Kinetic Control via Binding Sites within the Confined Space of Metal Metalloporphyrin-Frameworks for Enhanced Shape-Selectivity Catalysis.

One striking feature of enzyme is its controllable ability to trap substrates via synergistic or cooperative binding in the enzymatic pocket, which renders the shape-selectivity of product by the confined spatial environment. The success of shape-selective catalysis relies on the ability of enzyme to tune the thermodynamics and kinetics for chemical reactions. In emulation of enzyme's ability, we showcase herein a targeting strategy with the substrate being anchored on the internal pore wall of metal-organic frameworks (MOFs), taking full advantage of the sterically kinetic control to achieve shape-selectivity for the reactions.

Calcium vapor synthesis of extremely coercive SmCo.

Exceptionally coercive SmCo particles are produced through calcium vapor reduction of SmCoO powders synthesized by flame spray pyrolysis. The resulting powders are composed of oblate hexagonal particles approximately 2 microns across with smooth surfaces. This microstructure yields record-breaking room temperature coercivity >80 kOe, or >60 kOe when combined with advanced manufacturing approaches such as electrophoretic deposition or molding with tetraglyme inks.

Understanding Hydrogenation Chemistry at MgB Reactive Edges from Molecular Dynamics.

Solid-state hydrogen storage materials often operate via transient, multistep chemical reactions at complex interfaces that are difficult to capture. Here, we use direct molecular dynamics simulations at accelerated temperatures and hydrogen pressures to probe the hydrogenation chemistry of the candidate material MgB without assumption of reaction pathways. Focusing on highly reactive (101̅0) edge planes where initial hydrogen attack is likely to occur, we track mechanistic steps toward the formation of hydrogen-saturated BH units and key chemical intermediates, involving H dissociation, generation of functionalities and molecular complexes containing BH and BH motifs, and B-B bond breaking.

Synthesis, Magnetic Properties, and Electronic Structure of Magnetic Topological Insulator MnBiSe.

The intrinsic magnetic topological insulators MnBiTe and MnBiSe support novel topological states related to symmetry breaking by magnetic order. Unlike MnBiTe, the study of MnBiSe has been inhibited by the lack of bulk crystals, as the van der Waals (vdW) crystal is not the thermodynamic equilibrium phase. Here, we report the layer-by-layer synthesis of vdW MnBiSe crystals using nonequilibrium molecular beam epitaxy.

Suppression of low temperature magnetic ordering in samarium nanoparticles.

The role of finite size effects on magnetic order has been investigated in samarium nanoparticles prepared by physical vapor deposition. A dense layer composed of distinct nanoparticles with a mean particle diameter of 26 nm was deposited on a diamagnetic substrate. M(T) measurements identify the expected pair of antiferromagnetic ordering temperatures in the bulk Sm precursor, at 113 K and 14 K, where the magnetic unit cell for the lower ordering temperature is 10.

Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal-Organic Framework.

The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal-organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (ZrO(OH)(bpydc) with bpydc = 2,2'-bipyridine-5,5'-dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host.

Identifying the Role of Dynamic Surface Hydroxides in the Dehydrogenation of Ti-Doped NaAlH.

Solid-state metal hydrides are prime candidates to replace compressed hydrogen for fuel cell vehicles due to their high volumetric capacities. Sodium aluminum hydride has long been studied as an archetype for higher-capacity metal hydrides, with improved reversibility demonstrated through the addition of titanium catalysts; however, atomistic mechanisms for surface processes, including hydrogen desorption, are still uncertain. Here, operando and ex situ measurements from a suite of diagnostic tools probing multiple length scales are combined with ab initio simulations to provide a detailed and unbiased view of the evolution of the surface chemistry during hydrogen release.

Chemical Synthesis of Magnetically Hard and Strong Rare Earth Metal Based Nanomagnets.

We report a general chemical approach to synthesize strongly ferromagnetic rare-earth metal (REM) based SmCo and SmFeN nanoparticles (NPs) with ultra-large coercivity. The synthesis started with the preparation of hexagonal CoO+Sm O (denoted as SmCo-O) multipods via decomposition of Sm(acac) and Co(acac) in oleylamine. These multipods were further reduced with Ca at 850 °C to form SmCo NPs with sizes tunable from 50 to 200 nm.

Elucidating the mechanism of MgB initial hydrogenation via a combined experimental-theoretical study.

Mg(BH) is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB. Although several dehydrogenation pathways have been proposed, the hydrogenation process is less well understood.

Topological computation based on direct magnetic logic communication.

Non-uniform magnetic domains with non-trivial topology, such as vortices and skyrmions, are proposed as superior state variables for nonvolatile information storage. So far, the possibility of logic operations using topological objects has not been considered. Here, we demonstrate numerically that the topology of the system plays a significant role for its dynamics, using the example of vortex-antivortex pairs in a planar ferromagnetic film.

Three dimensional magnetic abacus memory.

Stacking nonvolatile memory cells into a three-dimensional matrix represents a powerful solution for the future of magnetic memory. However, it is technologically challenging to access the data in the storage medium if large numbers of bits are stacked on top of each other. Here we introduce a new type of multilevel, nonvolatile magnetic memory concept, the magnetic abacus.