Efficient CO2 capture by a task-specific porous organic polymer bifunctionalized with carbazole and triazine groups.

A porous triazine and carbazole bifunctionalized task-specific polymer has been synthesized via a facile Friedel-Crafts reaction. The resultant porous framework exhibits excellent CO2 uptake (18.0 wt%, 273 K and 1 bar) and good adsorption selectivity for CO2 over N2.

Dynamic and structural properties of room-temperature ionic liquids near silica and carbon surfaces.

The dynamic and structural properties of a room-temperature ionic liquid (RTIL) 1-butyl-3-methyl-imidazolium(trifluoromethanesulfonimide) ([C4mim][Tf2N]) confined in silica and carbon mesopores were investigated by molecular dynamics (MD) simulations and nuclear magnetic resonance (NMR) experiments. The complex interfacial microstructures of confined [C4mim][Tf2N] are attributed to the distinctive surface features of the silica mesopore. The temperature-dependent diffusion coefficients of [C4mim][Tf2N] confined in the silica or carbon mesopore exhibit divergent behavior. The loading fraction (f = 1.0, 0.5, and 0.25) has a large effect on the magnitude of the diffusion coefficient in the silica pore and displays weaker temperature dependence as the loading fraction decreases. The diffusion coefficients of mesoporous carbon-confined [C4mim][Tf2N] are relatively insensitive to the loading faction and exhibit a temperature dependence that is similar to the bulk dependence at all loading levels. Such phenomena can be attributed to the unique surface heterogeneity, dissimilar interfacial microstructures, and interaction potential profile of RTILs near silica and carbon walls.

New tricks for old molecules: development and application of porous N-doped, carbonaceous membranes for CO2 separation.

A new strategy is successfully applied to "old" acetyl compounds. A free-standing, porous, N-doped carbonaceous membrane is facilely prepared from the thermal treatment of a pyrrole-ring-containing polymeric membrane based on the superacid-catalyzed copolymerization of acetyl monomers. An exceptional ideal CO2 /N2 permselectivity of 43.2 is achieved with a good CO2 permeability of 1149.3 Barrer, exceeding the recent upper bound for CO2 /N2 .

Synthesis of porous, nitrogen-doped adsorption/diffusion carbonaceous membranes for efficient CO2 separation.

A porous, nitrogen-doped carbonaceous free-standing membrane (TFMT-550) is prepared by a facile template-free method using letrozole as an intermediate to a triazole-functionalized-triazine framework, followed by carbonization. Such adsorption/diffusion membranes exhibit good separation performance of CO2 over N2 and surpassing the most recent Robeson upper bound. An exceptional ideal CO2 /N2 permselectivity of 47.5 was achieved with a good CO2 permeability of 2.40 × 10(-13) mol m m(-2) s(-1) Pa(-1) . The latter results arise from the presence of micropores, narrow distribution of small mesopores and from the strong dipole-quadrupole interactions between the large quadrupole moment of CO2 molecules and the polar sites associated with N groups (e.g., triazine units) within the framework.

Efficient CO(2) capture by porous, nitrogen-doped carbonaceous adsorbents derived from task-specific ionic liquids.

The search for a better carbon dioxide (CO(2) ) capture material is attracting significant attention because of an increase in anthropogenic emissions. Porous materials are considered to be among the most promising candidates. A series of porous, nitrogen-doped carbons for CO(2) capture have been developed by using high-yield carbonization reactions from task-specific ionic liquid (TSIL) precursors. Owing to strong interactions between the CO(2) molecules and nitrogen-containing basic sites within the carbon framework, the porous nitrogen-doped compound derived from the carbonization of a TSIL at 500 °C, CN500, exhibits an exceptional CO(2) absorption capacity of 193 mg of CO(2) per g sorbent (4.39 mmol g(-1) at 0 °C and 1 bar), which demonstrates a significantly higher capacity than previously reported adsorbents. The application of TSILs as precursors for porous materials provides a new avenue for the development of improved materials for carbon capture.

Rotational and translational dynamics of rhodamine 6G in a pyrrolidinium ionic liquid: a combined time-resolved fluorescence anisotropy decay and NMR study.

NMR spectroscopy and time-resolved fluorescence anisotropy decay (TRFAD) are two of the most commonly used methods to study solute-solvent interactions. However, only a few studies have been reported to date using a combined NMR and TRFAD approach to systematically investigate the overall picture of diffusional and rotational dynamics of both the solute and solvent. In this paper, we combined NMR and TRFAD to probe fluorescent rhodamine dye in a pyrrolidinium-based room temperature ionic liquid (RTIL), an emergent environmentally friendly solvent type used in several energy-related applications. A specific interaction of the R6G cation and [Tf2N] anion was identified, resulting in near-stick boundary condition rotation of R6G in this RTIL. The diffusional rates of the R6G solute and [C4mpyr][Tf2N] solvent derived from (1)H NMR suggest the rates are proportional to their corresponding hydrodynamic radii. The (1)H and (13)C NMR studies of self-rotational dynamics of [C4mpyr][Tf2N] showed that the self-rotational correlation time of [C4mpyr](+) is 47 ± 2 ps at 300 K. At the same temperature, we find that the correlation time for N-CH3 rotation in [C4mpyr](+) is 77 ± 2 ps, comparable to overall molecular reorientation. This slow motion is attributed to properties of the cation structure.

Solid-state 17O NMR study of benzoic acid adsorption on metal oxide surfaces.

Solid-state (17)O NMR spectra of (17)O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the (17)O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. (27)Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

Physicochemical properties of imidazolium-derived ionic liquids with different C-2 substitutions.

Five room temperature ionic liquids based on C-2 substituted imidazolium cations and bis(trifluoromethanesulfonyl)imide (TFSI) anions were synthesized and their physicochemical properties: thermal property, density, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability, were systematically investigated. The temperature dependence of both viscosity and ionic conductivities of these ionic liquids can be described by the Vogel-Fulcher-Tamman (VFT) equation. Compared with the reference, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, the introduction of functional groups at the C-2 position generally increased the viscosity and lowered the ionic conductivity. The introduction of an ether group (-CH(2)OCH(2)CH(2)CH(2)CH(3)) at the C-2 position not only enhanced the reduction stability of the ionic liquids but also exhibited the lowest solid electrolyte interfacial resistance (R(SEI)). In contrast, the introduction of a cyano group (-CN) at the C-2 position not only decreased the reduction stability but also adversely increased the SEI resistance. The effect of the C-2 substitution on the reduction stability was explained by the change in the energy level of the lowest unoccupied molecular orbital. The self-diffusion coefficients (D) of each ion were measured by pulsed field gradient nuclear magnetic resonance (PFG-NMR). The lithium transference number (t(Li)) of 0.5 M LiTFSI/IL solutions calculated from the self-diffusion coefficients was in the range of 0.04 to 0.09.

Surface alumina species on modified titanium dioxide: A solid-state (27)Al MAS and 3QMAS NMR investigation of catalyst supports.

(27)Al MAS and 3QMAS NMR have been used to study Al(2)O(3)/TiO(2) catalyst supports synthesized via excess-solution impregnation and surface sol-gel methods. Temperature and alumina loading level strongly affect chemical states of aluminum oxide species observed. Surface cations, Al(H2O)6(3+), a surface alumina monolayer, and disordered transitional aluminas (multilayers) and alpha-alumina, coexist on the TiO(2) surface. Chemical shift and quadrupole coupling constants are reported for the major species identified in 3QMAS experiments. Gold particle catalysts prepared from supports calcined at 500 degrees C have optimum catalytic activity in CO oxidation, and smallest gold particle size for supports, which show maximum monolayer type octahedral alumina on the titania surface.

Layer-by-layer grafting of titanium phosphate onto mesoporous silica SBA-15 surfaces: synthesis, characterization, and applications.

Metal phosphates have many applications in catalysis, separation, and proton conduction, but their small surface areas and/or constrained pore structures limit their utilization. Here, we report two new methods for the liquid-phase grafting of titanium phosphate onto mesoporous silica (SBA-15) surfaces: (1) alternate grafting of Ti(OPr(i))(4) and then POCl(3) and (2) one-pot grafting of titanium phosphate formed in situ by employing Ti(OPr(i))(4) (a base) and POCl(3) (an acid) as an appropriate "acid-base pair". Both the size of mesopores and the content of titanium phosphate can be changed by increasing the number of modification cycles in a stepwise (or layer-by-layer) fashion. The obtained products were characterized by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, N(2) adsorption-desorption, transmission electron microscopy, (31)P and (29)Si magic-angle spinning NMR, and NH(3) temperature-programmed desorption, and their performance in acid catalysis and metal ion adsorption was investigated. This work provides new methodologies for the general synthesis of supported metal phosphates with large surface areas, ordered nanoporous structures, and acid properties.

The generation of intense radiofrequency fields in microcoils.

Large amplitude radiofrequency (rf) fields hold great promise in wide line NMR where it becomes possible to excite the full breadth of the line in a quantitative fashion. Applications in quadrupole NMR and in NMR of paramagnetic systems benefit greatly from intense fields. Spin manipulations in multiple quantum NMR experiments, specifically, the generation of multiple quantum coherence in MQ NMR, are more efficiently produced using intense rf fields. In this work we describe a microcoil probe that produces an rf field of 25 MHz, more than five times larger than the greatest rf field reported in the literature. We accomplish this in a robust, 127 microm diameter solenoid coil using 1 kW of rf power.

119Sn NMR chemical shift tensors in anhydrous and hydrated Si8O20(SnMe3)8 crystals.

(119)Sn chemical shift tensors of crystalline trialkyltin functionalized octameric spherosilicates, Si(8)O(20)(SnMe(3))(8), have been determined by fitting sideband intensities in solid-state magic angle spinning (MAS) NMR spectra. Tin chemical shift parameters are exquisitely sensitive to the presence of water of crystallization. Both hydrogen bonding and incipient oxygen-tin bonding from molecular water impact the local tin environment. Tin chemical shift tensors in the crystalline derivatives reflect the changes in geometry and coordination number at the tin centers. Chemical shift correlations on the crystalline derivatives, with known x-ray structures, are used to infer the tin coordination environment in an amorphous sample.

Synthesis and characterization of periodic mesoporous organosilicas as anion exchange resins for perrhenate adsorption.

A new methodology to immobilize ionic liquids through the use of a bridged silsesquioxane N-(3-triethoxysilylpropyl), N(3)-(3-trimethoxysilylpropyl-4,5-dihydroimidazolium iodide that incorporates an ionic functionality for the assembly of novel periodic mesoporous organosilica (PMO) materials has been developed. The resulting PMO materials were investigated for use as novel anion exchange resins for the separation of perrhenate anions in aqueous solution. As compared with cetyltrimethylammonium chloride, 1-hexadecane-3-methylimidazolium bromide has been demonstrated to be a more efficient surfactant template for the generation of mesopores and surface areas for such PMO materials.

Facile one-pot synthesis of gold nanoparticles stabilized with bifunctional amino/siloxy ligands.

A method for the direct one-pot synthesis of amine-stabilized gold nanoparticles using 3-(trimethoxysilylpropyl)diethylenetriamine (TMSP dien) is described. The amine groups of this bifunctional molecule act as a stabilizer for gold nanoparticles as they form by reduction of HAuCl4. Highly stable gold nanoparticles with sizes tunable between 8 and 20 nm can be readily obtained. This method is quite simple to implement and environmentally benign as there is no need to add an external reducing reagent. The incorporated siloxy functionality was subsequently used to form a silica shell around the gold particle.

Pyrolysis of mesoporous silica-immobilized 1,3-diphenylpropane. Impact of pore confinement and size.

Mesoporous silicas such as SBA-15 and MCM-41 are being actively investigated for potential applications in catalysis, separations, and synthesis of nanostructured materials. A new method for functionalizing these mesoporous silicas with aromatic phenols is described. The resulting novel hybrid materials possess silyl aryl ether linkages to the silica surface that are thermally stable to ca. 550 degrees C, but can be easily cleaved at room temperature with aqueous base for quantitative recovery of the organic moieties. The materials have been characterized by nitrogen physisorption, FTIR, NMR, and quantitative analysis of surface coverages. The maximum densities of 1,3-diphenylpropane (DPP) molecules that could be grafted to the surface were less than those measured on a nonporous, fumed silica (Cabosil) and were also found to decrease as a function of decreasing pore size (5.6-1.7 nm). This is a consequence of steric congestion in the pores that is magnified at the smaller pore sizes, consistent with parallel studies conducted using a conventional silylating reagent, 1,1,3,3-tetramethyldisilazane. Pyrolysis of the silica-immobilized DPP revealed that pore confinement leads to enhanced rates and altered product selectivity for this free-radical reaction compared with the nonporous silica, and the rates and selectivities also depended on pore size. The influence of confinement is discussed in terms of enhanced encounter frequencies for bimolecular reaction steps and pore surface curvature that alters the accessibility and resultant selectivity for hydrogen transfer steps.

13C NMR characterization of the organic constituents in ligand-modified hexagonal mesoporous silicas: media for the synthesis of small, uniform-size gold nanoparticles.

This paper reports the (13)C NMR characterization of functionalized MCM-41's and describes the chemistry that occurs in the pores of these materials in the process of forming gold nanoparticles. Nanoparticles formed on hexagonal mesoporous silica (MCM-41) by hydrogen reduction of chloroauric acid have little affinity for pure silica surfaces. The gold can be removed from the support with very mild treatment, for example, solvent extraction. The loss of gold from the substrate can be prevented using a pore functionalization methodology that entails synthesis of the silica containing polydentate amine functionality chemically bound in the mesopores. The synthetic scheme introduces solvents and templating reagents (surfactants) into the mesopores that are chemically reactive under the conditions required for gold particle formation. Extensive base-catalyzed elimination and nucleophilic substitution reactions involving the tetraalkylammonium surfactant occur during the reduction of chloroauric acid to gold.