A bottom-up
chemical synthesis of metal–organic frameworks
(MOFs) permits significant structural diversity because of various
combinations of metal centers and different organic linkers. However,
fabrication generally complies with the classic hard and soft acids
and bases (HSAB) theory. This restricts direct synthesis of desired
MOFs with converse Lewis type of metal ions and ligands. Here we present
a top-down strategy to break this limitation via the structural cleavage
of MOFs to trigger a phase transition using a novel “molecular
scalpel”. A conventional CuBDC MOF (BDC = 1,4-benzenedicarboxylate)
prepared from a hard acid (Cu2+) metal and a hard base
ligand was chemically cleaved by l-ascorbic acid acting as
chemical scalpel to fabricate a new Cu2BDC structure composed
of a soft acid (Cu1+) and a hard base (BDC). Controlled
phase transition was achieved by a series of redox steps to regulate
the chemical state and coordination number of Cu ions, resulting in
a significant change in chemical composition and catalytic activity.
Mechanistic insights into structural cleavage and rearrangement are
elaborated in detail. We show this novel strategy can be extended
to general Cu-based MOFs and supramolecules for nanoscopic casting
of unique architectures from existing ones.
Cr/W multilayer nanocomposites were presented in the paper as potential candidate materials for the plasma facing components in fusion reactors. We used neutron reflectometry to measure the depth profile of helium in the multienergy He ions irradiated [Cr/W (50 nm)]3 multilayers. Results showed that He-rich layers with low neutron scattering potential energy form at the Cr/W interfaces, which is in great agreement with previous modeling results of other multilayers. This phenomenon provided a strong evidence for the He trapping effects of Cr/W interfaces and implied the possibility of using the Cr/W multilayer nanocomposites as great He-tolerant plasma facing materials.
Antiferromagnetic topological insulator (AFTI) is a topological matter that breaks time-reversal symmetry. Since its proposal, explorations of AFTI in strong-correlated systems are still lacking. In this paper, we show for the first time that a novel AFTI phase can be realized in three-dimensional topological Kondo insulator (TKI). In a wide parameter region, the ground states of TKI undergo a second-order transition to antiferromagnetic insulating phases which conserve a combined symmetry of time reversal and a lattice translation, allowing us to derive a [Formula: see text]-classification formula for these states. By calculating the [Formula: see text] index, the antiferromagnetic insulating states are classified into AFTI or non-topological antiferromagnetic insulator (nAFI) in different parameter regions. On the antiferromagnetic surfaces in AFTI, we find topologically protected gapless Dirac cones inside the bulk gap, leading to metallic Fermi rings exhibiting helical spin texture with weak spin-momentum locking. Depending on model parameters, the magnetic transitions take place either between AFTI and strong topological insulator, or between nAFI and weak topological insulator. By varying some model parameters, we find a topological transition between AFTI and nAFI, driving by closing of bulk gap. Our work may account for the pressure-induced magnetism in TKI compound SmB, and helps to explore richer AFTI phases in heavy-fermion systems as well as in other strong-correlated systems.
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