films. A decrease of about 40 K with respect to the classical IR experiments reported in the literature results in a remarkably detailed evolution of the spectra as a function of CO pressure, allowing us to better understand the complex interaction of the CO molecule with the different cationic and anionic sites of the MgO surface. In particular, it has been possible to observe the precursors of the polymeric species, formed on the basic coordinatively unsaturated O2- sites, which dominate the room temperature spectra. Ab initio calculations, on simple models, have been used for the vibrational assignment of surface species. A qualitative agreement has been obtained between computed and experimental IR modes. The evolution of the spectra at decreasing MgO surface area (i.e. upon decreasing the surface defectivity) results in spectra whose features are well comparable with those obtained by IRAS on vacuum cleaved single crystals, but characterized by a much better signal/noise ratio. The temperature evolution of the intensity of the IR features of CO adsorbed on individual adsorption sites allows, unlike microcalorimetric experiments, the determination of site-specific adsorption enthalpies. The adsorption enthalpy of Mg2+...(CO) adducts on 5- and 4-fold coordinated magnesium cations are similar to12 and similar to22 kJ mol(-1) respectively. This relevant amount of new experimental data allows us to critically review experimental and theoretical works appeared in the literature on this case study of Surface Science. (C) 2004 Elsevier Ltd. All rights reserved.

Carbon monoxide MgO from dispersed solids to single crystals: a review and new advances

SPOTO, Giuseppe;RICCHIARDI, Gabriele;DAMIN, Alessandro Ali;SCARANO, Domenica;BORDIGA, Silvia;LAMBERTI, Carlo;ZECCHINA, Adriano
2004

Abstract

In this review we describe 30 years of research on the surface properties of magnesium oxide, considered as the model prototype oxide of cubic structure. The surface properties of single crystals, thin films and powdered samples (sintered at progressive higher temperatures) are considered and compared, with the aim of demonstrating that the gap between "believed perfect" single crystal surfaces, typical of "pure" Surface Science, and high surface area samples, typical of Catalysis Science, can be progressively reduced. The surface features considered in this review are the structural (morphological), optical, absorptive and reactive properties. As the carbon monoxide molecule is able to probe the surface properties of both anions and cations, it can give a complete information of the surface structure of MgO samples. For this reason the adsorption and spectroscopy of this molecule is preferentially considered in this review. Particular emphasis is given in reviewing results obtained by high resolution transmission microscopy and in situ IR spectroscopy of adsorbed species (in both reflection and transmission modes), but also UV-Vis diffuse reflectance, photoluminescence, TDS, EPR, electron based techniques are mentioned. Reviewed experimental results are also commented in view of the important theoretical literature available on this topic and are complemented by new transmission IR data concerning CO adsorbed, down to 60 K, on powdered MgO samples with increasing surface area. These innovative experiments allow us to perform, on powdered samples, the adsorption experiments typical of single crystals (or films) Surface Science, with an increase of the S/N of the vibrational features higher than two order of magnitude. As far the new results (never published before) are concerned, we report IR spectra of CO dosed at 60 K on polycrystalline MgO samples with different surface area obtained by Mg(OH)(2) decomposition and progressive sintering at high temperature. The samples morphology of each sintering stage has been controlled by high resolution TEM. The decomposition of the hydroxide to oxide is shown to occur with partial retention of the long range order, with formation of layers of compenetrated cubes oriented according to the original brucite planes. The CO adsorption experiments have been carried out using a new apparatus developed ad hoc to perform in situ mid-IR experiments, in transmission mode, on an activated (up to 1100 K) powdered samples in the desired atmosphere at any defined temperature in the 300-20 K interval. The influence of the surface area on the IR features characterizing the MgO/CO system at 60 K have been investigated by increasing the sintering treatment of the native Mg(OH)(2) and by preparing a low area MgO smoke sample, obtained by Mg combustion. New results have been compared with literature data obtained on powdered MgO at higher temperature and on MgO single crystals and thin films. A decrease of about 40 K with respect to the classical IR experiments reported in the literature results in a remarkably detailed evolution of the spectra as a function of CO pressure, allowing us to better understand the complex interaction of the CO molecule with the different cationic and anionic sites of the MgO surface. In particular, it has been possible to observe the precursors of the polymeric species, formed on the basic coordinatively unsaturated O2- sites, which dominate the room temperature spectra. Ab initio calculations, on simple models, have been used for the vibrational assignment of surface species. A qualitative agreement has been obtained between computed and experimental IR modes. The evolution of the spectra at decreasing MgO surface area (i.e. upon decreasing the surface defectivity) results in spectra whose features are well comparable with those obtained by IRAS on vacuum cleaved single crystals, but characterized by a much better signal/noise ratio. The temperature evolution of the intensity of the IR features of CO adsorbed on individual adsorption sites allows, unlike microcalorimetric experiments, the determination of site-specific adsorption enthalpies. The adsorption enthalpy of Mg2+...(CO) adducts on 5- and 4-fold coordinated magnesium cations are similar to12 and similar to22 kJ mol(-1) respectively. This relevant amount of new experimental data allows us to critically review experimental and theoretical works appeared in the literature on this case study of Surface Science. (C) 2004 Elsevier Ltd. All rights reserved.
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MgO; CO; FTIR; TEM; TDS; reflectance spectroscopy; photoluminescence spectroscopy; adsorption at surfaces; adsorption enthalpy; in situ spectroscopy; ab initio calculations
G. SPOTO; E.N. GRIBOV; G. RICCHIARDI; A. DAMIN; D. SCARANO; S. BORDIGA; C. LAMBERTI; A. ZECCHINA
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2318/22023
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