Ethanol and Water Adsorption on Close-Packed 3d, 4d, and 5d Transition-Metal Surfaces: A Density Functional Theory Investigation with van der Waals Correction

Nowadays, there is a great interest in the economic success of direct ethanol fuel cells; however, our atomistic understanding of the designing of stable and low-cost catalysts for the steam reforming of ethanol is still far from satisfactory, in particular due to the large number of undesirable intermediates. In this study, we will report a first-principles investigation of the adsorption properties of ethanol and water at low coverage on close-packed transition-metal (TM) surfaces, namely, Fe(110), Co(0001), Ni(111), Cu(111), Ru(0001), Rh(111), Pd(111), Ag(111), Os(0001), Ir(111), Pt(111), and Au(111), employing density functional theory (DFT) calculations. We employed the generalized gradient approximation with the formulation proposed by Perdew, Burke, and Erzenholf (PBE) to the exchange correlation functional and the empirical correction proposed by S. Grimme (DFT+D3) for the van der Waals correction. We found that both adsorbates binds preferentially near or on the on top sites of the TM surfaces through the 0 atoms. The PBE adsorption energies of ethanol and water decreases almost linearly with the increased occupation of the 4d and 5d d-band, while there is a deviation for the 3d systems. The van der Waals correction affects the linear behavior and increases the adsorption energy for both adsorbates, which is expected as the van der Waals energy due to the correlation effects is strongly underestimated by DFT-PBE for weak interacting systems. The geometric parameters for water/TM are not affected by the van der Waals correction, i.e., both DFT and DFT+D3 yield an almost parallel orientation for water on the TM surfaces; however, DFT+D3 changes drastically the ethanol orientation. For example, DFT yields an almost perpendicular orientation of the C-C bond to the TM surface, while the C-C bond is almost parallel to the surface using DFT +D3 for all systems, except for ethanol/Fe(110). Thus, the van der Waals correction decreases the distance of the C atoms to the TM surfaces, which might contribute to break the C-C bond. The work function decreases upon the adsorption of ethanol and water, and both follow the same trends, however, with different magnitude (larger for ethanol/TM) due to the weak binding of water to the surface. The electron density increases mainly in the region between the topmost layer and the adsorbates, which explains the reduction of the substrate work function.

Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Synthesis of high-surface-area gamma-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

Several types of alumina were synthesized from sodium aluminate (NaAlO2) by precipitation with sulfuric acid (H2SO4) and subsequently calcination at 500 degrees C to obtain gamma-Al2O3. The precursor aluminate was derived from aluminum scrap. The various gamma-Al2O3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N-2 (S-BET) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al2O3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m(2) g(-1)) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined. (C) 2012 Elsevier B.V. All rights reserved.

Physical and mineralogical changes of Hungarian monumental stones exposed to different conditions: stone-testing in-situ and under laboratory conditions

The Székesfehérvár Ruin Garden is a unique assemblage of monuments belonging to the cultural heritage of Hungary due to its important role in the Middle Ages as the coronation and burial church of the Kings of the Hungarian Christian Kingdom. It has been nominated for “National Monument” and as a consequence, its protection in the present and future is required. Moreover, it was reconstructed and expanded several times throughout Hungarian history. By a quick overview of the current state of the monument, the presence of several lithotypes can be found among the remained building and decorative stones. Therefore, the research related to the materials is crucial not only for the conservation of that specific monument but also for other historic structures in Central Europe. The current research is divided in three main parts: i) description of lithologies and their provenance, ii) physical properties testing of historic material and iii) durability tests of analogous stones obtained from active quarries. The survey of the National Monument of Székesfehérvár, focuses on the historical importance and the architecture of the monument, the different construction periods, the identification of the different building stones and their distribution in the remaining parts of the monument and it also included provenance analyses. The second one was the in situ and laboratory testing of physical properties of historic material. As a final phase samples were taken from local quarries with similar physical and mineralogical characteristics to the ones used in the monument. The three studied lithologies are: fine oolitic limestone, a coarse oolitic limestone and a red compact limestone. These stones were used for rock mechanical and durability tests under laboratory conditions. The following techniques were used: a) in-situ: Schmidt Hammer Values, moisture content measurements, DRMS, mapping (construction ages, lithotypes, weathering forms) b) laboratory: petrographic analysis, XRD, determination of real density by means of helium pycnometer and bulk density by means of mercury pycnometer, pore size distribution by mercury intrusion porosimetry and by nitrogen adsorption, water absorption, determination of open porosity, DRMS, frost resistance, ultrasonic pulse velocity test, uniaxial compressive strength test and dynamic modulus of elasticity. The results show that initial uniaxial compressive strength is not necessarily a clear indicator of the stone durability. Bedding and other lithological heterogeneities can influence the strength and durability of individual specimens. In addition, long-term behaviour is influenced by exposure conditions, fabric and, especially, the pore size distribution of each sample. Therefore, a statistic evaluation of the results is highly recommended and they should be evaluated in combination with other investigations on internal structure and micro-scale heterogeneities of the material, such as petrographic observation, ultrasound pulse velocity and porosimetry. Laboratory tests used to estimate the durability of natural stone may give a good guidance to its short-term performance but they should not be taken as an ultimate indication of the long-term behaviour of the stone. The interdisciplinary study of the results confirms that stones in the monument show deterioration in terms of mineralogy, fabric and physical properties in comparison with quarried stones. Moreover stone-testing proves compatibility between quarried and historical stones. Good correlation is observed between the non-destructive-techniques and laboratory tests results which allow us to minimize sampling and assessing the condition of the materials. Concluding, this research can contribute to the diagnostic knowledge for further studies that are needed in order to evaluate the effect of recent and future protective measures.

The adsorption of biomolecules to multi-walled carbon nanotubes is influenced by both pulmonary surfactant lipids and surface chemistry

Background During production and processing of multi-walled carbon nanotubes (MWCNTs), they may be inhaled and may enter the pulmonary circulation. It is essential that interactions with involved body fluids like the pulmonary surfactant, the blood and others are investigated, particularly as these interactions could lead to coating of the tubes and may affect their chemical and physical characteristics. The aim of this study was to characterize the possible coatings of different functionalized MWCNTs in a cell free environment. Results To simulate the first contact in the lung, the tubes were coated with pulmonary surfactant and subsequently bound lipids were characterized. The further coating in the blood circulation was simulated by incubating the tubes in blood plasma. MWCNTs were amino (NH2)- and carboxyl (-COOH)-modified, in order to investigate the influence on the bound lipid and protein patterns. It was shown that surfactant lipids bind unspecifically to different functionalized MWCNTs, in contrast to the blood plasma proteins which showed characteristic binding patterns. Patterns of bound surfactant lipids were altered after a subsequent incubation in blood plasma. In addition, it was found that bound plasma protein patterns were altered when MWCNTs were previously coated with pulmonary surfactant. Conclusions A pulmonary surfactant coating and the functionalization of MWCNTs have both the potential to alter the MWCNTs blood plasma protein coating and to determine their properties and behaviour in biological systems.

Peptide interfacial adsorption is kinetically limited by the thermodynamic stability of self association

We present a study of the adsorption of two peptides at the octane–water interface. The first peptide, Lac21, exists in mixed monomer–tetramer equilibrium in bulk solution with an appreciable monomer concentration. The second peptide, Lac28, exists as a tetramer in solution, with minimal exposed hydrophobic surface. A kinetic limitation to interfacial adsorption exists for Lac28 at moderate to high surface coverage that is not observed for Lac21. We estimate the potential energy barrier for Lac28 adsorption to be 42 kJ/mol and show that this is comparable to the expected free energy barrier for tetramer dissociation. This finding suggests that, at moderate to high surface coverage, adsorption is kinetically limited by the availability of interfacially active monomeric “domains” in the subinterfacial region. We also show how the commonly used empirical equation for protein adsorption dynamics can be used to estimate the potential energy barrier for adsorption. Such an approach is shown to be consistent with a formal description of diffusion–adsorption, provided a large potential energy barrier exists. This work demonstrates that the dynamics of interfacial adsorption depend on protein thermodynamic stability, and hence structure, in a quantifiable way.

Adsorption from a one-dimensional lattice gas and the Brunauer–Emmett–Teller equation

An exact treatment of adsorption from a one-dimensional lattice gas is used to eliminate and correct a well-known inconsistency in the Brunauer–Emmett–Teller (B.E.T.) equation—namely, Gibbs excess adsorption is not taken into account and the Gibbs integral diverges at the transition point. However, neither model should be considered realistic for experimental adsorption systems.

Selective adsorption of l- and d-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO3), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Assessment of CO2 adsorption capacity on activated carbons by a combination of batch and dynamic tests

In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance for three different activated carbons obtained from olives stones by chemical activation followed by physical activation with CO2 at varying times, i.e. 20, 40 and 60 h. Kinetic and thermodynamic CO2 adsorption tests from simulated flue-gas at different temperature and CO2 pressure are carried out both in batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with CO2/N2 mixture) conditions. The textural characterization of the activated carbon samples shows a direct dependence of both micropore and ultramicropore volume on the activation time, hence AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that, when CO2 pressure is lower than 0.3 bar, the lower the activation time the higher CO2 adsorption capacity and a ranking ωeq(AC20)>ωeq(AC40)>ωeq(AC60) can be exactly defined when T= 293 K. This result can be likely ascribed to a narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of a flue-gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight that the adsorption of N2 on the synthesized AC samples can be considered negligible. Finally, the importance of a proper analysis of characterization data and adsorption experimental results is highlighted for a correct assessment of CO2 removal performances of activated carbons at different CO2 pressure and operating temperature.

Water adsorption in hydrophilic zeolites: experiment and simulation

We have measured experimental adsorption isotherms of water in zeolite LTA4A, and studied the regeneration process by performing subsequent adsorption cycles after degassing at different temperatures. We observed incomplete desorption at low temperatures, and cation rearrangement at successive adsorption cycles. We also developed a new molecular simulation force field able to reproduce experimental adsorption isotherms in the range of temperatures between 273 K and 374 K. Small deviations observed at high pressures are attributed to the change in the water dipole moment at high loadings. The force field correctly describes the preferential adsorption sites of water at different pressures. We tested the influence of the zeolite structure, framework flexibility, and cation mobility when considering adsorption and diffusion of water. Finally, we performed checks on force field transferability between different hydrophilic zeolite types, concluding that classical, non-polarizable water force fields are not transferable.

High-Resolution N2 Adsorption Isotherms at 77.4 K: Critical Effect of the He Used During Calibration

Accurate characterization of the microporous structure in porous solids is of paramount importance for several applications such as energy and gas storage, nanoconfinement reactions, and so on. Among the different techniques for precise textural characterization, high-precision gas adsorption measurement of probe molecules at cryogenic temperatures (e.g., N2 at 77.4 K and Ar at 87.3 K) is the most widely used, after appropriate calibration of the sample holder with a probe gas, which does not experience physisorption processes. Although traditionally helium has been considered not to be adsorbed in porous solids at cryogenic temperatures, here we show that even at 77.4 K (high above its boiling temperature, 4 K) the use of He in the calibration step can give rise to erroneous interpretations when narrow micropores/constrictions are present.

Effects of carbon surface chemistry and solution pH on the adsorption of binary aromatic solutes

Adsorption of p-cresol, nitrobenzene and p-nitrophenol on treated and untreated carbons is investigated systematically. The effects of carbon surface chemistry and solution pH are studied and discussed. All adsorption experiments were carried out in pH-controlled solutions to examine the adsorption properties of the adsorption systems where the solutes are in molecular as well as ionic forms. Using the homogeneous Langmuir equation, the single solute parameters are determined. These parameters are then used to predict the binary solute adsorption isotherms and gain further insights into the adsorption process. (C) 2002 Elsevier Science Ltd. All rights reserved.

Study of hexane adsorption in nanoporous MCM-41 silica

We study here the adsorption of hexane on nanoporous MCM-41 silica at 303, 313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data.