Postsynthetic Improvement of the Physical Properties in a Metal–Organic Framework through a Single Crystal to Single Crystal Transmetallation

A single crystal to single crystal transmetallation process takes place in the three‐dimensional (3D) metal–organic framework (MOF) of formula Mg^II₂{Mg^II₄[Cu^II₂(Me₃mpba)₂]₃}?45 H₂O ( 1 ; Me₃mpba^4?=N,N′‐2,4,6‐trimethyl‐1,3‐phenylenebis(oxamate)). After complete replacement of the Mg^II ions within the coordination network and those hosted in the channels by either Co^II or Ni^II ions, 1 is transmetallated to yield two novel MOFs of formulae Co₂^II{Co^II₄[Cu^II₂(Me₃mpba)₂]₃}?56 H₂O ( 2 ) and Ni₂^II{Ni^II₄[Cu^II₂(Me₃mpba)₂]₃}? 54 H₂O ( 3 ). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties.     

Evaluation of an activated carbon from olive stones used as an adsorbent for heavy metal removal from aqueous phases

The performance of a microporous activated carbon prepared chemically from olive stones for removing Cu(II), Cd(II) and Pb(II) from single and binary aqueous solutions was investigated via the batch technique. The activated carbon sample was characterized using N₂ adsorption–desorption isotherms, SEM, XRD, FTIR, and Boehm titration. The effect of initial pH and contact time were studied. Adsorption kinetic rates were found to be fast and kinetic experimental data fitted very well the pseudo-second-order equation. The adsorption isotherms fit the Redlich–Peterson model very well and maximum adsorption amounts of single metal ions solutions follow the trend Pb(II) > Cd(II) > Cu(II). The adsorption behavior of binary solution systems shows a relatively high affinity to Cu(II) at the activated carbon surface of the mixture with Cd(II) or Pb(II). An antagonistic competitive adsorption phenomenon was observed. Desorption experiments indicated that about 59.5% of Cu(II) and 23% of Cd(II) were desorbed using a diluted sulfuric acid solution.     

Tuning CO2 Uptake and Reversible Iodine Adsorption in Two Isoreticular MOFs through Ligand Functionalization

The synthesis and characterization of two isoreticular metal–organic frameworks (MOFs), {[Cd(bdc)(4‐bpmh)]}_n?2 n(H₂O) ( 1 ) and {[Cd(2‐NH₂bdc)(4‐bpmh)]}_n?2 n(H₂O) ( 2 ) [bdc=benzene dicarboxylic acid; 2‐NH₂bdc=2‐amino benzene dicarboxylic acid; 4‐bpmh=N,N‐bis‐pyridin‐4‐ylmethylene‐hydrazine], are reported. Both compounds possess similar two‐fold interpenetrated 3D frameworks bridged by dicarboxylates and a 4‐bpmh linker. The 2D Cd‐dicarboxylate layers are extended along the a‐axis to form distorted square grids which are further pillared by 4‐bpmh linkers to result in a 3D pillared‐bilayer interpenetrated framework. Gas adsorption studies demonstrate that the amino‐functionalized MOF 2 shows high selectivity for CO₂ (8.4 wt % 273 K and 7.0 wt % 298 K) over CH₄, and the uptake amounts are almost double that of non‐functional MOF 1 . Iodine (I₂) adsorption studies reveal that amino‐functionalized MOF 2 exhibits a faster I₂ adsorption rate and controlled delivery of I₂ over the non‐functionalized homolog 1 .     

Moisture sorption in polyamide 6.6: Experimental investigation and comparison to four physical-based models

Water sorption in polyamide 6.6 has been characterized for a wide range of temperature (25°C to 80°C) and various water activities using a Dynamic Vapor Sorption testing machine. Complex sorption mechanisms govern the water uptake in the material. The competition between two main temperature dependant mechanisms has been observed: a Henry's sorption mechanism that mainly governs the sorption curve at low water activities, and a second mechanism at high water activities that could be related to the formation of water clusters. It is observed that the temperature dependency can mainly be attributed to the Henry's contribution. Four physically based models are then used and identified thanks to the extended experimental database. It is shown that a simple Flory-Huggins model is not able to capture the experimental observations at very high water activities for all the temperatures tested. The ENSIC model is a better choice, but good prediction for very high water activity cannot be obtained. Both modified Park and GAB models can accurately predict the volume fraction of water for the whole ranges of water activity and temperature, although the modified Park model should be preferred considering the number of parameters and the mathematical simplicity.     

Effect of 300 and 500 MPa pressure treatments on starch–water adsorption/desorption isotherms and hysteresis

Pressure treatments of 300 and 500?MPa during 15?min were found to change starch–water sorption (adsorption and desorption) isotherms and the hysteresis effect, particularly the 500?MPa. This last treatment shifted the adsorption/desorption isotherms downward, compared with non-treated starch and starch treated at 300?MPa. The observed hysteresis effect decreased with the increase in pressure level in the whole a_w range, indicating that adsorption and desorption isotherms became closer. Guggenheim–Anderson–De Boer and Brunauer–Emmett–Teller model parameters Cb, Cg, K and Mm also showed changes caused by pressure, the latter being lower in the pressure-processed samples, thus indicating possible changes on microbial and (bio)chemical stabilities of pressure-processed food products containing starch.     

Metal-doped apatitic calcium phosphates: preparation,characterization, and reactivity in the removal of hydrogen sulfide from gas phase

With the expansion of human activities, there are more and more living areas adjacent to industrial and/or agricultural activities such as chemical processes, petroleum processes, paint finishing, food processing, livestock farming, composting plants etc. Bad odor is part of several nuisances caused by industrial and/or agricultural activities. Hydrogen sulfide (H₂S) is a typical odorous molecule which causes foul odor at very low concentration. This molecule is formed in different industrial installations, in particular in coal combustion, and petrochemical refinery. The separation and/or transformation of H₂S from gas phase to odorless products are important processes for sustainable development. In this paper, we communicate the preparation of new sorbents for the sorption of H₂S from a synthetic gas effluent. These sorbents consist in an inorganic phase (hydroxyapatite) as host particles, and well-dispersed particles of a metal oxide as guest particles which are the active phase for the removal of H₂S. At room conditions, iron, lead, and zinc doped calcium phosphates were found to be effective for the removal of H₂S. The performance of the sorbents depends on preparation method and the nature of active phases. This opens new prospects for the treatment of H₂S from gas phase.     

Effect of preparation method on the properties of deposited copper-palladium deep-oxidation catalysts

Activity of alumocopper-palladium catalysts (0.5 at.% Pd, 0.1–3.0 at.% Cu) which differ in preparation method in CO, C₂H₄ and CH₄ oxidation is studied. It is shown that preliminary modification of a carrier by copper leads to an enhancement of catalyst activity as compared with an alumopalladium one. With the methods of EDRS, TPR-TRS, and TPR of adsorbed CO and O₂, the Pd/Cu/Al₂O₃, Cu/Pd/Al₂O₃ and (Pd−Cu)/Al₂O₃, systems are studied. It is established that premodification of the carrier leads to a weakening of its interaction with the second metal while the combined deposition from one impregnating solution in subsequent thermal treatment is accompanied by a strong metal aggregation. Institute of Physicoorganic Chemistry, National Academy of Sciences of Belarus, 13, Surganov St., Minsk, 220072. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 114–120, January–February, 1998.     

Preferential sorption and permeation of binary liquid mixtures in poly (vinyl chloride) membrane by pervaporation

Preferential sorptions and pervaporation selectivities in poly (vinyl chloride) (PVC) membrane for various binary liquid mixtures were investigated. Methanol/n-propanol, benzene/n-hexane, and ethanol/water mixtures were selected as the binary liquid mixture. In the methanol/n-propanol mixture, methanol was preferentially sorbed in the PVC membrane and predominantly permeated. In the benzene/n-hexane mixture, benzene was incorporated and permeated preferentially. In the ethanol/water mixture, ethanol was preferentially sorbed in the PVC membrane and water was preferentially permeated. The preferential sorptions were analyzed according to Mulder's model derived from Flory-Huggins thermodynamics. The pervaporation selectivity in these systems were discussed using a sorption selectivity and diffusion selectivity. © 1995 John Wiley & Sons, Inc.