Enrique Vilarrasa-García

“Low Cost” Pore Expanded SBA-15 Functionalized with Amine Groups Applied to CO2 Adsorption

The CO2 adsorption capacity of different functionalized mesoporous silicas of the SBA-15 type was investigated and the influence of textural properties and the effect of the silicon source on the CO2 uptake studied. Several adsorbents based on SBA-15 were synthesized using sodium silicate as silicon source, replacing the commonly used tetraethyl orthosilicate (TEOS). Thus, we synthesized three couples of supports, two at room temperature (RT, RT-F), two hydrothermal (HT, HT-F) and two hydrothermal with addition of swelling agent (1,3,5-triisopropylbenzene) (TiPB, TiPB-F). Within each couple, one of the materials was synthesized with ammonium fluoride (NH4F). The supports were functionalized via grafting 3-aminopropyltriethoxysilane (APTES) and via impregnation with polyethylenimine ethylenediamine branched (PEI). The adsorption behavior of the pure materials was described well by the Langmuir model, whereas for the amine-silicas, a Dualsite Langmuir model was applied, which allowed us to qualify and quantify two different adsorption sites. Among the materials synthesized, only the SBA-15 synthesized at room temperatures (RT) improved its properties as an adsorbent with the addition of fluoride when the silicas were functionalized with APTES. The most promising result was the TiPB-F/50PEI silica which at 75 °C and 1 bar CO2 captured 2.21 mmol/g.

Synthesis and Characterization of Metal-Supported Mesoporous Silicas Applied to the Adsorption of Benzothiophene

The present work reports adsorption/desorption studies of benzothiophene (BT) onto SBA-15 loaded with Fe, Pd and Cu employing in situ FT-IR spectroscopy and batch liquid-phase adsorption methods. The adsorbents were prepared by post-synthesis impregnation of metal salts onto pure siliceous SBA-15 by solid mixture and incipient wetness methods. The adsorbents were characterized by nitrogen adsorption isotherms, TEM, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The incorporated metals, in different oxidation states, were dispersed as nanoparticles on the mesoporous channels of SBA-15. The surface area decreased significantly for samples with incorporated metals, especially for those prepared by solid-mixture impregnation (Cu and Pd), although the hexagonal arrangement and the average pore size remained virtually unaltered. As revealed by batch adsorption isotherms, the incorporation of metals effectively increased the retention of the adsorbent towards the sulphur compound in the following order: Pd < Fe > Cu. DRIFT spectra (under in situ adsorption/desorption conditions) of the samples containing Fe and Pd showed that adsorption of BT onto the former is mainly reversible, whereas BT seems to be chemisorbed in the latter and did not desorb readily upon thermal treatment under He flow.

Influence of buffer solutions in the adsorption of human serum proteins onto layered double hydroxide

The adsorption of human immunoglobulin G (IgG) and human serum albumin (HSA) on a non-calcined Mg-Al layered double hydroxide (3:1 Mg-Al LDH) was studied in batch and fixed bed experiments, focusing on the effect of buffer solution and pH over sorbent uptake. Mg-Al LDH was synthesized and characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms at -196°C, X-ray photoelectron spectroscopy (XPS), Zero point charge (pHzpc), particle size distribution and Fourier transform infra-red (FTIR). Batch adsorption experiments were performed in order to investigate the effects of pH on IgG and HSA adsorption with different buffers: sodium acetate (ACETATE), sodium phosphate (PHOSPHATE), 3-(N-morpholino) propanesulfonic acid (MOPS), 4-(2-Hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES) and trizma-hydrochloric acid (TRIS-HCl). Maximum adsorption capacities estimated by the Langmuir model were 239mgg-1 for IgG and 105mgg-1 for HSA in TRIS-HCl buffer. On the other hand, the highest selectivity for IgG adsorption over HSA was obtained with buffer PHOSPHATE (pH 6.5). The maximum IgG and HSA adsorption uptake in this case were 165 and 36mgg-1, respectively. Fixed bed experiments were carried out with both proteins using PHOSPHATE buffer (pH 6.5), which confirmed that IgG was more selectively adsorbed than HSA on Mg-Al LDH and both could be fully recovered by elution with sodium chloride (NaCl).

CO2 Capture with Mesoporous Silicas Modified with Amines by Double Functionalization: Assessment of Adsorption/Desorption Cycles

CO2 adsorption on mesoporous silica modified with amine by double functionalization was studied. Adsorption microcalorimetry was used in order to investigate the influence of increasing the nitrogen surface density on double functionalized materials with respect to the only grafted materials. The distribution of sites and the rate-controlling mechanism of adsorption were evaluated. A Tian Calvet microcalorimeter coupled to a manometric setup was used to evaluate the energy distribution of adsorption sites and to calculate the thermokinetic parameters from the differential enthalpy curves. CO2 and N2 adsorption equilibrium isotherms at 50 and 75 °C were measured with a magnetic suspension balance, allowing for the computation of working capacity and selectivity at two temperatures. With these data, an Adsorbent Performance Indicator (API) was calculated and contrasted with other studied materials under the same conditions. The high values of API and selectivity confirmed that double functionalized mesoporous silica is a promising adsorbent for the post combustion process. The adsorption microcalorimetric study suggests a change in active sites distribution as the amine density increases. Maximum thermokinetic parameter suggests that physisorption on pores is the rate-controlling binding mechanism for the double-functionalized material.

Synthesis, Characterization, Uses and Applications of Porous Clays Heterostructures: A Review

Porous clay heterostructures (PCH) are obtained by the insertion of an organic bulky cation in the interlayer spacing of a smectite, causing a swelling of the clay mineral. Right after, oxides species, mainly silicon oxide, are incorporated as pillars galleries between adjacent layers to form a porous structure after the removal of the template. The ordering of the clay mineral as well the organic cation incorporated in the synthetic step favors the modulation of the textural properties of the PCH. In addition, the incorporation of heteroatoms in the pillars galleries can also modulate the acidity of the PCH. The modulation of the pore size and the acid properties provides to these materials a wide range of applications in the fields of adsorption and catalysis. This paper carries out a detailed review of the synthesis of PCH, characterization as well as uses and application reported in the literature.

Assessing the potential of nanoporous carbon adsorbents from polyethylene terephthalate (PET) to separate CO2 from flue gas

A series of nanoporous carbons was obtained by physical activation of polyethylene terephthalate and investigated for the separation of CO2 from flue gas. The prepared carbons exhibited extremely low functionalization—negligible content in oxygen and other heteroatoms—accompanied by well-developed porous networks consisting of gradually increasing surface areas and micropore volumes. Such features allowed to study the role of nanopore confinement in the separation of carbon dioxide in CO2/N2 gas mixtures. The analysis of the adsorption isotherms of individual gases and their mixtures revealed different trends for the CO2 uptake and the selectivity. Whereas CO2 uptake was larger in the carbons with higher burn-off degree, the selectivity of CO2 over N2 was favored in the carbons with a higher fraction of narrow micropores. The differential adsorption enthalpy curves are typical of highly microporous samples reaching values close to those found in zeolites for low loadings. Data also show that the choice of the best adsorbent for cyclic gas adsorption and separation processes should consider a broad context, taking into account various parameters simultaneously such as gas selectivity, working capacity, adsorption enthalpy and energy consumption in the synthesis of the adsorbent.