Water and Carbon Dioxide Adsorption on CaO(001) Studied via Single Crystal Adsorption Calorimetry

A new method to analyze microcalorimetry data was employed to study the adsorption energies and sticking probabilities of D2O and CO2 on CaO(001) at several temperatures. This method deconvolutes the line shapes of the heat detector response into an instrument response function and exponential decay functions, which correspond to the desorption of distinct surface species. This allows for a thorough analysis of the adsorption, dissociation, and desorption processes that occur during our microcalorimetry experiments. Our microcalorimetry results, show that D2O adsorbs initially with an adsorption energy of 85–90 kJ/mol at temperatures ranging from 120 to 300 K, consistent with prior spectroscopic studies that indicate dissociation. This adsorption energy decreases with increasing coverage until either D2O multilayers are formed at low temperatures (120 K) or the surface is saturated (> 150 K). Artificially producing defects on the surface by sputtering prior to dosing D2O sharply increases this adsorption energy, but these defects may be healed after annealing the surface to 1300 K. CO2 adsorbs on CaO(001) with an initial adsorption energy of ~ 125 kJ/mol, and decreases until the saturation coverage is reached, which is a function of surface temperature. The results showed that pre-adsorbed water blocks adsorption sites, lowers the saturation coverage, and lowers the measured adsorption energy of CO2. The calorimetry data further adds to our understanding of D2O and CO2 adsorption on oxide surfaces.

Ni Nanoparticles on CeO2 (111): Energetics, Electron Transfer and Structure by Ni Adsorption Calorimetry, Spectroscopies and DFT

<div>The morphology, interfacial bonding energetics and charge transfer of Ni clusters and nanoparticles on slightly-reduced CeO_2-x (111) surfaces at 100 to 300 K have been studied using single crystal adsorption calorimetry (SCAC), low-energy ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and density functional theory (DFT). The initial heat of adsorption of Ni vapor decreased with the extent of pre-reduction (x) of the CeO_2-x (111), showing that stoichiometric ceria adsorbs Ni more strongly than oxygen vacancies. On CeO_1.95 (111) at 300 K, the heat dropped quickly with coverage in the first 0.1 ML, attributed to nucleation of Ni clusters on stoichiometric steps, followed by the Ni particles spreading onto less favorable terrace sites. At 100 K, the clusters nucleate on terraces due</div><div>to slower diffusion. Adsorbed Ni monomers are in the +2 oxidation state, and they bind by ~45 kJ/mol more strongly to step sites than terraces. The measured heat of adsorption versus average particle size on terraces is favorably compared to DFT calculations. The Ce 3d XPS lineshape</div><div>showed an increase in Ce³⁺/Ce⁴⁺ ratio with Ni coverage, providing the number of electrons donated to the ceria per Ni atom. The charge transferred per Ni is initially large but strongly decreases with increasing cluster size for both experiments and DFT, and shows large differences between clusters at steps versus terraces. This charge is localized on the interfacial Ni and Ce atoms in their atomic layers closest to the interface. This knowledge is crucial to understanding the nature of the active sites on the surface of Ni-CeO₂ catalysts for which metal-oxide interactions play a very important role in the activation of O−H and C−H bonds. The changes in these interactions with Ni particle size (metal loading) and the extent of reduction of the ceria help to explain how previously reported catalytic activity and selectivity change with these same structural details.</div>

Ni Nanoparticles on CeO2 (111): Energetics, Electron Transfer and Structure by Ni Adsorption Calorimetry, Spectroscopies and DFT

<div>The morphology, interfacial bonding energetics and charge transfer of Ni clusters and nanoparticles on slightly-reduced CeO_2-x (111) surfaces at 100 to 300 K have been studied using single crystal adsorption calorimetry (SCAC), low-energy ion scattering spectroscopy (LEIS), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and density functional theory (DFT). The initial heat of adsorption of Ni vapor decreased with the extent of pre-reduction (x) of the CeO_2-x (111), showing that stoichiometric ceria adsorbs Ni more strongly than oxygen vacancies. On CeO_1.95 (111) at 300 K, the heat dropped quickly with coverage in the first 0.1 ML, attributed to nucleation of Ni clusters on stoichiometric steps, followed by the Ni particles spreading onto less favorable terrace sites. At 100 K, the clusters nucleate on terraces due</div><div>to slower diffusion. Adsorbed Ni monomers are in the +2 oxidation state, and they bind by ~45 kJ/mol more strongly to step sites than terraces. The measured heat of adsorption versus average particle size on terraces is favorably compared to DFT calculations. The Ce 3d XPS lineshape</div><div>showed an increase in Ce³⁺/Ce⁴⁺ ratio with Ni coverage, providing the number of electrons donated to the ceria per Ni atom. The charge transferred per Ni is initially large but strongly decreases with increasing cluster size for both experiments and DFT, and shows large differences between clusters at steps versus terraces. This charge is localized on the interfacial Ni and Ce atoms in their atomic layers closest to the interface. This knowledge is crucial to understanding the nature of the active sites on the surface of Ni-CeO₂ catalysts for which metal-oxide interactions play a very important role in the activation of O−H and C−H bonds. The changes in these interactions with Ni particle size (metal loading) and the extent of reduction of the ceria help to explain how previously reported catalytic activity and selectivity change with these same structural details.</div>

Isosteric Heat: Comparative Study between Clausius–Clapeyron, CSK and Adsorption Calorimetry Methods

This work presents the calorimetric study of five adsorbents with different chemical and textural characteristics: MOF-199, MCM-41, SBA-15, activated carbon prepared from corn cob (GACKP) and graphite. These solids were used to establish the differences between isosteric heats evaluated by three different methods: Clausius–Clapeyron (C-C), Chakraborty, Saha and Koyama (CSK) and Adsorption Calorimetry (A-Cal). The textural characterization results show solids that have values of specific surface area between 2271 m2·g−1 for the MOF-199 and 5.2 m2·g−1 for the graphite. According to the results obtained for the isosteric heats for each sample, the magnitude varies depending on the coverage of the adsorbate and the textural characteristics of each adsorbent. Solids with an organized structure have isosteric heat values that are coincident among the three methods. Meanwhile, heterogeneous solids such as activated carbon values evaluated by the CKS and C-C have a high dispersion method regarding the adsorption calorimetry method. The results obtained show that the adsorption calorimetry, being a direct experimental measurement method, presents less dispersed data. At low quantities, the isosteric heat of nitrogen adsorption decreased in the order MOF-199, GACKP, MCM-41, SBA-15 and Graphite. The order for the isosteric heats values was coherent with the surface characteristics of each of the solids, especially with the pore size distribution. Finally, throughout the coverage examined in this work, the isosteric heats for nitrogen adsorption determined by adsorption calorimetry (A-Cal) were larger than the evaluated by C-C and CSK indirect methods of vaporization. According to the results, it is shown that the adsorption calorimetry allows values of the isosteric heats of adsorption with an error of less than 2% to be established and also reveals the complex nature of the heterogeneity or homogeneity of the adsorbent.