Ethanol and Water Adsorption in Conventional and Hierarchical All-Silica MFI Zeolites.

Hierarchical zeolites containing both micro- (<2 nm) and mesopores (2-50 nm) have gained increasing attention in recent years because they combine the intrinsic properties of conventional zeolites with enhanced mass transport rates due to the presence of mesopores. The structure of the hierarchical self-pillared pentasil (SPP) zeolite is of interest because all-silica SPP consists of orthogonally intergrown single-unit-cell MFI nanosheets and contains hydrophilic surface silanol groups on the mesopore surface while its micropores are nominally hydrophobic. Therefore, the distribution of adsorbed polar molecules, like water and ethanol, in the meso- and micropores is of fundamental interest. Here, molecular simulation and experiment are used to investigate the adsorption of water and ethanol on SPP. Vapor-phase single-component adsorption shows that water occupies preferentially the mesopore corner and surface regions of the SPP material at lower pressures (P/P 0 < 0.5) while loading in the mesopore interior dominates adsorption at higher pressures. In contrast, ethanol does not exhibit a marked preference for micro- or mesopores at low pressures. Liquid-phase adsorption from binary water-ethanol mixtures demonstrates a 2 orders of magnitude lower ethanol/water selectivity for the SPP material compared to bulk MFI. For very dilute aqueous solutions of ethanol, the ethanol molecules are mostly adsorbed inside the SPP micropore region due to stronger dispersion interactions and the competition from water for the surface silanols. At high ethanol concentrations (C EtOH > 700 g L-1), the SPP material becomes selective for water over ethanol.

Catalyst-Enabled In Situ Linkage Reduction in Imine Covalent Organic Frameworks.

New linkages for covalent organic frameworks (COFs) have been continuously pursued by chemists as they serve as the structure and property foundation for the materials. Developing new reaction types or modifying known linkages have been the only two methods to create new COF linkages. Herein, we report a novel strategy that uses H3PO3 as a bifunctional catalyst to achieve amine-linked COFs from readily available amine and aldehyde linkers. The acidic proton of H3PO3 catalyzes the imine framework formation, which is then in situ reduced to the amine COF by the reductive P-H moiety. The amine-linked COF outperforms its imine analogue in promoting Knoevenagel condensation because of the more basic sites and higher stability.

Porosity, Powder X-Ray Diffraction Patterns, Skeletal Density, and Thermal Stability of NIST Zeolitic Reference Materials RM 8850, RM 8851, and RM 8852.

This paper reports the powder X-ray diffraction patterns, argon isotherms at 87 K, Brunauer-Emmett-Teller surface areas, pore size distributions, pore volumes, skeletal densities, and thermal gravimetric analyses for three National Institute of Standards and Technology zeolitic reference materials, RM 8850 (zeolite Y), RM 8851 (zeolite A), and RM 8852 (ZSM-5).

Vapor- and Liquid-Phase Adsorption of Alcohol and Water in Silicalite-1 Synthesized in Fluoride Media.

In this work, batch-adsorption experiments and molecular simulations are employed to probe the adsorption of binary mixtures containing ethanol or a linear alkane-1,n-diol solvated in water or ethanol onto silicate-1. Since the batch-adsorption experiments require an additional relationship to determine the amount of solute (and solvent adsorbed, as only the bulk liquid reservoir can be probed directly, molecular simulations are used to provide a relationship between solute and solvent adsorption for input to the experimental bulk measurements. The combination of bulk experimental measurements and simulated solute-solvent relationship yields solvent and solute loadings that are self-consistent with simulation alone, and allow for an assessment of the various assumptions made in literature. At low solution concentrations, the solute loading calculated is independent of the assumption made. At high concentrations, a negligent choice of assumption can lead to systematic overestimation or underestimation of calculated solute loading.

Experimental aspects of buoyancy correction in measuring reliable highpressure excess adsorption isotherms using the gravimetric method.

Addressing reproducibility issues in adsorption measurements is critical to accelerating the path to discovery of new industrial adsorbents and to understanding adsorption processes. A National Institute of Standards and Technology Reference Material, RM 8852 (ammonium ZSM-5 zeolite), and two gravimetric instruments with asymmetric two-beam balances were used to measure high-pressure adsorption isotherms. This work demonstrates how common approaches to buoyancy correction, a key factor in obtaining the mass change due to surface excess gas uptake from the apparent mass change, can impact the adsorption isotherm data. Three different approaches to buoyancy correction were investigated and applied to the subcritical CO2 and supercritical N2 adsorption isotherms at 293 K. It was observed that measuring a collective volume for all balance components for the buoyancy correction (helium method) introduces an inherent bias in temperature partition when there is a temperature gradient (i.e. analysis temperature is not equal to instrument air bath temperature). We demonstrate that a blank subtraction is effective in mitigating the biases associated with temperature partitioning, instrument calibration, and the determined volumes of the balance components. In general, the manual and subtraction methods allow for better treatment of the temperature gradient during buoyancy correction. From the study, best practices specific to asymmetric two-beam balances and more general recommendations for measuring isotherms far from critical temperatures using gravimetric instruments are offered.

Photoacoustic spectrometer with a calculable cell constant for measurements of gases and aerosols.

We benchmark the performance of a photoacoustic spectrometer with a calculable cell constant in applications related to climate change measurements. As presently implemented, this spectrometer has a detection limit of 3.1 × 10(-9) W cm(-1) Hz(-1/2) for absorption by a gas and 1.5 × 10(-8) W cm(-1) Hz(-1/2) for soot particles. Nonstatistical uncertainty limited the accuracy of the instrument to ∼1%, and measurements of the concentration of CO(2) in laboratory air agreed with measurements made using a cavity ring-down spectrometer, to within 1%. Measurements of the enhanced absorption resulting from ultrathin (<5 nm), nonabsorbing coatings on nanoscale soot particles demonstrate the sensitivity of this instrument. Together, these measurements show the instrument's ability to quantitatively measure the absorption coefficient for species of interest to the climate and atmospheric science communities. Because the system constant is known, in most applications the acoustic response of this instrument need not be calibrated against a sample of known optical density, a decided advantage in field applications. Routine enhancements, such as improved processing of the photoacoustic signal and higher laser beam power, should further increase the instrument's precision and sensitivity.

Tracing electronic pathways in molecules by using inelastic tunneling spectroscopy.

Using inelastic electron tunneling spectroscopy (IETS) to measure the vibronic structure of nonequilibrium molecular transport, aided by a quantitative interpretation scheme based on Green's function-density functional theory methods, we are able to characterize the actual pathways that the electrons traverse when moving through a molecule in a molecular transport junction. We show that the IETS observations directly index electron tunneling pathways along the given normal coordinates of the molecule. One can then interpret the maxima in the IETS spectrum in terms of the specific paths that the electrons follow as they traverse the molecular junction. Therefore, IETS measurements not only prove (by the appearance of molecular vibrational frequencies in the spectrum) that the tunneling charges, in fact, pass through the molecule, but also can be used to determine the transport pathways and how they change with the geometry and placement of molecules in junctions.

Structural and chemical characterization of monofluoro-substituted oligo(phenylene-ethynylene) thiolate self-assembled monolayers on gold.

Monolayers of oligo(phenylene-ethynylene) (OPE) molecules have exhibited promise in molecular electronic test structures. This paper discusses films formed from a novel molecule within this class, 2-fluoro-4-phenylethynyl-1-[(4-acetylthio)phenylethynyl]benzene (F-OPE). The conditions of self-assembled monolayer (SAM) formation were systematically altered to fabricate reproducible high-quality molecular monolayers from the acetate-protected F-OPE molecule. Detailed characterization of the F-OPE monolayers was performed by using an array of surface probes, including reflection absorbance infrared spectroscopy (RAIRS), contact angle (CA) measurements, spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and atomic force microscopy (AFM). XPS and RAIRS established that the SAM formed without removal of the F substituent and without oxidation of the thiol. The monolayer thickness, determined from SE and AFM based nanolithography, was consistent with the formation of a densely packed monolayer. The valence electronic structure of the SAM was consistent with an aromatic structure shifted by the electron-withdrawing fluorine substituent and intermolecular coupling within an oriented array of molecules.

Valence electron orbitals of an oligo(p-phenylene-ethynylene)thiol on gold.

This communication reports measurement of one-photon (21.2 eV) and one-color, two-photon (3.2-4.5 eV) photoemission spectra of 4,4'-bis-(phenylethynyl)benzenethiol chemisorbed on gold. Four features are observed in these spectra: two occupied, predominantly molecular levels below the Fermi level and two unoccupied, predominantly molecular levels above the Fermi level. The occupied and unoccupied bands closest to the Fermi level are assigned to delocalized pi-bands, and the other occupied and unoccupied bands, to localized pi-bands. With this assignment, the hole- and electron-injection barriers and the transport gap for those levels are deduced.