William R. Woerner

Mechanism of Carbon Dioxide Adsorption in a Highly Selective Coordination Network Supported by Direct Structural Evidence

Understanding the interactions between adsorbed gas molecules and a pore surface at molecular level is vital to exploration and attempts at rational development of gasselective nanoporous solids. Much current work focuses on the design of functionalized metal–organic frameworks (MOFs) or coordination networks (CNs) that selectively adsorb CO2. [1–9] While interactions between CO2 molecules and the p clouds of aromatic linkers in MOFs under ambient conditions have been explored theoretically, no direct structure evidence of such interactions are reported to date. Here we provide the first structural insight of such interactions in a porous calcium based CN using single-crystal X-ray diffraction methods, supported by powder diffraction coupled with differential scanning calorimetry (DSC-XRD), in situ IR/Raman spectroscopy, and molecular simulation data. We further postulate that such interactions are responsible for the high CO2/N2 adsorption selectivity, even in the case of a high relative humidity (RH). Our data suggest that the key interaction responsible for such selectivity, the room-temperature stability and the relative insensitivity to the RH of the CO2-CN adduct, is between two phenyl rings of the linker in the CN and the molecular quadrupole of CO2. The specific geometry of the linker molecule results in a “pocket” where carbon from the CO2 molecule is placed between two centroids of the aromatic ring. Our experimental confirmation of this variation on theoretically postulated interactions between CO2 and a phenyl ring will promote the search for other CNs containing phenyl ring pockets. Selective adsorption and sequestration of CO2 from sources of anthropogenic emissions, such as untreated waste from flue gas and products of the water gas shift reaction, is important to mitigate the growing level of atmospheric CO2. [10] Current separation methods use absorption in alkanolamine solutions, which are toxic, corrosive, and require significant energy for their regeneration. Hence microporous solid-state adsorbents, such as zeolites, hybrid zeolite–polymer systems, porous organic materials, and MOFs are proposed as alternatives, especially in combination with pressure swing processes. Rather than relying solely on tuning the pore diameters of microporous materials to select between gases based on size (the kinetic diameters of CO2, CH4 and N2 are 3.30, 3.76 3.64 , respectively ) selective separation relies on differences in electronic properties, such as the quadrupole moment and polarizability. Attempts to produce MOFs or CNs with adsorption properties competitive with those of commercially established aluminosilicate zeolites, relies on strategies that include pore surface modification with strongly polarizing functional groups, such as amines 7, 9,15] and desolvating metals centers 8, 16] to produce low-coordinated sites suitable for CO2 adsorption. The amine-functionalized materials offer a high selectivity toward CO2 adsorption, but a low effective surface area and thus, a low total uptake capacity. Strong interactions with polarizing functional groups, as well as with open metal sites presents other drawbacks including an increase in the costs for material regeneration. Furthermore, water effectively competes with CO2 at low-coordinated cation sites, impeding the performance of frameworks in commercial flue gas. We recently described a porous framework, CaSDB (SDB: sulfonyldibenzoate, compound 1) with a high CO2/N2 selectivity. At 0.15 bar of CO2 and 0.85 bar of N2, a typical composition of flue gas mixture from power plants, the selectivity is in the range of 48 to 85 at 298 K. CaSDB shows a reversible uptake of CO2 of 5.75 wt% at 273 K and 1 bar pressure and 4.37 wt% at room temperature, with heats of adsorption for CO2 and N2 of 31 and 19 kJmol , respectively. The as-synthesized compound contains not coordinated water molecules and is easily activated for gas adsorption by heating to 563 K in vacuum; remarkably the activated framework does not readsorb water, even if exposed to a RH greater than [*] A. M. Plonka, W. R. Woerner, Prof. Dr. J. B. Parise Department of Geosciences, Stony Brook University Stony Brook, NY 11794-2100 (USA) E-mail: john.parise@stonybrook.edu

From 1D Chain to 3D Network: A New Family of Inorganic–Organic Hybrid Semiconductors MO3(L)x (M = Mo, W; L = Organic Linker) Built on Perovskite-like Structure Modules

MO3 (M = Mo, W) or VI-VI binary compounds are important semiconducting oxides that show great promise for a variety of applications. In an effort to tune and enhance their properties in a systematic manner we have applied a designing strategy to deliberately introduce organic linker molecules in these perovskite-like crystal lattices. This approach has led to a wealth of new hybrid structures built on one-dimensional (1D) and two-dimensional (2D) VI-VI modules. The hybrid semiconductors exhibit a number of greatly improved properties and new functionality, including broad band gap tunability, negative thermal expansion, largely reduced thermal conductivity, and significantly enhanced dielectric constant compared to their MO3 parent phases.

Effect of ligand geometry on selective gas-adsorption: the case of a microporous cadmium metal organic framework with a V-shaped linker.

A microporous cadmium metal organic framework is synthesized and structurally characterized. The material possesses a 3-D framework with a 1-D sinusoidal chain and shows high selectivity for CO2 over N2. The selectivity is attributed to CO2 interacting with two phenyl rings of a V-shaped linker as estimated by the in situ XRD-DSC study.

Maskelynite formation via solid-state transformation: Evidence of infrared and X-ray anisotropy

We present the results of a combined study of shocked labradorite from the Lonar crater, India, using optical microscopy, micro-Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, high-energy X-ray total scattering experiments, and micro-Fourier transform infrared (micro-FTIR) spectroscopy. We show that maskelynite of shock class 2 is structurally more similar to fused glass than to crystalline plagioclase. However, there are slight but significant differences—preservation of original preimpact igneous zoning, anisotropy at infrared wavelengths, X-ray anisotropy, and preservation of some intermediate range order—which are all consistent with a solid-state transformation from plagioclase to maskelynite.

Solid solution in the fluorapatite-chlorapatite binary system: High-precision crystal structure refinements of synthetic F-Cl apatite

Abstract Apatite sensu lato, Ca10(PO4)6(F,OH,Cl)2, is the tenth most abundant mineral on Earth, and is fundamentally important in geological processes, biological processes, medicine, dentistry, agriculture, environmental remediation, and material science. The steric interactions among anions in the [0,0,z] anion column in apatite make it impossible to predict the column anion arrangements in solid solutions among the three end-members. In this work we report the measured atomic arrangements of synthetic apatite in the F-Cl apatite binary with nominal composition Ca10(PO4)6(F1Cl1), synthesized in vacuum at high temperature to minimize both hydroxyl- and oxy-component of the apatite. Four crystals from the high-temperature synthesis batch were prepared to assess the homogeneity of the batch and the precision of the location of small portions of an atom in the apatite anion column by single-crystal X-ray diffraction techniques. Crystals were ground to spheres of 80 μm diameter, and full-spheres of MoKα diffraction data were collected to θ = 33°, with average redundancies >16. Final R1 values ranged from 0.0145 to 0.0158; the lattice parameters ranged from a = 9.5084(2)-9.5104(3), c = 6.8289(3)-6.8311(2) Å. Based on this study, solid solution in P63/m apatites along the F-Cl join is attained by creation of an off-mirror fluorine site at (0,0,0.167), a position wherein the fluorine atom relaxes away from its normal position within the {00l} mirror plane in P63/m apatites; that relaxation is coupled with relaxation of a chlorine atom at the adjacent mirror plane away from the off-mirror fluorine, allowing acceptable F-Cl distances in the anion column. There are a total of four partially occupied anion positions in the anion column, including two for fluorine [(0,0,1/4) and (0,0,0.167)] and two for chlorine [(0,0,0.086) and (0,0,0)]; the chlorine site at the origin was previously postulated but not observed in calcium apatite solid solutions.

A novel technique for fluorapatite synthesis and the thermodynamic mixing behavior of F-OH apatite crystalline solutions

Abstract Successful synthesis of fluorapatite has been achieved through ion-exchange between NIST hydroxlyapatite SRM 2910a and optical-grade fluorite. Additional intermediate F-OH apatite compositions were made through ion-exchange between the newly synthesized fluorapatite and the original hydroxylapatite. Based on solution calorimetric data collected on seven fluorapatite-hydroxlyapatite crystalline solutions at 50 °C in 20.0 wt% HCl under isoperibilic conditions, fluorine-rich series members display ideal thermodynamic behavior, whereas hydroxyl-rich compositions show negative enthalpies of F-OH mixing. Unit-cell volumes for the series are linear with composition. Relative to enthalpy and volume, therefore, there are no energy barriers to complete solid solution between the F and OH end-members.

Photocatalytic hydrogen evolution using nanocrystalline gallium oxynitride spinel

Photocatalytic hydrogen evolution from water was observed over nanocrystalline gallium oxynitride spinel under simulated solar light irradiation (320 nm < λ < 800 nm). Up to 8 μmol h−1 of H2 was evolved without co-catalyst loading. The photocatalyst was synthesized by the ammonolysis of gallium nitrate hydrate (Ga(NO3)3·xH2O). Optical measurements indicate an indirect gap (Eg) in the visible region (Eg = 2.50 eV) which is ascribed to photoexcitations from the N 2p valence states. A direct gap has an onset at ultraviolet energies (Eg = 3.69 eV), which is ascribed to photoexcitations from lower energy O 2p valence states.

Optical constants of synthetic potassium, sodium, and hydronium jarosite

Abstract The hydroxy sulfate jarosite [(K,Na,H3O)Fe3(SO4)2(OH)6] has both been discovered on Mars, and is associated with areas of highly acidic runoff on Earth. Because jarosite is extremely sensitive to formation conditions, it is an important target mineral for remote sensing applications. Yet at visible and near infrared (VNIR) wavelengths, where many spacecraft spectrometers collect data, the spectral abundance of a mineral in a mixture is not linearly correlated with the surface abundance of that mineral. Radiative transfer modeling can be used to extract quantitative abundance estimates if the optical constants (the real and imaginary indices of refraction, n and k) for all minerals in the mixture are known. Unfortunately, optical constants for a wide variety of minerals, including sulfates like jarosite, are not available. This is due, in part, to the inherent difficulty in obtaining such data for minerals that tend to crystallize naturally as fine-grained (~10 μm) powders, like many sulfates including jarosite. However, the optical constants of powders can be obtained by inverting the equation of radiative transfer and using it to model laboratory spectra. In this paper, we provide robust n and k data for synthetic potassium, hydronium, and sodium jarosite in the VNIR. We also explicitly describe the calculation procedures (including access to our Matlab code) so that others may obtain optical constants of additional minerals. Expansion of the optical constants library in the VNIR will facilitate the extraction of quantitative mineral abundances, leading to more in-depth evaluations of remote sensing target locations.

Combined Theoretical and in Situ Scattering Strategies for Optimized Discovery and Recovery of High-Pressure Phases: A Case Study of the GaN–Nb2O5 System

The application of pressure in solid-state synthesis provides a route for the creation of new and exciting materials. However, the onerous nature of high-pressure techniques limits their utility in materials discovery. The systematic search for novel oxynitrides-semiconductors for photocatalytic overall water splitting-is a representative case where quench high-pressure synthesis is useful and necessary in order to obtain target compounds. We utilize state of the art crystal structure prediction theory (USPEX) and in situ synchrotron-based X-ray scattering to speed up the discovery and optimization of novel compounds using high-pressure synthesis. Using this approach, two novel oxynitride phases were discovered in the GaN-Nb2O5 system. The (Nb2O5)0.84:(NbO2)0.32:(GaN)0.82 rutile structured phase was formed at 1 GPa and 900 °C and gradually transformed to a α-PbO2-related structure above 2.8 GPa and 1000 °C. The low-pressure rutile type phase was found to have a direct optical band gap of 0.84 eV and an indirect gap of 0.51 eV.

Unexpected visible light driven photocatalytic activity without cocatalysts and sacrificial reagents from a (GaN)1–x(ZnO)x solid solution synthesized at high pressure over the entire composition range

Optical and photocatalytic properties were determined for the solid solution series (GaN)1–x(ZnO)x synthesized at high pressure over the entire compositional range (x = 0.07 to 0.9). We report for the first time photocatalytic H2 evolution activity from water for (GaN)1–x(ZnO)x without cocatalysts, pH modifiers and sacrificial reagents. Syntheses were carried out by reacting GaN and ZnO in appropriate amounts at temperatures ranging from 1150 to 1200 °C, and at a pressure of 1 GPa. ZnGa2O4 was observed as a second phase, with the amount decreasing from 12.8 wt% at x = 0.07 to ∼0.5 wt% at x = 0.9. The smallest band gap of 2.65 eV and the largest average photocatalytic H2 evolution rate of 2.31 μmol h−1 were observed at x = 0.51. Samples with x = 0.07, 0.24 and 0.76 have band gaps of 2.89 eV, 2.78 eV and 2.83 eV, and average hydrogen evolution rates of 1.8 μmol h−1, 0.55 μmol h−1 and 0.48 μmol h−1, respectively. The sample with x = 0.9 has a band gap of 2.82 eV, but did not evolve hydrogen. An extended photocatalytic test showed considerable reduction of activity over 20 hours.