The solid-solution metal oxide (NiMgCuZnCo)O is the first known high-entropy (HE) metal oxide synthesized, forming a poster child of the emerging high-entropy oxide materials, which is derived from high-temperature synthesis methodologies (>900 °C). In this work, we report the mechanochemical synthesis of this known HE metal oxide (NiMgCuZnCo)O under ambient conditions. The advantage of this approach was further demonstrated by the introduction of up to 5 wt % noble metal into (NiMgCuZnCo)O, as single atoms or nanoclusters, which showed good stability at high temperature and produced a high catalytic activity in the hydrogenation of atmospheric CO 2 to CO. The latter work demonstrated the unique advantage of using HE materials to disperse catalysis centers.
Understanding
the nature of phonon transport in solids and the
underlying mechanism linking lattice dynamics and thermal conductivity
is important in many fields, including the development of efficient
thermoelectric materials where a low lattice thermal conductivity
is required. Herein, we choose the pair of synthetic chalcopyrite
CuFeS2 and talnakhite Cu17.6Fe17.6S32 compounds, which possess the same elements and very
similar crystal structures but very different phonon transport, as
contrasting examples to study the influence of lattice dynamics and
chemical bonding on the thermal transport properties. Chemically,
talnakhite derives from chalcopyrite by inserting extra Cu and Fe
atoms in the chalcopyrite lattice. The CuFeS2 compound
has a lattice thermal conductivity of 2.37 W m–1 K–1 at 625 K, while Cu17.6Fe17.6S32 features Cu/Fe disorder and possesses an extremely
low lattice thermal conductivity of merely 0.6 W m–1 K–1 at 625 K, approaching the amorphous limit
κmin. Low-temperature heat capacity measurements
and phonon calculations point to a large anharmonicity and low Debye
temperature in Cu17.6Fe17.6S32, originating
from weaker chemical bonds. Moreover, Mössbauer spectroscopy
suggests that the state of Fe atoms in Cu17.6Fe17.6S32 is partially disordered, which induces the enhanced
alloy scattering. All of the above peculiar features, absent in CuFeS2, contribute to the extremely low lattice thermal conductivity
of the Cu17.6Fe17.6S32 compound.
To treat impairments in hard tissues or overcome pathological calcification in soft tissues, a detailed understanding of mineralization pathways of calcium phosphate materials is needed. Here, we report a detailed mechanistic study of hydroxyapatite (HA) mineralization pathways in an artificial saliva solution via in situ liquid cell transmission electron microscopy (TEM). It is found that the mineralization of HA starts by forming ion-rich and ion-poor solutions in the saliva solution, followed by coexistence of the classical and nonclassical nucleation processes. For the nonclassical path, amorphous calcium phosphate (ACP) functions as the substrate for HA nucleation on the ACP surface, while the classical path features direct HA nucleation from the solution. The growth of HA crystals on the surface of ACP is accompanied by the ACP dissolution process. The discoveries reported in this work are important to understand the physiological and pathological formation of HA minerals, as well as to engineer the biomineralization process for bone healing and hard tissue repairs.
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