Ising-like antiferromagnetism on the octahedral sublattice of a cobalt-containing garnet and the potential for quantum criticality

In this contribution, we report that CaY2Co2Ge3O12 exhibits an unusual anisotropic and chainlike antiferromagnetic arrangement of spins despite crystallizing in the highly symmetric garnet structure. Using low-temperature powder neutron diffraction and symmetry analysis, we identify a magnetic structure consisting of chainlike motifs oriented along the body diagonals of the cubic unit cell with moments pointing parallel to the chain direction due to the strong Ising character of the Co ions. Antiferromagnetic order sets in below 6 K and exhibits both temperature- and field-induced magnetic transitions at high fields. Combining the results, we present a magnetic phase diagram that suggests CaY2Co2Ge3O12 undergoes a quantum phase transition at low temperatures and moderate fields

An assessment of strategies for the development of solid-state adsorbents for vehicular hydrogen storage

Nanoporous adsorbents are a diverse category of solid-state materials that hold considerable promise for vehicular hydrogen storage. Although impressive storage capacities have been demonstrated for several materials, particularly at cryogenic temperatures, materials meeting all of the targets established by the U.S. Department of Energy have yet to be identified. In this Perspective, we provide an overview of the major known and proposed strategies for hydrogen adsorbents, with the aim of guiding ongoing research as well as future new storage concepts. The discussion of each strategy includes current relevant literature, strengths and weaknesses, and outstanding challenges that preclude implementation. We consider in particular metal-organic frameworks (MOFs), including surface area/volume tailoring, open metal sites, and the binding of multiple H2 molecules to a single metal site. Two related classes of porous framework materials, covalent organic frameworks (COFs) and porous aromatic frameworks (PAFs), are also discussed, as are graphene and graphene oxide and doped porous carbons. We additionally introduce criteria for evaluating the merits of a particular materials design strategy. Computation has become an important tool in the discovery of new storage materials, and a brief introduction to the benefits and limitations of computational predictions of H2 physisorption is therefore presented. Finally, considerations for the synthesis and characterization of hydrogen storage adsorbents are discussed

Thermodynamics of Methane Adsorption on Copper HKUST-1 at Low Pressure

Metal-organic frameworks (MOFs) can be engineered as natural gas storage materials by tuning the pore structures and surface properties. Here we report the direct measurement of CH4 adsorption enthalpy on a paddlewheel MOF (Cu HKUST-1) using gas adsorption calorimetry at 25 °C at low pressures (below 1 bar). In this pressure region, the CH4-CH4 intermolecular interactions are minimized and the energetics solely reflects the CH4-MOF interactions. Our results suggest moderately exothermic physisorption with an enthalpy of -21.1 ± 1.1 kJ/mol CH4 independent of coverage. This calorimetric investigation complements previous computational and crystallographic studies by providing zero coverage enthalpies of CH4 adsorption. The analysis of the new and literature data suggests that in initial stages of adsorption the CH4-HKUST-1 interaction tends to be more sensitive to the pore dimension than to the guest polarizability, suggesting a less specific chemical binding role for the open Cu site