The Adsorption sur Solides Poreux (ASP) research team of the Universite de Bourgogne in France has many years of experience in the measurement of gas and vapor adsorption in nanoporous solids. For more than 40 years, it has acquired extensive adsorption data and developed its own adsorption database. This base contains more than 1000 adsorption equilibrium data sets (adsorption isotherms, isobars, and heats of adsorption) for 49 gases or vapors on adsorbents representing similar to 15 different classes of porous solids. This ASP database is now open free of charge to the scientific community. This article provides some basic thermodynamic definitions used in this database and presents the experimental techniques used. It also includes references to the adsorption data published to date and explains how to use the database.

Carbonyl compounds are ubiquitous quality trackers that provide information about food product degradation as well as air and water pollution levels. In addition, they are used as biomarkers for medical diagnoses. With more user-friendly sensors, their fast detection and easy quantification are highly relevant. The synthesis, characterization, and performance assessment of a new sensor based on aniline fluorescence to monitor carbonyls in real time is reported. A cost-effective synthesis using a straightforward sol-gel process led to the construction of a nontoxic silica-based material with high porosity, which can be used with almost no sample preparation. The material exhibits a rapid (< 1 min) fluorescence decrease upon interaction with carbonyl groups. The limit of detection is as low as ca. 5 x 10(-4)mol center dot L-1 for hexanal, while fluorescence extinction occurs at much higher concentrations (5 x 10(-1)center dot mol L-1), which enables the sensor to be used with a very broad range of detection. Real-time monitoring is possible since the fluorescence loss correlates with the concentration of carbonyl moieties. The performance was validated in simulating as well as in real media, making this sensor suitable for use in a wide range of applications.

Background: Pristine SBA-15 and amine or thiol-functionalized SBA-15 materials were synthesized, characterized, and highlighted by studying the glutathione (GSH) adsorption process in aqueous solutions. Methods: In this study, SBA-15 mesoporous materials were functionalized with 3-aminopropyltriethoxysilane (APTS) and (3-mercaptopropyl)triethoxysilane (MPTES) in order to introduce amine and thiol groups onto the surface by using a post-grafting method, respectively. For comparison, the SBA-15-based materials were used as adsorbents to further investigate the adsorption behaviour of GSH under various experimental conditions. Significant findings: To examine the underlying mechanism of the adsorption process, the kinetics of the GSH adsorption onto SBA-15-based adsorbents were fitted using pseudo-first order, pseudo-second order, Elovich, and Aharoni models. Adsorption isotherms showed that the Freundlich isotherm model was the most appropriate to simulate the adsorption of GSH molecules onto SBA-15-NH2 adsorbent and the Langmuir isotherm model for the two other substrates. In addition, the adsorption thermodynamics confirmed the exothermic behaviour of GSH adsorption process onto the SBA-15-SH adsorbent. In contrast, the capture of GSH molecules by the SBA-15-OH and SBA-15-NH2 adsorbents follows an endothermic reaction process. Finally, the adsorption nature of GSH onto SBA-15 adsorbents is classified as physisorption.

A healthy breath is mainly composed of water, carbon dioxide, molecular nitrogen, and oxygen and it contains many species, in small quantities, which are related to the ambient atmosphere and the metabolism. The breath of a person affected by lung cancer presents a concentration of 1-propanol higher than usual. In this context, the development of specific sensors to detect 1-propanol from breath is of high interest. The amount of propanol usually detected on the breath is of few ppb; this small quantity is a handicap for a reliable diagnostic. This limitation can be overcome if the sensor is equipped with a pre-concentrator. Our studies aim to provide an efficient material playing this role. This will contribute to the development of reliable and easy to use lung cancer detectors. For this, we investigate the properties of a few hydrophobic porous materials (chabazite, silicalite-1, and dealuminated faujasite). Hydrophobic structures are used to avoid saturation of materials by the water present in the exhaled breath. Our experimental and simulation results suggest that silicalite -1 (MFI) is the most suitable structure to be used as a pre-concentrator.

We evaluated the potential of several novel porous materials for toluene capture in air under humid conditions. Four novel porous solids of different nature were studied and compared to two reference materials: two hypercross-linked polymers HCP and SMP, the metal organic framework MAF-6 and the activated carbon derived from MAF-6 (AC-MAF-6) with references (Norit RB3 and a dealuminated Y zeolite (DAY)). The affinity of the sorbents for toluene was determined from adsorption isotherms recorded at 25 degrees C and the low pressure part of the isotherms (<100 Pa) were successfully fitted with the Unilan equation allowing extrapolation to sub ppm (<0.1 Pa) concentration range. These equilibrium measurements were complemented by recording the breakthrough curves at 10 Pa of toluene under dry and humid conditions (50% relative humidity). While MAF-6 and DAY show low dynamic capacities under these conditions, HCP and AC-MAF-6 exhibit much better performances which in the case of AC-MAF-6 are close to RB3 activated carbon even under humid conditions. Moreover, these sorbents can be successfully regenerated under mild conditions (200 degrees C) and show stable performance through adsorption/desorption cycles. Our work suggests that HCP and MAF-6-derived activated carbon are promising materials for toluene capture in air under realistic conditions.

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, 30.8, 16.7, 25, and 28.8 ppb of benzene, toluene, ethylbenzene, ortho- and para-xylene, respectively, were detected in a short analysis time (∼10 min) even in the presence of 60% relative humidity at 25 °C. The DM2C showed excellent stability over a period of 4 months and more than 500 tests, as well as repeatability, which makes it a very reliable adsorbent for the detection of trace VOCs in indoor air under realistic conditions in the presence of humidity.

Active films are produced by a grafting reaction based on the reactivity between chitosan amino groups and lignin hydroxyl groups. This opens a new route for the valorization of lignin, with the possibility of tuning the anti-oxidant activity.

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 on a hydrophobic FAU zeolite reveals that high silica zeolites could be promising adsorbents for the capture of formaldehyde in the presence of water.

Cisplatin ( cis-diaminedichloroplatinum(II), CDDP) plays a crucial role in the treatment of various malignant tumors. However, its clinical efficacy and applicability are restricted by issues of toxicity and resistance. Here, for drug delivery purposes, the outer surface of MCM-41 mesoporous silica nanoparticles (MSNs) was functionalized with poly(ethylene glycol) ( Mw = 10 000 g/mol) or low-molecular-weight ( Mw = 1800 g/mol) branched polyethyleneimine (PEI). Given the strong affinity of sulfur for platinum, thiol-functionalized MSNs were synthesized for comparison by co-condensation with (3-mercaptopropyl)triethoxysilane. CDDP loading was performed either by adsorption or impregnation in aqueous media without the use of dimethyl sulfoxide as a solubilizer. CDDP loading capacities obtained by impregnation were higher than those obtained by adsorption and varied from 3.9 to 16.1 wt %, depending on the functional group. Loaded nanomaterials were characterized by scanning electron microscopy, scanning transmission electron microscopy-high-angle annular dark-field, and Raman spectroscopy. Depending on the functional groups, platinum-based species were either dispersed in the nanomaterials as nanocrystals or uniformly distributed as molecular species. The spectral signature of CDDP was strongly modified when platinum species were homogeneously distributed within the nanomaterials. Preliminary drug release studies performed at 37 °C showed that the behavior of CDDP-loaded MSNs strongly depends on the nature of the present functional groups. Among the functionalization routes investigated in this paper, PEI-based functionalization showed the most promising results for further applications in controlled drug release with the absence of burst release and a sustained release over 72 h.

The mechanism of hydrolysis of lithium oxide (Li2O) was studied by thermogravimetry, calorimetry and in situ infrared spectroscopy under water (H2O) vapor pressure at 298 K. Additional infrared measurements were also performed with heavy water (D2O) to go deeper in the understanding of the mechanism. First, this study showed that the pristine oxide is composed of micrometric particles of lithium oxide core surrounded by a thin protective layer of lithium hydroxide (LiOH). When exposed to a pressure below 5 hPa, the hydrolysis of the particles proceeds mainly through the adsorption of water molecules on the external surface of the lithium hydroxide layer and to a lesser extent to the formation of lithium hydroxide for the smallest particles. By increasing the pressure, the reaction proceeds through the alternative formation of lithium hydroxide monohydrate (LiOH·H2O) and lithium hydroxide. The kinetics of this reaction is controlled by water diffusion through the lithium hydroxide layer. In such a process, the formation of the monohydrate starts when the LiOH layer reaches some critical thickness.

The analysis of exhaled volatile organic compounds (VOCs) related to lung cancer is a very promising way in medical diagnosis because it is non-invasive and much less expensive than traditional medical analysis used so far. In that sense, a silicon micro-analytical platform consisting of a micro-preconcentrator coupled to a silicon spiral gas chromatographic micro-column was built, and a metal oxide-based gas sensor was used as a miniaturized gas detector. This micro-fabricated device was successfully tested to selectively detect low concentrations of VOCs considered as lung cancer biomarkers, within a few minutes even in presence of high concentrations of water vapor and carbon dioxide. (C) 2017 Elsevier B.V. All rights reserved.

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 (<20 molec/uc) exchanged zeolites X in the selectivity diminishes with increasing cation size from 5.7 for MgX to 2.4 for KX: MgX > MnX > LiX > CaX ≈ NaX > KX ≈ BaX. In contrast, at high loading the selectivity is not influenced by the material composition being around 1.5 ± 0.2 for all studied materials. For cation-free zeolites (CHA and MFI) the latter value is observed for all loadings. The key role of cations in D2/H2 selectivity is explained by the fact that at low loading the adsorption proceeds through strong guest-cation interactions while at high loading weaker interactions are involved. Surprisingly, the selectivity in the low loading range is found to be correlated with the cation size and not with the interaction strength (estimated from the value of the Langmuir constant). This behavior of FAU type zeolites is thus different from that of MOFs or that predicted by simple theoretical models based on a one dimensional gas in a harmonic potential.

The reaction of lithium hydride (LiH) powder with pure water vapor (H2O and D2O) was studied by thermogravimetry and in situ infrared spectroscopy at 298 K over a large pressure range. The mean particle size of LiH is around 27 mu m. At very low pressure, the hydrolysis starts with the formation of lithium oxide (Li2O). Then, both Li2O and lithium hydroxide (LiOH) are formed on increasing pressure, thus, creating a Li2O/LiOH bilayer. The reaction takes place through the consumption of LiH and the formation of Li2O at the LiH/Li2O interface and through the consumption of Li2O and the formation of LiOH at the Li2O/LiOH interface. Above 10 hPa, only the monohydrate LiOH center dot H2O is formed. This hydration reaction of LiOH into LiOH center dot H2O occurs at a lower pressure (8 hPa) after the first hydration-dehydration cycle. The hydrolysis mechanism proposed in this paper suggests that the diffusion of ionic species across the intermediate Li2O layer is the rate limiting step of the reaction. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Background: In the field of PCPs or MOF, besides strategies to design compounds with huge porosity, a great trend is the molecular engineering of the ligands. Their functionalization allows rendering walls of pores as an active surface able to specifically interact with guest molecules. Quite recently, bipyridinium (called also viologen) cores bearing carboxylate groups have been considered as ligands in the field of PCPs because of the electron acceptor character of bipyridinium units which are able to strongly interact with electron donor guest molecules. Objectives: The main objective of this study was to prepare new PCPs materials based on the viologencarboxylate ligand 1-(4-carboxyphenyl)-4,4'-bipyridinium. Methods: The compounds [Cd(hpc1)(BPDC)].2H2O (1) and [Cd2(hpc1)2(BPDC)(BPDC)].4H2O.DMF (2) have been synthesized from a mixture of Hhpc1Cl, Cd(NO3)2, H2BPDC -biphenyl-4,4′-dicarboxylic acid- (and H2BDC -terephtalic acid- for 2), DMF, EtOH and H2O heated at 100°C for 48h in a 25mL teflon-lined stainless steel autoclave, and slowly cooled to room temperature in 8 hours. Crystals were collected, washed with DMF and air-dried. X-ray diffraction data were collected on a Bruker-Nonius KAPPA-CDD with MoKα radiation (λ=0.71073 Å) for 1 (T= 293 K), and on an Agilent Supernova with CuKα radiation (λ=1.5418 Å) for 2 (T= 150 K). All experiments were carried out under a nitrogen atmosphere. The methanol adsorption isotherms of 1 and 2 at 298K were measured using a home-built McBain type balance. N2 adsorption isotherms at 77K were recorded on a Micromeritics ASAP 2020 instrument. In both cases before measurements the solids were degassed under vacuum (<10-5 hPa) at 150°C for 4h. Results: Two porous coordination polymers based on Cd2+ cations and the zwiterrionic viologencarboxylate ligand 4,4'-bipyridinium-1-(4-carboxyphenyl) (hpc1), [Cd(hpc1)BPDC].2H2O (1), and [Cd2(hpc1)2(BDC)(BPDC)] .4 H2O. DMF (2) have been discovered. The structures of these two compounds are isoreticular with half BPDC2- anions present in 1 being replaced by BDC2- anions in 2. The overall structures which result from the interpenetration of five 3D networks, exhibit channels containing guest molecules. Upon desorption, a breathing effect of the structure of 1 is observed as revealed by X-ray diffraction and methanol adsorption measurements. In fact, methanol adsorption on 1 occurs through a two-step isotherm characteristic of a gate opening in a flexible framework, while 2 exhibits a type I isotherm. Interestingly, the MeOH adsorption allows to suppose that the closed rhomboid channels which are present in the room temperature crystal structure of the as-synthesized compound become open to accommodate methanol molecules when the MeOH pressure is high (P/P°>0.5). Conclusion: Our results show that the association of Cd2+, the 4,4’-bipyridinium-1-(4-carboxyphenyl) viologen- carboxylate ligand and either the terephthalate anion BDC2- or the mixture of BDC2- and the biphenyl- 4,4′-dicarboxylate BPDC2- anion afford two isoreticular PCP compounds whose different structural characteristics, rigid vs flexible, have consequence on their adsorption properties. Keywords: Porous coordination polymers, viologen, adsorption, breathing effect, viologen-carboxylate ligand, isoreticular.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Among the different methods to separate hydrogen isotopes one is based on the phys-isorption 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 adsorption capacity increases with the molecular weight of the isotopes. Isosteric enthalpies evidence a heterogeneous adsorption process with two type of hydrogen isotopes differently linked to the zeolitic structure. The calculated pair distribution functions at high loadings exhibit a liquid-like structuration in the supercages of NaX, which may explain the different adsorption capacities for H-2, D-2 and T-2 and the heterogeneity of the adsorption process. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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: [Cd-3(pc2) (BTC)(2)(H2O)(2)]center dot 6H(2)O ([1(H2O)(2)]center dot 6H(2)O; 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]center dot 2H(2)O. On the other hand, the partial dehydration of the as-synthesized compound leads to the intermediate phase [1(H2O)]center dot 3H(2)O in which one H2O molecule is bound to Cd2+ ions of trinudear building units, and three others are localized in the pores. The structural analysis also reveals that the pyridiniumN+ Lewis sites, which interact with water molecules in [1(H2O)(2)]center dot 6H(2)O, interact with carboxylate groups after structural reorganization in [1]center dot 2H(2)O. The water adsorption isotherm clearly shows that the dehydrated compound is highly hydrophilic and adsorbs water in three steps: first and second at P/P-s < 0.01 and third at P/P-s similar to 0.1 with the overall water adsorption reaching 0.13 g H2O/g. This material is also able to reversibly adsorb ammonia (up to 0.3 g/g or 17.6 mmol/g).

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 activated carbon microspheres W5 and the zeolite NaY, which exhibit high specific surface areas and large micropore volumes, are the best adsorbent materials to capture toluene present at very low concentration in the gas phase.

A novel porous coordination polymer [Mn(pc3)(H2O)2]·xH2O (3 < x < 4) is synthesized in water at pH = 7 using the anionic viologen-carboxylate ligand 4,4'-bipyridinium,1,1'-bis-(2,4-dicarboxyphenyl) (pc32-). Dehydration of the material results in the formation of open pores containing two types of accessible Lewis acid sites: exposed Mn2+ cations and N+ atoms of viologen units. Due to this property the PCP shows high affinity and capacity in the adsorption of H2O, CO2 and NH3. Despite the presence of strong adsorption sites this material is stable in liquid water and in gaseous NH3.