Cellulose-based materials in tailoring a novel defective titanium­carbon­phosphorus hybrid composites for highly efficient photocatalytic activity.

Until now, black titania has attracted much interest as a potential photocatalyst. In this contribution, we report the first demonstration of the effective strategy to fundamentally improve the photocatalytic performance using a novel sustainable defective titanium­carbon-phosphorous (TCPH) hybrid nanocomposite. The prepared TCPH was used for photocatalytic degradation of the main organic pollutants, which is methyl orange (MO) dye. The physico-chemical properties of as-prepared samples were characterized by various techniques to observe the transformations after carbonization and the interaction between different composite phases. The existence of Ti+3 and oxygen vacancies at the surface, and a notable increase in surface area, are all demonstrated by TCPH, together with the distinct core-shell structure. These unique properties exhibit excellent photocatalytic performance due to the boosted charge transport and separation. The highest degradation efficiency of methyl orange (MO) was attained in the case of TCPH when compared with titanium-cellulose-phosphorous (TCeP) and titanium­carbon-phosphorous (TCPN). Accordingly, the highest degradation efficiency was achieved by applying the optimal operational conditions of 1 g/L of TCPH catalyst, 10 mg/L of MO, pH of 7 and the temperature at 25 ± 3 °C after 3 min under LED lamp (365 nm) with light intensity 100 mW/cm2. The degradation mechanism was investigated, and the trapping tests showed the dominance of hydroxyl radicals in the degradation of MO. TCPH showed high stability under a long period of operation in five consecutive cycles, which renders the highly promising on an industrial scale. The fabrication of highly active defective titanium­carbon-phosphorous opens new opportunities in various areas, including water splitting, and CO2 reduction.

Calorimetric Heats of Intrusion of LiCl Aqueous Solutions in Hydrophobic MFI-Type Zeosil: Influence of the Concentration.

For the first time, we report calorimetric measurements of intrusion of aqueous LiCl solutions in a hydrophobic pure siliceous MFI zeolite (silicalite-1) under high pressure. Our results show that the intrusion heats are strongly dependent on the LiCl concentration. The intrusion process is endothermic for diluted solutions (molar H2O/LiCl = 12) as well as for water, but it becomes exothermic for a concentration close to saturation (molar H2O/LiCl = 4). Analysis of the data in the framework of wetting thermodynamics shows that besides surface wetting, other phenomena occur during intrusion, such as hydrogen-bond weakening and composition change. In all cases, water is preferentially intruded so that the intruded phase becomes more diluted than the bulk solution. In the case of the most diluted solution, only water molecules seemed to be intruded. Furthermore, silicalite-1 is shown to be very stable in the presence of LiCl solution, with no noticeable structural and textural modifications observed after intrusion.

Carboxymethylation of Cinnamyl Alcohol with Dimethyl Carbonate over Graphitic Carbon Nitrides.

A set of graphitic carbon nitride samples was prepared using a straightforward experimental procedure without templates and any subsequent treatments. The materials were studied in-depth using a range of physical and chemical methods such as X-ray diffraction, FTIR spectroscopy, elemental analysis (CHN), nitrogen physisorption, SEM, XPS, TPD CO2 . The resulting g-C3 N4 was shown to be highly efficient in carboxymethylation of cinnamyl alcohol with dimethyl carbonate yielding up to ca. 82 % of the desired cinnamyl methyl carbonate. In the studied conditions, an increase in the surface N atomic content leads to an increase in selectivity towards the desired carbonate, while a higher surface O content was beneficial for side products. Metal-free graphitic carbon nitride was shown to be one of the most productive (ca. 2 mol/h kgcat ) in the investigated reaction among studied heterogeneous catalysts.

High Efficiency of Na- and Ca-Exchanged Chabazites in D2/H2 Separation by Quantum Sieving.

Quantum sieving is a promising approach for separation of hydrogen isotopes using porous solids as sorbents at cryogenic temperatures (<77 K). In the present work, we characterized the properties of two aluminum-rich chabazites: Na-CHA and Ca-CHA (Si/Al = 2.1). The single-gas D2 and H2 adsorption isotherms were measured, and the thermodynamic selectivities were determined through coadsorption experiments in the temperature range 38-77 K. We found that at 38 K, Na-CHA shows a selectivity of 25.8 at a loading of 10.6 mmol·g-1. At the same temperature, Ca-CHA has slightly lower selectivity (18.3), but its uptake (12.9 mmol·g-1) is higher than that for Na-CHA. Comparison with the literature shows that the obtained values of selectivity are among the highest reported so far. This property combined with robustness and availability on the industrial scale of Al-rich chabazites makes them very promising materials for separation of hydrogen isotopes by quantum sieving.

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

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.

New force field for GCMC simulations of D2/H2 quantum sieving in pure silica zeolites.

We report a study on adsorption and coadsorption of H2 and D2 in FAU, MFI and CHA pure silica zeolites having different pore sizes and shapes. Adsorption capacities, selectivities, enthalpies and entropies are determined by combining experiments and GCMC simulations. We show that the force fields available in the literature cannot predict the adsorption equilibria below 77 K with sufficient accuracy. Here we propose a new force field adjusted by using our experimental data obtained for the pure silica MFI zeolite at 65 K and 77 K. With this new force field, it is possible to predict the adsorption and coadsorption equilibria on the three zeolite structures in a temperature range between 47 and 77 K with satisfactory precision. We corroborate that the step appearing on the single adsorption isotherms in CHA is the result of a molecular rearrangement of the adsorbed phase due to the apparition of a new adsorption site characterized by weaker interactions of H2 with the adsorbent. We conclude that the quantum sieving of H2 and D2 not only depends on the pore size but also on the pore shape, in particular, at high loading when the confinement effects become important.

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.

Loading of Cisplatin into Mesoporous Silica Nanoparticles: Effect of Surface Functionalization.

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.

Size and Surface Chemistry Tuning of Silicon Carbide Nanoparticles.

Chemical transformations on the surface of commercially available 3C-SiC nanoparticles were studied by means of FTIR, XPS, and temperature-programmed desorption mass spectrometry methods. Thermal oxidation of SiC NPs resulted in the formation of a hydroxylated SiO2 surface layer with C3Si-H and CHx groups over the SiO2/SiC interface. Controllable oxidation followed by oxide dissolution in HF or KOH solution allowed the SiC NPs size tuning from 17 to 9 nm. Oxide-free SiC surfaces, terminated by hydroxyls and C3Si-H groups, can be efficiently functionalized by alkenes under thermal or photochemical initiation. Treatment of SiC NPs by HF/HNO3 mixture produces a carbon-enriched surface layer with carboxylic acid groups susceptible to amide chemistry functionalization. The hydroxylated, carboxylated, and aminated SiC NPs form stable aqueous sols.

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 (NH3) follows a different pattern, reaching an exceptional uptake of 0.39 g/g (22.3 mmol/g) after the first adsorption cycle. Although the crystalline structure of 1 collapses after the first adsorption, the solid can be regenerated and maintains the capacity of 0.29 g/g (17 mmol/g) in the following cycles. We found that the high NH3 uptake is due to a combination of pore filling taking place below 150 h·Pa and chemisorption occurring at higher pressures. The latter process was shown to involve two phenomena: (i) coordination of NH3 molecules to Cd(2+) cations as follows from (113)Cd NMR and (ii) strong donor-acceptor interactions between NH3 molecules and pc1 ligands.

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 photosensitive, giving an eye-detectable color change upon exposure to the light of the microscope in air within 1-2 min. A very nice and interesting feature is the regular discoloration of crystals from the "edge" to the "core" upon exposition to O2 (reoxidation of organic radicals) due to the diffusion of O2 inside the pores, with this discoloration being slower in an oxygen-poor atmosphere. The formation of organic radicals is explained by an electron transfer from the oxygen atoms of the carboxylate groups to pyridinium cycles. In the structure of 3', [Zn10(hpc1)4(BDC)7(OH)6(H2O)2], resulting from the heating of sample 3 (desolvation and loss of CO molecules due to the decomposition of formate anions), no suitable donor-acceptor interaction is present, and as a consequence, this compound does not exhibit any chromic properties. The presence of permanent porosity in desolvated 1, 2, and 3' is confirmed by methanol adsorption at 25 °C with the adsorbed amount reaching 5 wt % for 1, 10 wt % for 3', and 13 wt % for 2. The incomplete desorption of methanol at 25 °C under vacuum points to strong host-guest interactions.

Capture of formaldehyde by adsorption on nanoporous materials.

The aim of this work is to assess the capability of a series of nanoporous materials to capture gaseous formaldehyde by adsorption in order to develop air treatment process and gas detection in workspaces or housings. Adsorption-desorption isotherms have been accurately measured at room temperature by TGA under very low pressure (p<2 hPa) on various adsorbents, such as zeolites, mesoporous silica (SBA15), activated carbon (AC NORIT RB3) and metal organic framework (MOF, Ga-MIL-53), exhibiting a wide range of pore sizes and surface properties. Results reveal that the NaX, NaY and CuX faujasite (FAU) zeolites are materials which show strong adsorption capacity and high affinity toward formaldehyde. In addition, these materials can be completely regenerated by heating at 200°C under vacuum. These cationic zeolites are therefore promising candidates as adsorbents for the design of air depollution process or gas sensing applications.

Nanocrystalline ZnCO3-A novel sorbent for low-temperature removal of H2S.

The reactivity of a nanocrystalline ZnCO3 toward H2S (0.2vol% in N2/H2 mixture) at 140-180°C was characterized by thermal gravimetric analysis and by breakthrough curves measurements. We have found that under used conditions transformation of ZnCO3 into ZnS is complete and the rate determining step of the sulfidation is the surface reaction. Such behavior is in strike contrast with that of ZnO whose sulfidation is severely limited by diffusion. The higher reactivity of ZnCO3 in comparison with ZnO is attributed to the different microstructure of ZnS layer formed in these materials after a partial sulfidation. As in ZnO-ZnS transformation the molar volume increases (from 14.5 to 23.8cm(3)/mol), a continuous protective ZnS layer is formed hampering the access of H2S to the non reacted ZnO core. By contrast, in ZnCO3-ZnS transformation the molar volume decreases (from 27.9 to 23.8cm(3)/mol), which produces a discontinuous non-protective ZnS layer enabling a complete transformation of ZnCO3 even at 140°C. The higher reactivity of ZnCO3 results in a considerable increase of the breakthrough sulfur capacity of the carbonate in comparison with oxide. The material has therefore a good potential for being used as a disposable sorbent for H2S capture at low temperature.

Hyperstoichiometric interaction between silver and mercury at the nanoscale.

Breaking through the stoichiometry barrier: as the diameter of silver particles is decreased below a critical size of 32 nm, the molar ratio of aqueous Hg(II) to Ag(0) drastically increases beyond the conventional Hg/Ag ratio of 0.5:1, leading to hyperstoichiometry with a maximum ratio of 1.125:1. Therein, around 99% of the initial silver is retained to rapidly form a solid amalgam with reduced mercury.

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

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-extrusion cycle is attributed to the creation of silanol groups during the first water intrusion. Detailed FTIR and solid-state NMR spectroscopic characterizations provided a molecular evidence of chemical modification of zeolite framework with the formation of local silanol defects created by the breaking of siloxane bonds.