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. For this purpose, a series of binding site-accessible metal metalloporphyrin-frameworks (MMPFs) have been investigated to shed light on the nature of enzyme-mimic catalysis. They exhibit a different density of binding sites that are well arranged into the nanospace with corresponding distances of opposite binding sites. Such a structural specificity results in a facile switch in selectivity from an exclusive formation of the thermodynamically stable product to the kinetic product. Thus, the proposed targeting strategy, based on the combination of porous materials and binding events, paves a new way to develop highly efficient heterogeneous catalysts for shifting selectivity.

Synthesis, Magnetic Properties, and Electronic Structure of Magnetic Topological Insulator MnBi2Se4.

The intrinsic magnetic topological insulators MnBi2Te4 and MnBi2Se4 support novel topological states related to symmetry breaking by magnetic order. Unlike MnBi2Te4, the study of MnBi2Se4 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 MnBi2Se4 crystals using nonequilibrium molecular beam epitaxy. Atomic-resolution scanning transmission electron microscopy and scanning tunneling microscopy identify a well-ordered vdW crystal with septuple-layer base units. The magnetic properties agree with the predicted layered antiferromagnetic ordering but disagree with its predicted out-of-plane orientation. Instead, our samples exhibit an easy-plane anisotropy, which is explained by including dipole-dipole interactions. Angle-resolved photoemission spectroscopy reveals the gapless Dirac-like surface state, which demonstrates that MnBi2Se4 is a topological insulator above the magnetic-ordering temperature. These studies show that MnBi2Se4 is a promising candidate for exploring rich topological phases of layered antiferromagnetic topological insulators.

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+Sm2 O3 (denoted as SmCo-O) multipods via decomposition of Sm(acac)3 and Co(acac)3 in oleylamine. These multipods were further reduced with Ca at 850 °C to form SmCo5 NPs with sizes tunable from 50 to 200 nm. The 200 nm SmCo5 NPs were dispersed in ethanol, and magnetically aligned in polyethylene glycol (PEG) matrix, yielding a PEG-SmCo5 NP composite with the room temperature coercivity (Hc ) of 49.2 kOe, the largest Hc among all ferromagnetic NPs ever reported, and saturated magnetic moment (Ms ) of 88.7 emu g-1 , the highest value reported for SmCo5 NPs. The method was extended to synthesize other ferromagnetic NPs of Sm2 Co17 , and, for the first time, of Sm2 Fe17 N3 NPs with Hc over 15 kOe and Ms reaching 127.9 emu g-1 . These REM based NPs are important magnetic building blocks for fabrication of high-performance permanent magnets, flexible magnets, and printable magnetic inks for energy and sensing applications.

Elucidating the mechanism of MgB2 initial hydrogenation via a combined experimental-theoretical study.

Mg(BH4)2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB2. Although several dehydrogenation pathways have been proposed, the hydrogenation process is less well understood. Here, we present a joint experimental-theoretical study that elucidates the key atomistic mechanisms associated with the initial stages of hydrogen uptake within MgB2. Fourier transform infrared, X-ray absorption, and X-ray emission spectroscopies are integrated with spectroscopic simulations to show that hydrogenation can initially proceed via direct conversion of MgB2 to Mg(BH4)2 complexes. The associated energy landscape is mapped by combining ab initio calculations with barriers extracted from the experimental uptake curves, from which a kinetic model is constructed. The results from the kinetic model suggest that initial hydrogenation takes place via a multi-step process: molecular H2 dissociation, likely at Mg-terminated MgB2 surfaces, is followed by migration of atomic hydrogen to defective boron sites, where the formation of stable B-H bonds ultimately leads to the direct creation of Mg(BH4)2 complexes without persistent BxHy intermediates. Implications for understanding the chemical, structural, and electronic changes upon hydrogenation of MgB2 are discussed.

Understanding Hydrogenation Chemistry at MgB2 Reactive Edges from Ab Initio 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 ab initio molecular dynamics simulations at accelerated temperatures and hydrogen pressures to probe the hydrogenation chemistry of the candidate material MgB2 without a priori 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 BH4- units and key chemical intermediates, involving H2 dissociation, generation of functionalities and molecular complexes containing BH2 and BH3 motifs, and B-B bond breaking. The genesis of higher-order boron clustering is also observed. Different charge states and chemical environments at the B-rich and Mg-rich edge planes are found to produce different chemical pathways and preferred speciation, with implications for overall hydrogenation kinetics. The reaction processes rely on B-H bond polarization and fluctuations between ionic and covalent character, which are critically enabled by the presence of Mg2+ cations in the nearby interphase region. Our results provide guidance for devising kinetic improvement strategies for MgB2-based hydrogen storage materials, while also providing a template for exploring chemical pathways in other solid-state energy storage reactions.

Calcium vapor synthesis of extremely coercive SmCo5.

Exceptionally coercive SmCo5 particles are produced through calcium vapor reduction of SmCo5O9 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 H c,i >80 kOe, or >60 kOe when combined with advanced manufacturing approaches such as electrophoretic deposition or molding with tetraglyme inks. These techniques enable straightforward low-loss fabrication of bulk parts. The high coercivity is extremely robust at elevated temperatures, exceeding 10 kOe even at 600 °C. The oxide precursor approach removes the need for strict environmental control during synthesis that is common to other nanoparticle-based routes and can readily be scaled to kilogram quantities of feedstock production. Magnet powders produced by calcium vapor reduction can thus function as the building blocks for traditional or advanced manufacturing techniques, while the high coercivity enables consistent performance across a wide range of temperatures.

Spontaneous dynamical disordering of borophenes in MgB2 and related metal borides.

Layered boron compounds have attracted significant interest in applications from energy storage to electronic materials to device applications, owing in part to a diversity of surface properties tied to specific arrangements of boron atoms. Here we report the energy landscape for surface atomic configurations of MgB2 by combining first-principles calculations, global optimization, material synthesis and characterization. We demonstrate that contrary to previous assumptions, multiple disordered reconstructions are thermodynamically preferred and kinetically accessible within exposed B surfaces in MgB2 and other layered metal diborides at low boron chemical potentials. Such a dynamic environment and intrinsic disordering of the B surface atoms present new opportunities to realize a diverse set of 2D boron structures. We validated the predicted surface disorder by characterizing exfoliated boron-terminated MgB2 nanosheets. We further discuss application-relevant implications, with a particular view towards understanding the impact of boron surface heterogeneity on hydrogen storage performance.

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 10.36 nm along the c-axis. The high temperature ordering of the hexagonal sites in the Sm nanocrystals is slightly decreased with respect to that of bulk Sm, while the low temperature transition associated with the cubic sites is significantly suppressed. The observed changes are attributed to finite size effects, with ordering suppressed as the particle radius approaches the length of the magnetic unit cell, and surface moments become more prominent.

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 (Zr6O4(OH)4(bpydc)6 with bpydc2- = 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. Notably, the B-, N-, and Mg-edge XAS data confirm the coordination of Mg(II) to the N atoms of the chelating bipyridine groups. In situ 11B MAS NMR studies helped elucidate the reaction mechanism and revealed that complete hydrogen release from Mg(BH4)2 occurs as low as 200 °C. Sieverts and thermogravimetric measurements indicate an increase in the rate of hydrogen release, with the onset of hydrogen desorption as low as 120 °C, which is approximately 150 °C lower than that of the bulk material. Furthermore, density functional theory calculations support the improved dehydrogenation properties and confirm the drastically lower activation energy for B-H bond dissociation.

Identifying the Role of Dynamic Surface Hydroxides in the Dehydrogenation of Ti-Doped NaAlH4.

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. In contrast to some previously proposed mechanisms, the titanium dopant does not directly facilitate desorption at the surface. Instead, oxidized surface species, even on well-protected NaAlH4 samples, evolve during dehydrogenation to form surface hydroxides with differing levels of hydrogen saturation. Additionally, the presence of these oxidized species leads to considerably lower computed barriers for H2 formation compared to pristine hydride surfaces, suggesting that oxygen may actively participate in hydrogen release, rather than merely inhibiting diffusion as is commonly presumed. These results demonstrate how close experiment-theory feedback can elucidate mechanistic understanding of complex metal hydride chemistry and potentially impactful roles of unavoidable surface impurities.

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. Utilising the dynamical properties and geometrical confinement, direct logic communication between the topological memory carriers is realised. This way, no additional magnetic-to-electrical conversion is required. More importantly, the information carriers can spontaneously travel up to ~300 nm, for which no spin-polarised current is required. The derived logic scheme enables topological spintronics, which can be integrated into large-scale memory and logic networks capable of complex computations.

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. Instead of storing information in individual magnetic layers, thereby having to read out each magnetic layer separately, the magnetic abacus adopts a new encoding scheme. It is inspired by the idea of second quantisation, dealing with the memory state of the entire stack simultaneously. Direct read operations are implemented by measuring the artificially engineered 'quantised' Hall voltage, each representing a count of the spin-up and spin-down layers in the stack. This new memory system further allows for both flexible scaling of the system and fast communication among cells. The magnetic abacus provides a promising approach for future nonvolatile 3D magnetic random access memory.