Experimental and theoretical evidence points to first-order character of the fergusonite–scheelite transition in LaNbO4, and dopant Mo6+ and interstitial O2− defects exhibit competing effects on local oxide ion mobility.
The impact of porosity of MOFs on their structural evolution during reaction with electrolyte and their use as pre-catalysts for electrochemical reduction of CO2 provide new insights into the design of new MOFs-derived catalysts.
Formation of multi-carbon (C2+) products by electrochemical reduction of CO2 using two porous Cu(ii)-based materials (HKUST-1 and CuMOP, MOP = metal–organic polyhedra) under electrochemical conditions in the presence of TNCQ.
In the United Kingdom, decommissioning
of legacy spent fuel storage
facilities involves the retrieval of radioactive sludges that have
formed as a result of corrosion of Magnox nuclear fuel. Retrieval
of sludges may re-suspend a colloidal fraction of the sludge, thereby
potentially enhancing the mobility of radionuclides including uranium.
The colloidal properties of the layered double hydroxide (LDH) phase
hydrotalcite, a key product of Magnox fuel corrosion, and its interactions
with U(VI) are of interest. This is because colloidal hydrotalcite
is a potential transport vector for U(VI) under the neutral-to-alkaline
conditions characteristic of the legacy storage facilities and other
nuclear decommissioning scenarios. Here, a multi-technique approach
was used to investigate the colloidal stability of hydrotalcite and
the U(VI) sorption mechanism(s) across pH 7–11.5 and with variable
U(VI) surface loadings (0.01–1 wt %). Overall, hydrotalcite
was found to form stable colloidal suspensions between pH 7 and 11.5,
with some evidence for Mg
2+
leaching from hydrotalcite
colloids at pH ≤ 9. For systems with U present, >98% of
U(VI)
was removed from the solution in the presence of hydrotalcite, regardless
of pH and U loading, although the sorption mode was affected by both
pH and U concentrations. Under alkaline conditions, U(VI) surface
precipitates formed on the colloidal hydrotalcite nanoparticle surface.
Under more circumneutral conditions, Mg
2+
leaching from
hydrotalcite and more facile exchange of interlayer carbonate with
the surrounding solution led to the formation of uranyl carbonate
species (e.g., Mg(UO
2
(CO
3
)
3
)
2–
(aq)
). Both X-ray absorption spectroscopy
(XAS) and luminescence analysis confirmed that these negatively charged
species sorbed as both outer- and inner-sphere tertiary complexes
on the hydrotalcite surface. These results demonstrate that hydrotalcite
can form pseudo-colloids with U(VI) under a wide range of pH conditions
and have clear implications for understanding the uranium behavior
in environments where hydrotalcite and other LDHs may be present.
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