Conspectus
Current projections for global mining indicate
that unsustainable
practices will cause supply problems for many elements, called critical
raw materials, in the next 20 years. These include elements necessary
for renewable technologies as well as artisanal sources. Energy critical
elements (ECEs) comprise a group used for clean, renewable energy
applications that are in low abundance in the Earth’s crust
or require an economic premium to extract from ores. Sustainable practices
of acquiring ECEs is an important problem to address through fundamental
research to provide alternative energy technologies such as wind turbines
and electric vehicles at cheaper costs for our global energy generation
and usage. Some of these green technologies incorporate rare-earth
(RE) metals (Sc, Y and the lanthanides), which are challenging to
separate from mineral sources because of their similar sizes (i.e.,
ionic radii) and chemical properties. The current process used to
provide REs at requisite purities for these applications is counter-current
solvent–solvent extraction, which is scalable and works efficiently
for any ore composition. However, this method produces large amounts
of caustic waste that is environmentally damaging, especially to areas
in China that house major separation facilities. Advancement of the
selectivity of this process is challenging since exact molecular speciation
that affords separations is still relatively unknown. In this context,
we developed a program to investigate new RE separations systems that
were aimed at minimizing solvent use, controlled by molecular speciation,
and could be targeted at problems in recycling these critical metals.
The first ligand system that was developed to impart solubility
differences between light and heavy rare-earth ions was [{(2-
t
BuNO)C6H4CH2}3N]3– (TriNOx3–)
(graphic below). A differential solubility allowed for a separation
of Nd and Dy of SFNd:Dy = ∼300 in a single step.
In other words, a 50:50 Nd/Dy sample was enriched to give 95% pure
Nd and Dy through a simple filtration, which is potentially impactful
to recycling magnetic materials found in wind turbines. This separations
system compares favorably to other state-of-the-art molecular extractants
that are based on energetic differences of the thermodynamic parameter
to affect separations for neighboring elements. This straightforward,
thermodynamically driven method to separate REs primed our future
research for new coordination chemistry approaches to separations.
Another separations system was accomplished through the variable
rate of a redox event from one arm of the TriNOx3– ligand. It was determined that the rate of this one electron oxidation,
which operated through an electrochemical-chemical-electrochemical
mechanism, was dependent on the identity of the RE ion. This kinetically
driven separation afforded a separation factor (SF) of SFEu:Y = 75. We have also described other transformations such as ligand
exchange, substituent dependent, and redox-driven chelation processes
with well-define...