CIT-7, a crystalline, molecular sieve with pores bounded by 8 and 10-membered rings

A new crystalline molecular sieve, denoted CIT-7, is synthesized using an imidazolium-based diquaternary organic structure directing agent (OSDA). The framework structure is determined from a combination of rotation electron diffraction and synchrotron X-ray powder diffraction data. The structure has 10 crystallographically unique tetrahedral atoms (T-atoms) in the unit cell, and can be described as an ordered arrangement of the [4^(2)5^(4)6^(2)] mtw building unit and a previously unreported [4^(4)5^(2)] building unit. The framework contains a 2-dimensional pore system that is bounded by 10 T-atom rings (10-ring, 5.1 Å × 6.2 Å opening) that are connected with oval 8-rings (2.9 Å × 5.5 Å opening) through medium-sized cavities (~7.9 Å) at the channel intersections. CIT-7 can be synthesized over a broad range of compositions including pure-silica and heteroatom, e.g., aluminosilicate and titanosilicate, containing variants

Second-Order Perturbation Theory in Continuum Quantum Monte Carlo Calculations

We report on the first results for the second-order perturbation theory correction to the ground-state energy of a nuclear many-body system in a continuum quantum Monte Carlo calculation. Second-order (and higher) perturbative corrections are notoriously difficult to compute in most \textit{ab~initio} many-body methods, where the focus is usually on obtaining the ground-state energy. By mapping our calculation of the second-order energy correction to an evolution in imaginary time using the diffusion Monte Carlo method, we are able to calculate these corrections for the first time. After benchmarking our method in the few-body sector, we explore the effect of charge-independence breaking terms in the nuclear Hamiltonian. We then employ the new approach to investigate the many-body, perturbative, order-by-order convergence that is fundamental in modern theories of the nucleon-nucleon interaction derived from chiral effective field theory. Our approach is quite general and promises to be of wide applicability.Comment: 6 pages, 3 figures, 1 tabl

Influence of Organic Structure Directing Agent Isomer Distribution on the Synthesis of SSZ-39

The aluminosilicate molecular sieve with the AEI framework topology (SSZ-39) is currently of great interest for use in a number of important applications such as exhaust gas NO_x reduction and the methanol-to-olefins reaction. It is likely that advances in the synthesis of this molecular sieve will be needed for applications to proceed. Here, dimethylpiperidine based organic structure directing agents (OSDAs) are used to prepare SSZ-39, and the influence of diastereo- and structural isomeric mixtures on the synthesis of SSZ-39 is reported. Although differences in the rates of molecular sieve formation as well as preferential isomer incorporation occur, the synthesis of SSZ-39 is possible over a wide range of isomeric mixtures. These findings demonstrate that the synthesis of SSZ-39 can be accomplished with OSDA isomer mixtures that naturally occur from the synthesis of the organic precursors used to prepare the OSDAs

Hydrodynamic electron flow and Hall viscosity

The authors acknowledge support from the Emergent Phenomena in Quantum Systems initiative of the Gordon and Betty Moore Foundation (T. S.) and NSF DMR-1507141 and a Simons Investigatorship (J. E. M.). We also acknowledge the support of the Max Planck Society and the UK Engineering and Physical Sciences Research Council under Grant No. EP/I032487/1.In metallic samples of small enough size and sufficiently strong momentum-conserving scattering, the viscosity of the electron gas can become the dominant process governing transport. In this regime, momentum is a long-lived quantity whose evolution is described by an emergent hydrodynamical theory. Furthermore, breaking time-reversal symmetry leads to the appearance of an odd component to the viscosity called the Hall viscosity, which has attracted considerable attention recently due to its quantized nature in gapped systems but still eludes experimental confirmation. Based on microscopic calculations, we discuss how to measure the effects of both the even and odd components of the viscosity using hydrodynamic electronic transport in mesoscopic samples under applied magnetic fields.PostprintPeer reviewe

Riparian vegetation, Colorado River, and climate: Five decades of spatiotemporal dynamics in the Grand Canyon with river regulation

Documentation of the interacting effects of river regulation and climate on riparian vegetation has typically been limited to small segments of rivers or focused on individual plant species. We examine spatiotemporal variability in riparian vegetation for the Colorado River in Grand Canyon relative to river regulation and climate, over the five decades since completion of the upstream Glen Canyon Dam in 1963. Long-term changes along this highly modified, large segment of the river provide insights for management of similar riparian ecosystems around the world. We analyze vegetation extent based on maps and imagery from eight dates between 1965 and 2009, coupled with the instantaneous hydrograph for the entire period. Analysis confirms a net increase in vegetated area since completion of the dam. Magnitude and timing of such vegetation changes are river stage-dependent. Vegetation expansion is coincident with inundation frequency changes and is unlikely to occur for time periods when inundation frequency exceeds approximately 5%. Vegetation expansion at lower zones of the riparian area is greater during the periods with lower peak and higher base flows, while vegetation at higher zones couples with precipitation patterns and decreases during drought. Short pulses of high flow, such as the controlled floods of the Colorado River in 1996, 2004, and 2008, do not keep vegetation from expanding onto bare sand habitat. Management intended to promote resilience of riparian vegetation must contend with communities that are sensitive to the interacting effects of altered flood regimes and water availability from river and precipitation. å©2015. American Geophysical Union. All Rights Reserved

High-silica, heulandite-type zeolites prepared by direct synthesis and topotactic condensation

There are both natural minerals and synthetic zeolites that possess the HEU framework topology. These materials have a limited compositional range (Si/Al < 6), and the natural zeolites often contain a large amount of impurities such as Fe^(3+). The preparation of impurity-free HEU-type zeolites with higher Si/Al ratio could open many areas of application, particularly in catalysis. Here, we report the first high-silica HEU-type zeolite that can be prepared via two different procedures. In the first method high-silica HEU (denoted CIT-8) is prepared using a topotactic condensation mechanism (layered precursor denoted CIT-8P); CIT-8P is obtained from a low-water synthesis in fluoride media. CIT-8 prepared in this manner has a product Si/Al ratio of 9.8 ± 0.7 and a micropore volume of 0.10 cm^3 g^(−1) (measured by nitrogen adsorption). The variable temperature powder X-ray diffraction shows that CIT-8 forms via topotactic condensation from CIT-8P along the b axis. Additionally, high-silica heulandite can be synthesized directly from a hydroxide-mediated reaction mixture (denoted CIT-8H), and has a Si/Al ratio of 6.4 ± 0.3 and a micropore volume of 0.10 cm^3 g^(−1). Both synthesis methods produce zeolites that expand the compositional range of HEU-type zeolites. These synthetic methods allow for the addition of other heteroatoms, and titanium-containing CIT-8 is prepared as an illustrative example

Facile Preparation of Aluminosilicate RTH across a Wide Composition Range Using a New Organic Structure-Directing Agent

RTH type zeolite (aluminosilicate) is a potentially useful catalytic material that is limited by the inability to easily prepare the material over a wide composition range. Here, we report the use of pentamethylimidazolium to prepare aluminosilicate RTH across a wide range of compositions in both fluoride and hydroxide inorganic systems. RTH type zeolites are crystallized with a calcined product Si/Al of 7–27 from fluoride media and 6–59 from hydroxide media. The use of this new, simple organic structure-directing agent that can be prepared in one step allows for dramatic improvement in the compositional space where aluminosilicate RTH can be formed. RTH is tested as a catalyst for the methanol-to-olefins reaction and at complete conversion shows a high propylene/ethylene ratio of 3.9 at a propylene selectivity of 43%

Enantiomerically enriched, polycrystalline molecular sieves

Zeolite and zeolite-like molecular sieves are being used in a large number of applications such as adsorption and catalysis. Achievement of the long-standing goal of creating a chiral, polycrystalline molecular sieve with bulk enantioenrichment would enable these materials to perform enantioselective functions. Here, we report the synthesis of enantiomerically enriched samples of a molecular sieve. Enantiopure organic structure directing agents are designed with the assistance of computational methods and used to synthesize enantioenriched, polycrystalline molecular sieve samples of either enantiomer. Computational results correctly predicted which enantiomer is obtained, and enantiomeric enrichment is proven by high-resolution transmission electron microscopy. The enantioenriched and racemic samples of the molecular sieves are tested as adsorbents and heterogeneous catalysts. The enantioenriched molecular sieves show enantioselectivity for the ring opening reaction of epoxides and enantioselective adsorption of 2-butanol (the R enantiomer of the molecular sieve shows opposite and approximately equal enantioselectivity compared with the S enantiomer of the molecular sieve, whereas the racemic sample of the molecular sieve shows no enantioselectivity)