Water adsorption on O-covered Ru{0001}: coverage-dependent change from dissociation to molecular adsorption

When water is coadsorbed with oxygen at coverages above 0.25ML an intact water species is observed in high resolution X-ray photoelectron spectroscopy up to 220 K, which is significantly more stable than intact water on the clean surface. The presence of this species causes a shift in the O 1s binding energy of the pre-adsorbed oxygen, which indicates the formation of hydrogen bonds between the two adsorbates. Low coverages of oxygen induce partial dissociation and recombinative desorption in the same temperature range, which illustrates that desorption temperatures alone cannot be used to determine whether water is molecularly intact or not.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Water adsorption isotherms and isosteric sorption heat of spray-dried and freeze-dried dehydrated passion fruit pulp with additives and skimmed milk

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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.

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.

Adsorption techniques in drinking water treatment : papers and discussion from the NATO/CCMS symposium held in Reston, Virginia, USA, April 30 through May 2, 1979 /

Mode of access: Internet.

Trace elements removal from water using modified activated carbon

This paper present the possible alternative options for the remove of trace elements from drinking water supplies in the trace. Arsenic and chromium are two of the most toxic pollutants, introduced into natural waters from a variety of sources and causing various adverse effects on living bodies. The performance of three filter bed methods was evaluated in the laboratory. Experiments were conducted to investigate the sorption of arsenic and chromium on carbon steel and removal of trace elements from drinking water with a household filtration process. The affinity of the arsenic and chromium species for Fe / Fe3C (iron / iron carbide) sites is the key factor controlling the removal of the elements. The method is based on the use of powdered block carbon, powder carbon steel and ceramic spheres in the ion-sorption columns as a cleaning process. The modified powdered block carbon is a satisfactory and economical sorbent for trace elements (arsenite and chromate) dissolved in water due to its low unit cost of about $23 and compatibility with the traditional household filtration system.

Modification of MCM-41 by surface silylation with trimethylchlorosilane and adsorption study

Siliceous MCM-41 samples were modified by silylation using trimethylchlorosilane (TMCS). The surface coverage of functional groups was studied systematically in this work. The role of surface silanol groups during modification was evaluated using techniques of FTIR and Si-29 CP/MAS NMR. Adsorption of water and benzene on samples of various hydrophobicities was measured and compared. It was found that the maximum degree of surface attachments of trimethylsilyl (TMS) groups was about 85%, corresponding to the density of TMS groups of 1.9 per nm(2). The degree of silylation is found to linearly increase with increasing pre-outgassing temperature prior to silylation. A few types of silanol groups exist on MCM-41 surfaces, among which both free and geminal ones are responsible for active silylation. Results of water adsorption show that aluminosilicate MCM-41 materials are more or less hydrophilic, giving a type IV isotherm, similar to that of nitrogen adsorption, whereas siliceous MCM-41 are hydrophobic, exhibiting a type V adsorption isotherm. The fully silylated Si-MCM-41 samples are more hydrophobic giving a type III adsorption isotherm. Benzene adsorption on all MCM-41 samples shows type IV isotherms regardless of the surface chemistry. Capillary condensation occurs at a higher relative pressure for the silylated MCM-41 than that for the unsilylated sample, though the pore diameter was found reduced markedly by silylation. This is thought attributed to the diffusion constriction posed by the attached TMS groups. The results show that the surface chemistry plays an important role in water adsorption, whereas benzene adsorption is predominantly determined by the pore geometry of MCM-41.

Effects of surface chemistry on aromatic compound adsorption from dilute aqueous solutions by activated carbon

Adsorption of one nondissociating and four dissociating aromatic compounds onto three untreated activated carbons from dilute aqueous solutions were investigated. All adsorption experiments were preformed in pH-controlled solutions. The experimental isotherms were analyzed using the homogeneous Langmuir model. The surface chemical properties of the activated carbons were characterized using a combination of water adsorption, X-ray photoemission spectroscopy, and mass titration. These data give rise to a new insight into the adsorption mechanism of aromatic solutes, in their molecular and ionic forms, onto untreated activated carbons. It was found that, for the hydrophilic activated carbons, the dominant adsorption forces were observed to be dipolar interactions when the solutes were in their molecular form whereas dispersive forces, such as pi-pi interactions, were most likely dominant in the case of the basic hydrophobic carbons. However, when the solutes were in their ionic form adsorption occurs in all cases through dispersive forces.

Adsorption of hydrogen sulfide by modified cellulose nano/microcrystals

Hydrogen sulfide is toxic and hazardous pollutant. It has been under great interest for past few years because of all the time tighten environmental regulations and increased interest of mining. Hydrogen sulfide gas originates from mining and wastewater treatment systems have caused death in two cases. It also causes acid rains and corrosion for wastewater pipelines. The aim of this master thesis was to study if chemically modified cellulose nanocrystals could be used as adsorbents to purify hydrogen sulfide out from water and what are the adsorption capacities of these adsorbents. The effects of pH and backgrounds on adsorption capacities of different adsorbents are tested. In theoretical section hydrogen sulfide, its properties and different purification methods are presented. Also analytical detection methods for hydrogen sulfide are presented. Cellulose nano/microcrystals, properties, application and different modification methods are discussed and finally theory of adsorption and modeling of adsorption is shortly discussed. In experimental section different cellulose nanocrystals based adsorbents are prepared and tested at different hydrogen sulfide concentrations and in different conditions. Result of experimental section was that the highest adsorption capacity at one component adsorption had wet MFC/CaCO3. At different pH the adsorption capacities of adsorbents changed quite dramatically. Also change of hydrogen sulfide solution background did have effect on adsorption capacities. Although, when tested adsorbents’ adsorption capacities are compared to those find in literatures, it seems that more development of MFC based adsorbents is needed.

Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

Theoretical study of MgO(001) surfaces: Pure, doped with Fe, Ca, and Al, and with and without adsorbed water

Ab initio calculations of large cluster models have been performed in order to study water adsorption at the five-fold coordinated adsorption site on pure Mg(001) and MgO(001) surfaces doped with Fe, Ca, and Al. The geometric parameters of the adsorbed water molecule have been optimized preparatory to analysis of binding energies, charge transfer, preferential sites of interaction, and bonding distances. We have used Mulliken population analysis methods in order to analyze charge distributions and the direction of charge transfer. We have also investigated energy gaps, HOMO energies, and SCF orbital energies as well as the acid-base properties of our cluster model. Numerical results are compared, where possible, with experiment and interpreted in the framework of various analytical models. (C) 2001 John Wiley & Sons, Inc.

Synthesis and luminescence properties of water dispersible Eu3+-doped boehmite nanoparticles

Nanocrystallized boehmite gamma-AlOOH center dot nH(2)O had been synthesized by spray-drying (SD) of a solution of aluminium tri-sec-butoxide peptized by nitric acid. The sub-micronic spherical particles obtained had an average diameter of 500 nm and were built of 100 nm or less platelet-like sub-particles. The average crystallite size calculated from XRD was 1.6 nm following the b axis (i.e. one unit cell) and 3-4 nm perpendicular to b. As a result of the nanometric sizes of crystallites, there was a large surface free for water adsorption and it was found to be n = 1.18 +/- 0.24H(2)O per AlOOH. The SD spheres spontaneously dispersed in water at room temperature and formed stable-over months-suspensions with nanometre-size particles (25-85 nm). Luminescent europium-doped nanocrystallized boehmites AlOOH: Eu (Al0.98Eu0.02OOH center dot nH(2)O) were synthesized the same way by SD and demonstrated the same crystallization properties and morphologies as the undoped powders. It is inferred from the Eu3+ luminescence spectroscopy that partly hydrated europium species are immobilized on the boehmite nanocrystals where they are directly bonded to alpha(OH) groups of the AlOOH surface. The europium coordination is schematically written [Eu3+(OH)(alpha)(H2O)(7-alpha/2)]. The europium-doped boehmite from SD spontaneously dispersed in water: the luminescence spectroscopy proves that most of the Eu3+ ions were detached from the NPs during water dispersion. The AlOOH: Eu nanoparticles were modified by the amine acid asparagine (ASN). The modification aimed to render the NPs compatible for further bio-functionalization. After surface modification, the NPs easily dispersed in water; the luminescence spectra after dispersion prove that the Eu3+ ions were held at the boehmite surface.

Adsorption of reactive dye on seawater-neutralised bauxite refinery residue

This investigation has demonstrated the need for thermal treatment of seawater neutralised red mud (SWRM) in order to obtain reasonable adsorption of Reactive Blue dye 19 (RB 19). Thermal treatment results in a greater surface area, which results in an increased adsorption capacity due to more available adsorption sites. Adsorption of RB 19 has been found to be best achieved in acidic conditions using SWNRM400 (heated to 400 °C) with an adsorption capacity of 416.7. mg/g compared to 250.0. mg/g for untreated SWNRM. Kinetic studies indicate a pseudosecond-order reaction mechanism is responsible for the adsorption of RB 19 using SWNRM, which indicates adsorption occurs by electrostatic interactions. © 2013 Elsevier Inc.