Formaldehyde: Catalytic Oxidation as a Promising Soft Way of Elimination

International audience; Compared to other molecules such as benzene, toluene, xylene, and chlorinated compounds, the catalytic oxidation of formaldehyde has been studied rarely. However, standards for the emission level of this pollutant will become more restrictive because of its extreme toxicity even at very low concentrations in air. As a consequence, the development of a highly efficient process for its selective elimination is needed. Complete catalytic oxidation of formaldehyde into CO2 and H2O using noble-metal-based catalysts is a promising method to convert this pollutant at room temperature, making this process energetically attractive from an industrial point of view. However, th…

Adsorption of gaseous p-xylene and m-xylene on NaY, KY, and BaY zeolites: Part 1. Adsorption equilibria of pure xylenes

Abstract Isothermal and isobaric adsorptions of p -xylene and m -xylene on NaY, KY, and BaY are studied by thermogravimetry between 25°C and 400°C, and 10 Pa and 1014 Pa. At low filling BaY shows a stronger affinity for xylenes than the other zeolites. At high temperature and low pressure its adsorption capacity is greater than those of NaY and KY. These two zeolites have a similar behavior and adsorb more m -xylene than p -xylene. At low temperature and high pressure KY adsorbs p -xylene like NaY and m -xylene like BaY, and, unlike NaY, the adsorption capacities of KY and BaY are higher for p -xylene than for m -xylene. The substitution of K + or Ba 2+ for Na + decreases the adsorption cap…

Microporous volume and external surface of Y zeolites accessible to p-xylene and m-xylene

Abstract Isothermal adsorption of p-xylene and m-xylene on NaY, KY and BaY zeolites was studied by thermogravimetry at 25°C. Adsorption isotherms showed type H4 hysteresis associated with a xylenes adsorption process activated by the pressure. Experimental data were analysed with the t-method to distinguish the amounts of xylene adsorbed in the α-cages and on the external surface of crystallites. Results were compared with those previously achieved by calorimetry. Whatever may be the isomer and the Y zeolite, the adsorption capacity of α-cages at 25 °C is equal to 3.5 molecule α−1. At saturation, the amount of xylenes adsorbed on the external surface represents 13% of the total amount adsor…

Flexible vs Rigid Networks of Two Isoreticular Viologen-Carboxylate based PCPs: the Ligand Size Effect

International audience

Inside Back Cover: Mesoporous Silica-Confined Manganese Oxide Nanoparticles as Highly Efficient Catalysts for the Low-Temperature Elimination of Formaldehyde (ChemCatChem 1/2014)

Thermal Effects of Water Intrusion in Hydrophobic Nanoporous Materials.

Liquid water intrusion in hydrophobic nanoporous silicalite-1, a pure siliceous zeolite, in isothermal conditions under high pressure produces an endothermic effect. After intrusion, confined water in zeolite pores is in a different state from that of the liquid bulk water. Such forced intrusion also chemically modifies the material and tends to render it slightly more hydrophilic.

MCM-41 silica monoliths with independent control of meso- and macroporosity

Centimetre sized macroporous silica monoliths consisting of MCM-41 have been prepared by a two-step procedure allowing an independent control of the meso- and macro-porosity. In the first step a monolith with a macroporosity tailored between 2 and 20 μm is prepared under acidic medium by a phase separation, named spinodal decomposition, leading to a bicontinuous structure of a silica/polymer phase and a water phase. The monolith is then reacted in an alkaline solution of cetyltrimethyl ammonium to transform the silica skeleton into MCM-41 under conditions which preserve the original morphology and macroporosity of the material. The combination of spinodal decomposition and pseudomorphic tra…

Detection of lung cancer bio-markers in human breath using a micro-fabricated air analyzer

International audience; The analysis of volatile organic compounds (VOCs) that are linked to lung cancer is a very promising way in medical diagnostics because it is non-invasive and potentially inexpensive. In that sense, a silicon micro-analytical platform consisting of a three-dimensional micro-preconcentrator coupled to a silicon spiral gas chromatographic micro-column was built. A metal oxide-based gas sensor acted as a miniaturized gas detector. This system allowed selective detection of VOCs at the sub-ppm level. The present study is focused first on the chromatographic air analyzer fabrication and second on the selection of an appropriate adsorbent. Various adsorbents such as activa…

New Generation of Zeolite Materials for Environmental Applications.

International audience; The influence of the morphology (microcrystals, nanocrystals, nanosponges and nanosheets) of MFI and *BEA-type zeolites on their adsorption capacities and adsorption rate of n-hexane at 25 ˚C has been investigated. The capacity of n-hexane adsorption sensitive to micro- and mesopore volume is enhanced by the use of zeolite nanocrystals or hierar-chical nanoporous materials (nanosheets and nanosponges). In the case of hierarchical zeolites MFI and *BEA nano-sponges, the n-hexane adsorption capacities reached values of about 790 and 693 mg/g, respectively, that are much higher than those in the corresponding microcrystals (130 and 103 mg/g, respectively). On the opposi…

Adsorption and desorption surface dynamics of gaseous adsorbate on silicate-1 by molecular dynamics simulation

The dynamics of adsorption and desorption of gaseous molecules on the external surface of a crystal and a membrane of zeolite silicate-1 is investigated by molecular dynamics simulation. The gases ...

Porous Coordination Polymer Based on Bipyridinium Carboxylate Linkers with High and Reversible Ammonia Uptake

The zwitterionic bipyridinium carboxylate ligand 1,1'-bis(4-carboxyphenyl)-4,4'-bipyridinium (pc1) in the presence of cadmium chloride affords novel porous coordination polymers (PCPs): [Cd4(pc1)3Cl6]·CdCl4·guest (1) crystallizing in the P3̅1c space group. In the structure, [Cd4Cl6(CO2)6] building units are linked together by six pc1 ligands, leading to a 3D high-symmetrical network exhibiting hexagonal channels along the c axis. The walls of this PCP consist of cationic electron-acceptor bipyridinium units. The PCP 1 reversibly adsorbs H2O and CH3OH up to about 0.1 g/g at saturation showing the adsorption isotherms characteristic of a moderately hydrophilic sorbent. Adsorption of ammonia (…

Structural Changes in Nanoporous MFI Zeolites Induced by Tetrachloroethene Adsorption: A Joint Experimental and Simulation Study

A joint experimental and molecular simulation study was performed to investigate the adsorption of tetrachloroethene on two MFI zeolites, ZSM-5 with a Si/Al ratio of 26.5, and silicalite-1, which is the pure silica form of ZSM-5. Adsorption isotherms and isosteric heats of adsorption of tetrachloroethene were measured and compared to molecular simulation results. Experimental curves for both MFI zeolites show a step at loading of 4 molecules·uc−1 that was interpreted in terms of a structural change of the host framework. A thermodynamic analysis based on the osmotic ensemble scheme allowed attributing this step to a symmetry change from ORTHO (orthorhombic form with Pnma symmetry) to PARA (…

Characterization of [Cu]-MCM-41 by XPS and CO or NO adsorption heat measurements

We report the characterization of copper doped MCM-41 prepared by original direct synthesis by XPS and adsorption calorimetry of CO and NO, which are selective molecular probes for Cu(I) and Cu(II) respectively. Investigation of the nature of the copper ions in this particular calcined Cu-MCM-41 by NO adsorption calorimetry shows that two types of energetically distinct adsorption sites exist, meaning the presence of two populations of Cu(II) species differently coordinated to the silica surface in quasi-equimolar concentration, as ascertained by XPS data. A small amount of Cu(I) was also detected, probably stemming from a partial reduction upon the successive vacuum treatments. The respect…

Characterization of materials toward toluene traces detection for air quality monitoring and lung cancer diagnosis

International audience; The aim of this work was to identify a nanoporous material able to trap toluene traces in order to develop a gas detection device for indoor air quality monitoring or biomedical diagnosis. A set of various adsorbents such as zeolites and activated carbon microspheres was studied here. First a detailed characterization of their porous properties was performed by nitrogen adsorption. Then adsorption of toluene and other interfering compounds which can selectively adsorbed with it, such as water and carbon dioxide, was studied in order to select the most suitable material. Results revealed that the activatedcarbon microspheres W5 and the zeolite NaY, which exhibit high …

Chromatographic Air Analyzer Microsystem for the Selective and Sensitive Detection of Explosive-related Compounds

Abstract The detection of explosives and explosive-related compounds is of major importance for the monitoring of explosive- contaminated sites. Current methods need to become cheaper and portable while maintaining a high sensitivity and selectivity level. In that sense, a silicon micro-analytical platform consisting of a three-dimensional micro-preconcentrator based on a hydrophobic zeolite, coupled to a silicon spiral micro-column was built. A chemical gas sensor acted as a miniaturized gas detector. This system allowed selective detection of orthonitrotoluene (ONT), an explosive-related compound at the sub-ppm level in the presence of toluene and moisture.

Adsorption of hydrogen isotopes in the zeolite NaX: Experiments and simulations

Abstract Among the different methods to separate hydrogen isotopes one is based on the physisorption at low temperature (below 100 K) where quantum effects induce a particular behavior. In the present work, we study the adsorption of single H 2 and D 2 on the zeolite NaX by combining experiments (manometry) from 30 to 150 K and molecular dynamics simulations at 40 and 77 K. Simulations also include the adsorption analysis for T 2 . Adsorption on NaX membranes is simulated and quantum corrections are introduced by using the well-known Feynman–Hibbs approach into the interaction potentials. Experimental adsorption isotherms are reproduced by using the Toth equation and it is shown that the ad…

Reactive adsorption of thiophene on Ni/ZnO: role of hydrogen pretreatment and nature of the rate determining step.

Abstract Reactive adsorption of thiophene on reduced and unreduced NiO/ZnO adsorbents was studied by thermal gravimetric analysis and by sulfidation in a fixed bed reactor at 330–375 °C and 10–40 mbar of thiophene in hydrogen. The adsorbents (12 wt% Ni) were prepared by co-precipitation of corresponding nitrates with sodium carbonate followed by calcination at 400 °C. We have found that such solids can react with thiophene without any prior reduction. Metallic Ni, indispensable for thiophene decomposition, is formed in this case in situ upon the contact with thiophene/H 2 reaction mixture. The reduction of NiO/ZnO in H 2 (360 °C, 6 h) results in the formation of Ni–Zn alloyed particles (as …

Development of a micro-analytical prototype for selective trace detection of orthonitrotoluene

Abstract A silicon micro-analytical platform consisting of a micro-preconcentrator based on a hydrophobic zeolite, coupled to a silicon spiral micro-column was built. A chemical gas sensor acted as a miniaturized gas detector. This system allowed selective detection of orthonitrotoluene (ONT), an explosive-related compound at the sub-ppm level (365 ppb) in the presence of toluene and moisture.

Macroscopic and Molecular Insights from CO Adsorption on NaY Zeolite: A Combined FTIR and Manometric Study

International audience; This survey combines both quantitative and IR molecular descriptions and aims to provide new insights for the description of CO adsorption on NaY zeolite at 77 K. Quantitative measurements of the number of CO molecules trapped in the microporous super cage are compared to the corresponding IR spectra of CO as adsorbed species. We demonstrate that polycarbonyls formed during the completion of the accessible S-II Na+ coordinative vacancies result in the formation of mono-, di- and tricarbonyls but not consecutively. Quantitative analysis and measurements of the CO molecules that are adsorbed prove that polycarbonyls coexist with different proportions over the adsorptio…

Degradation of fluoride-free MIL-100(Fe) and MIL-53(Fe) in water: Effect of temperature and pH

Abstract The degradation in liquid water of two iron-containing MOFs MIL-100(Fe) and MIL-53(Fe) synthesized in fluoride-free conditions was studied. It was found that dispersing the MOFs in deionized water (1 mg/mL) results in the decrease of pH to 2.9 for MIL-100(Fe) and to 4.5 for MIL-53(Fe). Given this finding the stability of the MOFs in liquid water was characterized under two different sets of conditions: 1) reflux in water at 100 °C under obtained pH and 2) at ambient temperature under adjusted pH 7. After reflux of MIL-100(Fe) at 100 °C its XRD pattern remains unchanged, however a strong decrease of its BET surface area and appearance of α-Fe 2 O 3 nanoparticles point out to a parti…

Molecular simulation studies of water physisorption in zeolites

We report a series of Grand Canonical Monte Carlo simulations of water adsorption in NaY and NaX faujasite, as well as in silicalite-1. Computed adsorption isotherms and heats of adsorption were in good agreement with the available experiments. The existence of cyclic water hexamers in NaX located in the 12-ring windows, recently disclosed by neutron diffraction experiments (Hunger et al., J. Phys. Chem. B, 2006, 110, 342-353) was reproduced in our simulations. Interestingly enough, such cyclic hexamer clusters were also observed in the case of NaY, in which no stabilizing cation is present in the 12-ring window. We also report cation redistribution upon water adsorption for sodium faujasit…

Characterization of adsorbed water in MIL-53(Al) by FTIR spectroscopy and ab-initio calculations

Here, we report ab-initio calculations developed with a twofold purpose: understand how adsorbed water molecules alter the infrared spectrum of the metal-organic framework MIL-53(Al) and to investigate which are the associated physico-chemical processes. The analyzed structures are the two anhydrous narrow (np⊘) and large (lp⊘) pore forms and the hydrated narrow pore form (np-H2O) of the MIL-53(Al). For these structures, we determined their corresponding infrared spectra (FTIR) and we identified the vibrational modes associated to the dominant spectral lines. We show that wagging and scissoring modes of CO2 give flexibility to the structure for facilitating the lp⊘- np⊘ transition. In our s…

Detection and quantification of lung cancer biomarkers by a micro-analytical device using a single metal oxide-based gas sensor

International audience; The analysis of exhaled volatile organic compounds (VOCs) related to lung cancer is a very promising wayin medical diagnosis because it is non-invasive and much less expensive than traditional medical analysisused so far. In that sense, a silicon micro-analytical platform consisting of a micro-preconcentrator cou-pled to a silicon spiral gas chromatographic micro-column was built, and a metal oxide-based gas sensorwas used as a miniaturized gas detector. This micro-fabricated device was successfully tested to selec-tively detect low concentrations of VOCs considered as lung cancer biomarkers, within a few minuteseven in presence of high concentrations of water vapor …

Diffusion of Oxygen through Cork Stopper: Is It a Knudsen or a Fickian Mechanism?

International audience; The aim of this work is to identify which law governs oxygen transfer through cork: Knudsen or Fickian mechanism. This is important to better understand wine oxidation during post-bottling aging. Oxygen transfer through cork wafers is measured at 298 K using a manometric permeation technique. Depending on the mechanism, we can extract the transport coefficients. Increasing the initial pressure of oxygen from 50 to 800 hPa leads to a change in the values of the transport coefficients. This implies that oxygen transport through cork does not obey the Knudsen law. From these results, we conclude that the limiting step of oxygen transport through cork occurs in the cell …

Interaction of Ni/SiO2 with thiophene.

Abstract The interaction between Ni/SiO 2 (18 wt%) and thiophene was studied by thermal gravimetric analysis (TGA) and in a fixed-bed reactor. The samples were prepared by incipient wetness impregnation and reaction was realized in hydrogen flow at 280–360 °C in the presence of 10–40 mbar of thiophene. It is found that sulfidation of Ni is not complete in TGA experiments and the maximum achievable transformation degree depends not only on the temperature and thiophene pressure, but also on the sample weight and the gas flow rate. The maximum transformation degree is shown to vary reversibly when conditions are changed. Analysis of the reaction products during sulfidation in a fixed-bed reac…

Reaction of thiophene with mono- and bimetallic Ni–Co particles supported on γ-Al2O3 and HDS activities of obtained sulfides

Abstract Reaction between thiophene and M/γ-Al2O3 (20 wt.%, M = Ni, Co, 2Ni–Co and 2Co–Ni) was studied by thermal gravimetric analysis (TGA) and by sulfidation in a fixed bed microreactor. The samples were prepared by incipient wetness impregnation followed by drying and reduction in hydrogen flow at 450 °C. Formation of bimetallic particles in samples containing both Ni and Co was confirmed by HRTEM with EDX analysis. The reaction with thiophene (20 or 40 mbar) was done at 360 °C in hydrogen atmosphere. TGA of the reaction with thiophene revealed that the initial rate of sulfidation drops sharply when going from Ni/γ-Al2O3 to Co/γ-Al2O3 (by a factor of 40 under used conditions). It follows…

Confinement of Water in Hydrophobic Nanopores: Effect of the Geometry on the Energy of Intrusion

International audience; Water confinement in the hydrophobic nanopores of highly siliceous zeolite having MFI and CHA topology is investigated by high pressure manometry coupled to differential calorimetry. Surprisingly, the intrusion of water is endothermic for MFI but exothermic for CHA. This phase transition depends on the geometry of the environment in which water is confined: channels (MFI) or cavities (CHA). The energy of intrusion is mainly governed by the change in the coordination of water molecules when they are forced to enter the nanopores and to adopt a weaker, hydrogen-bonded structure. At such a nanoscale, the properties of the molecules are governed strongly by geometrical r…

Sulfidation Mechanism of Pure and Cu-Doped ZnO Nanoparticles at Moderate Temperature: TEM and In Situ XRD Studies

International audience; Sulfidation mechanism of pure and Cu-doped ZnO nanoparticles (Cu0.03Zn0.97O and Cu0.06Zn0.94O) at 250 and 350 degrees C was studied by transmission electron microscopy (TEM) and in situ synchrotron XRD. For nondoped ZnO, we observed by TEM that partial reaction with H2S is accompanied by the formation of voids at the ZnO/ZnS interface. This phenomenon (known as the Kirkendall effect) confirms that sulfidation of nanosized ZnO by gaseous H2S proceeds via the outward growth of ZnS: Zn2+ and O2- are transferred to the external (ZnS/gas) surface, where zinc is combined with sulfur and oxygen reacts with protons yielding H2O. During sulfidation of Cu-doped ZnO, the caviti…

Insight into the Mechanism of Water Adsorption/Desorption in Hydrophilic Viologen-Carboxylate Based PCP

A water stable and highly hydrophilic porous coordination polymer based on viologen-carboxylate type ligand, the 4,4′-bipyridinium,1,1-bis(3-carboxyphenyl) (pc2), is obtained by the solvothermal method: [Cd3(pc2) (BTC)2(H2O)2]·6H2O ([1(H2O)2]·6H2O; BTC3– = 1,3,5-carboxybenzene). Its crystal structure and the ones of two partially dehydrated phases have been determined, allowing insight into the mechanism of water adsorption/desorption of this PCP material. It is shown that the dehydrated compound [1] first adsorbs two water molecules which fill the pores, leading to [1]·2H2O. On the other hand, the partial dehydration of the as-synthesized compound leads to the intermediate phase [1(H2O)]·3…

Adsorption equilibria of water vapor on cork.

International audience; We report here for the first time a complete thermodynamic study of water vapor adsorption on crude cork powder and plate. Adsorption−desorption isotherms were accurately measured by thermogravimetry at 283, 298, and 313 K in a large range of relative pressure. Adsorption enthalpies were determined by calorimetry as a function of loading. Adsorption−desorption isotherms exhibit a hysteresis due to the swelling of the material. The influence of the presence of lenticels on the adsorption properties of cork is found to be negligible. A detailed analysis and interpretation of adsorption data allow proposal of an adsorption mechanism in two steps. (i) First, water adsorb…

Structural variations as a function of surface adsorption in nanostructured particles

Macroscopic (adsorption isotherm and micro-calorimetry measurement) and microscopic (in situ X-ray diffraction and IR spectroscopy) approaches were used to study the influence of water adsorption on γ-Fe 2 O 3 nanoparticles. A nonmonotonic variation of γ-Fe 2 O 3 lattice parameter is revealed when the relative water pressure (p/p 0 ) increases from 0.03 to 0.96 with a maximum deviation for p/p 0 0.1. With IR spectroscopy, similar results were observed since a modification of γ-Fe 2 O 3 structural bands has been shown. In situ investigations as well as thermodynamics considerations lead to one important conclusion: the variation of the lattice parameter is in relation with the strains induce…

Selective adsorption of ethyl mercaptan on NaX zeolite.

Adsorption on microporous solid is an alternative technique to remove mercaptans from natural gases. The present study gives equilibrium adsorption data on NaX faujasite for some pure gases representative of natural gas impurities (ethyl mercaptan, toluene and n-heptane) and their binary mixtures. The first part of the paper is devoted to the adsorption of pure gases. Experimental results show that the zeolite has a high adsorption affinity for ethyl mercaptan, toluene and n-heptane. In the second part, we examine adsorption isotherms for binary mixtures of ethyl mercaptan and toluene or n-heptane over a large domain of composition. Coadsorption enthalpies are also determined. These experim…

Sorption of n-hexane in amorphous polystyrene

Sorption properties of pure n-hexane vapor in amorphous polystyrene (PS) were studied at 298 K by thermogravimetry under controlled vapor pressure. Two sorption-desorption cycles were performed by varying the relative pressure between 0 and 0.91. Mixing of PS with n-hexane resulted in a strong plasticization, which was evidenced by quite significant depression in the glass transition temperature of the polymer as shown by differential scanning calorimetry. Maximum quantity of n-hexane sorbed in the PS at 298 K and at a pressure close to saturation was about 12.4 wt %. The thermogravimetry yielded an isotherm with a strong hysteresis loop, explanation of which was hypothesized with the help …

Preparation and characterization of activated carbon from date stones by physical activation with steam

Abstract Activated carbons are produced from wastes of Algerian date stones by pyrolysis and physical activation in the presence of water vapor into a heated fixed-bed reactor. The effect of pyrolysis temperature and activation hold time on textural and chemical surface properties of raw date stones and carbon materials produced are studied. As expected, the percentage yield decreases with increase of activation temperature and hold time. The characterization of carbon materials is performed by scanning electron microscopy (SEM). X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption (BET). Results show the presence of cellulose and hemicellulose in …

Diffusion of oxygen in cork.

International audience; This work reports measurements of effective oxygen diffusion coefficient in raw cork. Kinetics of oxygen transfer through cork is studied at 298 K thanks to a homemade manometric device composed of two gas compartments separated by a cork wafer sample. The first compartment contains oxygen, whereas the second one is kept under dynamic vacuum. The pressure decrease in the first compartment is recorded as a function of time. The effective diffusion coefficient D-eff is obtained by applying Fick's law to transient state using a numerical method based on finite differences. An analytical model derived from Fick's law applied to steady state is also proposed. Results give…

Adsorption of gaseous p-xylene and m-xylene on NaY, KY, and BaY zeolites. Part 2: Modeling. Enthalpies and entropies of adsorption

Abstract The adsorption isotherms of xylenes are described by Henry's law and Langmuir's model on NaY and KY and the Dubinin-Radushkevich model on BaY. The isoteric enthalpies of adsorption show on each zeolite that the adsorbate-adsorbent interactions are nearly the same with both isomers. They are stronger on BaY than on NaY and KY. The adsorbate-adsorbate interactions are stronger with m-xylene than with p-xylene and especially outstanding on KY. The entropies of adsorption show that the mobility of the adsorbate is lower with m-xylene than with p-xylene. The isosteric free enthalpies of adsorption are related to the acidity of each zeolite. BaY has a stronger acidity and a greater abili…

Adsorption of p-Xylene/m-Xylene Gas Mixtures on BaY and NaY Zeolites. Coadsorption Equilibria and Selectivities

Coadsorption of the gases p-xylene and m-xylene on BaY and NaY was studied at 150 °C in the range of pressure 10-2-3 hPa. For BaY coadsorption isotherms and single-component adsorption isotherms are perfectly superimposed in the whole range of investigated pressure. The capacity of adsorption of BaY is 3 molecules α-1 for each single component as well as for each mixture under 3 hPa. For NaY coadsorption isotherms lie between those of single p-xylene and m-xylene. The capacity of adsorption of NaY for mixtures is in proportion to the composition of the initial adsorptive mixture and varies from the capacity of adsorption for single p-xylene (3.3 molecules α-1) to that for single m-xylene (3…

Sticking Probability on Zeolites

The sticking coefficient, i.e., the probability that, on hitting the surface of a nanoporous particle (zeolite), a molecule shall be able to enter the intracrystalline space, is a key quantity for the application of such materials in heterogeneous catalysis and molecular sieving. On the basis of pulsed field gradient NMR diffusion measurements and molecular dynamics simulations, typical values of this probability are found to be close to one. They exceed previous estimates on the basis of IR uptake measurements by many orders of magnitude.

The cork viewed from the inside

International audience; Cork is the natural material stripped from the outer bark of cork oak. It is still the most used stopper to seal wine bottles and to preserve wine during storage. Cork stoppers are sorted in different classes according to apparent defects, named lenticels, which can be related to the cork macroporosity. The more lenticels there are, the worst cork quality is. The present work aims at investigating defects analysis of cork stoppers from two classes by comparing images recorded by digital photography and neutron imaging. Surface analysis of defects obtained from photography leads to more surface defects in class 4 (6.7%) than in class 0 (4.1%). Neutron radiography and …

D2 and H2 adsorption capacity and selectivity in CHA zeolites: Effect of Si/Al ratio, cationic composition and temperature

International audience; The work deals with the effect of composition of CHA zeolites on the adsorption and separation of H2 and D2 under cryogenic temperatures. In the first part of this work the effect of Si/Al ratio and cationic composition on single gas adsorption of H2 and D2 was studied at 77.4 K. It was found that the adsorption capacities increase with Al content up to Si/Al = 2.1. Unexpectedly, Na-CHA zeolite with the highest Al content (Si/Al = 1.1) adsorbs only negligible amount because of the collapse of the zeolite structure upon dehydration at 400°C. The Na-and Li-containing chabazites with Si/Al = 2.1 possess similar adsorption capacities. In contrast, progressive replacement…

Sorption Equilibria of Ethanol on Cork

International audience; We report here for the first time a thermodynamic study of gaseous ethanol sorption on raw cork powder and plate. Our study aims at a better understanding of the reactivity of this material when used as a stopper under enological conditions, thus in close contact with a hydroethanolic solution, wine. Sorption−desorption isotherms were accurately measured by thermogravimetry at 298 K in a large range of relative pressures. Sorption enthalpies were determined by calorimetry as a function of loading. Sorption−desorption isotherms exhibit a hysteresis loop probably due to the swelling of the material and the absorption of ethanol. Surprisingly, the sorption enthalpy of e…

Selective adsorption of formaldehyde and water vapors in NaY and NaX zeolites

International audience; Coadsorption of formaldehyde and water vapors on NaX and NaY zeolites is studied at 298 K in the pressure range 0-2 hPa by manometry coupled with gas phase chromatography and calorimetry. Coadsorption isotherms, adsorption selectivities and coadsorption heats are measured. Results show that the coadsorption process is selective for water at low filling and for formaldehyde at high filling. The adsorption selectivity for formaldehyde over water is however too low to consider the possibility of using such adsorbents for the development of air handling units. On the other hand, a preliminary study carried out on the adsorption of formaldehyde and water in pure gas phase…

Effects of pyrolysis conditions on the porous structure development of date pits activated carbon

International audience; Activated carbons were prepared from biomass of Algerian date pits for developing efficient and cheap adsorbents in the aim to remove heavy metals from waste water. Carbon adsorbents were obtained following two successive treatments: pyrolysis under dry nitrogen flow and physical activation under wet nitrogen flow. Pyrolysis process was optimized by varying some operating parameters such as temperature, nitrogen flow, heating rate and pyrolysis hold time in order to determine their effects on the porous structure development of date pits activated carbon. Chars obtained from pyrolysis process were activated with the same operating conditions (activation temperature o…

Low Temperature H2S Removal with Metal-Doped Nanostructure ZnO Sorbents: Study of the Origin of Enhanced Reactivity in Cu-Containing Materials

Sulfidation of pure and metal-doped ZnO nanostructure sorbents (M0.03Zn0.97O, M = Fe, Co, Ni, Cu) was studied in order to clarify the effect of metal on the transformation kinetics at 200−350 °C. The solids were prepared by coprecipitation from metal nitrate solution followed by calcination at 400 °C. Reaction with H2S was studied by thermal gravimetric analysis (TGA) using a gas mixture containing 0.2 vol % H2S in equimolar H2−N2. It was found that at 350 °C the TGA sulfidation profiles of all studied samples are similar, with the interface reaction being the main rate-determining step. After lowering the temperature to 250 °C the transformation of Cu0.03Zn0.97O continues to be controlled …

Temperature-Induced Structural Transitions in the Gallium-Based MIL-53 Metal–Organic Framework

We report a structural and thermodynamic investigation of the phase behavior of Ga(OH,F)-MIL-53, a gallium-based metal–organic framework (MOF) having the MIL-53 topology containing 0.7 wt % fluorine bonded to the metal. Despite some small structural differences, especially for the hydrated form, the overall physical chemistry behavior of Ga(OH,F)-MIL-53 is very similar to standard fluorine free Ga-MIL-53 material. A combination of in situ X-ray diffraction, in situ Fourier transform infrared spectroscopy, differential scanning calorimetry, and heat capacity measurements allowed us to establish that Ga(OH,F)-MIL-53 under vacuum (i.e., the empty material) exhibits two stable phases: a nonporo…

Novel Porous Carbon Material for the Detection of Traces of Volatile Organic Compounds in Indoor Air

International audience; A highly sensitive and selective silicon-based microanalytical prototype was used to identify a few ppb of volatile organic compounds (VOCs) in indoor air. Herein, a new nonactivated tannin-derived carbon synthesized by an environmentally friendly method, DM2C, a MIL-101(Cr) MOF, and a DaY zeolite were selected for the preconcentration of BTEX compounds (i.e., benzene, toluene, ethylbenzene, and xylenes). Integrating a small amount of these nanoporous solids inside a miniaturized preconcentration unit led to excellent preconcentration performance. By taking advantage of the high adsorption−desorption capacities of the DM2C adsorbent, concentrations as low as 23.5, 30…

New insights in the formation of silanol defects in silicalite-1 by water intrusion under high pressure.

International audience; The "water-silicalite-1" system is known to act as a molecular spring. The successive intrusion-extrusion cycles of liquid water in small crystallites (6 × 3 × 0.5 μm(3)) of hydrophobic silicalite-1 were studied by volumetric and calorimetric techniques. The experiments displayed a decrease of the intrusion pressure between the first intrusion-extrusion cycle and the consecutive ones, whereas the extrusion pressures remained unchanged. However, neither XRD studies nor SEM observations revealed any structural and morphological modifications of silicalite-1 at the long-range order. Such a shift in the value of the intrusion pressure after the first water intrusion-extr…

MIL-53(Al) under reflux in water: Formation of γ-AlO(OH) shell and H2BDC molecules intercalated into the pores

Abstract It is shown that treatment of MIL-53(Al) (Al(OH)BDC·H2O, BDC = 1,4-benzene dicarboxylate) under reflux in water results in a progressive transformation of the solid into a new well crystallized phase. After reflux for 10 h or more the new phase is obtained in a pure form and its XRD pattern was indexed in a monoclinic system with the following cell parameters: a = 19.47 A, b = 8.98 A, c = 6.60 A, β = 107.7°. Characterization of the obtained solid by TGA, FT-IR, NMR, TEM and XRD has revealed that its composition is [0.8Al(OH)BDC·0.2H2BDC] + 0.2γ-AlO(OH). Formation of this material indicates that under reflux in water a partial hydrolysis of the MOF network occurs producing H2BDC mol…

Study of Selective Adsorption of Gases by Calorimetry

This chapter is devoted to the study of coadsorption of gases in nanoporous solids by using the differential calorimetry. In the first part, the thermodynamic principles of adsorption of gases are recalled. Some of them have already presented in chapter one. However a special attention has been paid here to the determination of the adsorption enthalpies and entropies and we focused on the selective adsorption of binary mixtures. Then the specific experimental technique based on the combination of differential calorimetry with manometry and gas phase chromatography or mass spectrometry is shown in details. In the last part, the thermodynamic concepts on coadsorption are illustrated with expe…

Photo- and Thermochromic and Adsorption Properties of Porous Coordination Polymers Based on Bipyridinium Carboxylate Ligands

The zwitterionic bipyridinium carboxylate ligand 1-(4-carboxyphenyl)-4,4'-bipyridinium (hpc1) in the presence of 1,4-benzenedicarboxylate anions (BDC(2-)) and Zn(2+) ions affords three porous coordination polymers (PCPs): [Zn5(hpc1)2(BDC)4(HCO2)2]·2DMF·EtOH·H2O (1), [Zn3(hpc1)(BDC)2(HCO2)(OH)(H2O)]·DMF·EtOH·H2O (2), and [Zn10(hpc1)4(BDC)7(HCO2)2(OH)4(EtOH)2]·3DMF·3H2O (3), with the formate anions resulting from the in situ decomposition of dimethylformamide (DMF) solvent molecules. 1 and 3 are photo- and thermochromic, turning dark green as a result of the formation of bipyridinium radicals, as shown by electron paramagnetic resonance measurements. Particularly, crystals of 3 are very photo…

Selection and characterization of adsorbents for the analysis of an explosive-related molecule traces in the air

International audience; This study is focused on the development of a 3D micro-preconcentrator for a sensitive analysis of an explosive-related compound: orthonitrotoluene (ONT). A set of potentially efficient adsorbents for the pre-concentration of ONT was investigated here. An in-depth characterization of their textural properties was carried out in order to better understand their adsorption behavior toward the target analyte. More particularly, this study allowed highlighting the interesting adsorption features of a hydrophobic zeolite and a porous activated carbon in relation to their preconcentration performances toward ONT at the ppb level. Moreover, we found a difference in the adso…

Pore shape affects the determination of the pore size of ordered mesoporous silicas by mercury intrusion.

MCM-41 and SBA-15 micelle-templated silicas are ideal reference materials to study the effect of surface roughness on pore size measurement by mercury intrusion, as the inner surface of the mesoporous channels is much rougher in the case of SBA-15 than MCM-41. In the case of MCM-41, the pressure of mercury intrusion is related to the pore size by the classical Washburn−Laplace law, while in the case of SBA-15, the pressure of intrusion is much higher than expected and classical models underevaluate the size of the channels. Defects on the pore surface of SBA-15 affect the mercury intrusion in a similar way as the deviation from cylindrical geometry does for the pores of spongelike silica gl…

Communication: Evidence of structural phase transitions in silicalite-1 by infrared spectroscopy

The adsorption of trichloroethylene, perchloroethylene, and p-xylene on a MFI (Mobile-FIve) zeolite is studied using in situ FTIR spectroscopy at 298 K. Spectra of self-supported zeolites in contact with increasing pressures of pure gas were recorded at equilibrium in the mid-infrared domain. Analysis of the evolution of the shape and location of vibrational bands of the zeolite as a function of the amount adsorbed allowed the observation of structural modifications of the adsorbent for the first time by infrared spectroscopy.

Enhancement of D 2 /H 2 Selectivity in Zeolite A through Partial Na–K Exchange: Single-Gas and Coadsorption Studies at 45–77 K

International audience; We report D2/H2 adsorption selectivities under cryogenic temperatures (45-77 K) in Na and K-Na exchanged zeolites A (LTA structural code) measured by co-adsorption technique. These values are systematically compared with Ideal Adsorbed Solution Theory (IAST) predictions based on the single gas adsorption isotherms. For NaA zeolite the evolution of the selectivity as a function of total pressure and gas mixture composition at 77 K shows ideal behavior. In contrast, as temperature decreases, D2/H2 selectivity rises exponentially and its values can no longer be predicted by IAST. We found that in these conditions the evolution of the selectivity can be described by a si…

Adsorption of water vapor on X and Y zeolites exchanged with barium

Abstract The adsorption of water vapor on BaY and BaX zeolites is studied by thermogravimetry and calorimetry under isothermal or isobaric conditions. The faujasite zeolite exhibits a stronger adsorption affinity for water molecules with barium than with sodium or potassium as exchangeable cations. The adsorption–desorption isotherm at 150°C shows a hysteresis loop attributed to the migration of compensating cations during their interaction with water molecules. Calorimetric measurements and the Dubinin–Radushkevich’s model both show that the adsorption of water occurs via a three-step mechanism: adsorption on compensating cations, formation of a monolayer on the walls and multilayer adsorp…

Martian zeolites as a source of atmospheric methane

The origin of the martian methane is still poorly understood. A plausible explanation is that methane could have been produced either by hydrothermal alteration of basaltic crust or by serpentinization of ultramafic rocks producing hydrogen and reducing crustal carbon into methane. Once formed, methane storage on Mars is commonly associated with the presence of hidden clathrate reservoirs. Here, we alternatively suggest that chabazite and clinoptilolite, which belong to the family of zeolites, may form a plausible storage reservoir of methane in the martian subsurface. Because of the existence of many volcanic terrains, zeolites are expected to be widespread on Mars and their Global Equival…

Mechanism of water adsorption in the large pore form of the gallium-based MIL-53 metal-organic framework

Abstract Water adsorption in the large pore ( lp_empty ) form of Ga-MIL-53 was studied by TGA, DSC and in situ XRD and FTIR at 298 K. The large pore form can be stabilized at room temperature after activation under vacuum at 553 K. The isotherm of water adsorption in this large pore form (pore dimensions: 1.67 × 1.33 nm) is very similar to that measured on the narrow pore ( np_empty ) form (pore dimensions: 1.97 × 0.76 nm). Such a similarity is rather unusual given that the pore sizes of these two phases are very different. In order to understand the origin of this effect in situ XRD and FTIR measurements were particularly helpful. It was found that the adsorption of even small amount of wa…

Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria

Abstract Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have…

Determination of water intrusion heat in hydrophobic microporous materials by high pressure calorimetry

International audience; The understanding of interactions between a solid surface and a non-wetting liquid still remains of fundamental interest in numerous research fields, from chemistry to biology. This work focuses on the mechanisms of water intrusion in hydrophobic microporous materials through the thermal analysis of the phenomenon. A specific calorimetric technique coupled to high pressure equipment has been developed to investigate equilibrium thermal effects in such thermodynamic systems from 0 to 400 MPa under isothermal conditions. First validation tests of this method were carried out by compressing degassed water in a constant volume V with successive small pressure increments …

Water Adsorption in Flexible Gallium-Based MIL-53 Metal–Organic Framework

Understanding the adsorption of water in metal–organic frameworks (MOF), and particularly in soft porous crystals, is a crucial prerequisite before considering MOFs for industrial applications. We report here a joint experimental and theoretical study on the behavior of a gallium-based breathing MOF, Ga-MIL-53, upon water adsorption. By looking at the energetics and thermodynamics of Ga-MIL-53, we demonstrate why it behaves differently from its sibling Al-MIL-53, showing a different phase at room temperature (a nonporous phase) and the presence of a hydrated narrow-pore structure at gas saturation pressure. Moreover, we present a complete water vapor pressure vs temperature phase diagram of…

2.8NiO–H1.8Ni0.6(OH)MoO4—Novel nanocomposite material for the reactive adsorption of sulfur-containing molecules at moderate temperature

Abstract It has been found that a poorly crystalline green precipitate that forms in boiling ammonia solution of Ni(NO 3 ) 2 and (NH 4 ) 6 Mo 7 O 24 yields on annealing a Ni-rich material (Ni/Mo = 3.4) containing slit shaped mesopores and exhibiting the BET surface area of 230 m 2 /g. Characterization of the material by TGA, XRD, TEM, SEM, and EXAFS allowed to determine that it is a nanocomposite consisting of Ni–Mo (hydro)oxide layers H 1.8 Ni 0.6 (OH)MoO 4 which are pillared by NiO nanoparticles ( D  = 3 nm). The structure of the layers appears to be similar to that found in the previously described crystalline molybdate (NH 4 )HNi 2 (OH) 2 (MoO 4 ) 2 prepared in the similar conditions. T…

Interaction Mechanisms between guaiacols and lignin: the conjugated double bond makes the difference.

Lignin is considered to be responsible for a selective sorption of phenolic compounds on wood. In order to investigate the mechanisms involved, two similar guaiacol compounds--only differing by the nature of the para side chain--were adsorbed on oak wood extracted lignin. Vapor sorption-desorption isotherms indicated that about 3.5 wt % of 4-vinylguaiacol is adsorbed near saturation whereas it is only 0.8% for 4-ethylguaiacol. For both compounds, the isotherms displayed a hysteresis though significantly greater for 4-vinylguaiacol. Analyses of the hydroxyl stretching region of FTIR spectra of the lignin/4-ethylguaiacol and lignin/4-vinylguaiacol complexes indicated that physisorption via hy…

Mesoporous Silica-Confined Manganese Oxide Nanoparticles as Highly Efficient Catalysts for the Low-Temperature Elimination of Formaldehyde

Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO.

Abstract Kinetics of thiophene reactive adsorption on Ni/SiO2 and Ni/ZnO was studied by thermal gravimetric analysis at 280–360 °C under 5–40 mbar of thiophene in H2. In the case of Ni/SiO2 the interaction proceeds in two steps: a rapid surface reaction is followed by a slower bulk transformation into Ni3S2. Maximum Ni conversion depends on reaction conditions and observed conversion profiles can be described by an exponential equation corresponding to a reaction of first order relatively to both sulfidable Ni amount and thiophene. The interaction between Ni/ZnO and thiophene proceeds in a rather different manner. A rapid increase of weight, similar to the first stage observed on Ni/SiO2, i…

Enhanced quantum sieving of hydrogen isotopes via molecular rearrangement of the adsorbed phase in chabazite

Coadsorption experiments reveal an unexpected increase of the D2/H2 selectivity with loading in pure silica chabazite at 47 K. This effect is correlated with the appearance of a step in the adsorption isotherms of H2 and D2. Grand canonical Monte Carlo simulations show that this phenomenon is related to a molecular rearrangement of the adsorbed phase induced by its strong confinement. In the case of a H2 and D2 mixture, this rearrangement favors the adsorption of D2 having a smaller size due to quantum effects.

D2/H2 adsorption selectivity on FAU zeolites at 77.4 K: Influence of Si/Al ratio and cationic composition

Abstract Equilibrium D2/H2 adsorption selectivity was determined at 77.4 K below 1000 hPa for a series of FAU type zeolites X exchanged with different cations (Li+, Na+, K+, Mg2+, Ca2+, Ba2+ and Mn2+). In addition NaY, DAY (dealuminated Y) and pure silica CHA and MFI zeolites were studied. Two experimental approaches were used to determine the D2/H2 adsorption selectivity: direct determination at the thermodynamic equilibrium from manometric coadsorption experiments and calculations by Ideal Adsorbed Solution Theory (IAST) from single gas adsorption isotherms. While these two approaches are not in quantitative agreement, they reveal similar trends. At low loading (  MnX > LiX > CaX ≈ NaX > …

CCDC 1061553: Experimental Crystal Structure Determination

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CCDC 1534485: Experimental Crystal Structure Determination

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CCDC 1061554: Experimental Crystal Structure Determination

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CCDC 1061551: Experimental Crystal Structure Determination

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CCDC 1061552: Experimental Crystal Structure Determination

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CCDC 1534001: Experimental Crystal Structure Determination

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