The structural phase
transition of synthetic ZnFe2O4 nanoparticles
(ZFO NPs) is investigated as a function of
pressure up to 40.6 GPa at room temperature for the first time, and
its associated intriguing electrical transport properties are resolved
from in situ impedance spectra and magnetoresistivity measurements.
Significant anomalies are observed in the properties of the grain
boundary resistance (R
gb), the relaxation
frequency (f
max), and the relative permittivity
(εr) in the ZFO NPs under the pressures around 17.5–21.5
GPa. These anomalies are believed to be correlated with a cubic-to-orthorhombic
phase transition of ZnFe2O4 at the pressures
between 21.9 and 25.7 GPa, which is found to be partially reversible.
The pressure-tuned dielectric properties are measured for the cubic
and the orthorhombic phases of ZFO, respectively. Remarkably, R
gb decreases up to 6 orders of magnitude as
a function of pressure in the cubic phase. The dielectric polarization
is obviously strengthened with increased f
max and decreased εr with pressure in the orthorhombic
phase. Furthermore, it is confirmed that the external pressure effectively
improves the electrochemical stability of the sample based on the
cycled measurements of the impedance spectra at various pressures.
The changes in the complex permittivity (ε′, ε″)
and the dielectric loss tangent (tan δ) with frequency
reveal the irreversible increase in the dielectric loss accompanied
by phase transition. The MR measurements indicate that ZFO NPs are
superparamagnetic under high pressure of up to 40 GPa. The transmission
electron microscopy images reflect the decrease in the grain boundary
number and some local amorphization of grains after compression, which
provides good explanations for the changes in the electrical transport
properties as a function of pressure. Herein, the structural and electrical
properties of ZnFe2O4 NPs generated are preserved
by quenching the high-pressure phase to ambient conditions, thus providing
great choices of ferrites materials for a variety of applications.
The pursuit of di-coordinate boron radical has been continued for more than a half century, and their stabilization and structural characterization remains a challenge. Here we report the isolation and structural characterization of a linear di-coordinate boron radical cation, achieved by stabilizing the two reactive atomic orbitals of the central boron atom by two orthogonal π-donating and π-accepting functionalities. The electron deficient radical cation undergoes facile one-electron reduction to borylene and binds Lewis base to give heteroleptic tri-coordinate boron radical cation. The co-existence of half-filled and empty p orbitals at boron also allows the CO-regulated electron transfer to be explored. As the introduction of CO promotes the electron transfer from a tri-coordinate neutral boron radical to a boron radical cation, the removal of CO under vacuum furnishes the reverse electron transfer from borylene to yield a solution consisting of two boron radicals.
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