US researchers achieve a major milestone after successfully trapping plutonium ion between two Keggin ion molecular cages.
A collaborative effort from researchers at the Lawrence Livermore National Laboratory , Sandia National Laboratories, and Oregon State University has successfully ‘caged’ a plutonium atom inside a Keggin ion.
This is the first time researchers have been able to trap plutonium within a Keggin ion.It was only about 90 years ago that scientists discovered the element Plutonium, but its use ranges from generating energy in nuclear reactors to deep-space exploration. The silvery-gray metal is radioactive and has nearly 20 isotopes. Each of these isotopes has a different radioactive decay rate and therefore a different half-life. Researchers have synthesized multiple compounds with this metal, and to further material science, they need to understand its atomic structure in greater detail. What we know about plutoniumPlutonium forms known alloys with many other metals and can also exist in multiple metallic phases. In addition, it forms coordination compounds. These are molecules in which a central metal atom is bound by other molecules or ions. Researchers know that in such compounds, plutonium acts as a cation, a positively charged ion, and forms bonds with other molecules in its surroundings. Scientists are aware of hundreds of such plutonium coordination structures, but very few of them involve plutonium and polyoxometalates . POMs are a special class of molecules that are large oxygen-based clusters that can act as inorganic molecular cages for metal ions. Until recently, only five plutonium-POM compounds had been isolated. This is less than one percent of the known molecules and compounds that plutonium can make, showing how little we know about plutonium and its chemistry. Researchers at LLNL, SNL, and Oregon State University were investigating how POMs interact with challenging actinide elements and attempted to isolate plutonium within a POM. How did they do it? In their work, the researchers used a POM called a Keggin ion. This is a negatively charged molecular cluster built using tungsten and oxygen atoms. At the center of the Keggin ion is a phosphorus atom. This POM had been used to trap multiple metal ions, but never plutonium. The team used a specially prepared chemical solution containing just six millionths of a gram of plutonium and successfully bound the actinide metal ion between two Keggin cages. To confirm the stability of this new plutonium-POM complex, the researchers used advanced tools, including X-ray crystallography, optical spectroscopy, nuclear magnetic resonance, and X-ray scattering, which also provided more detailed structural information. After comparing the plutonium-POM complex with similar complexes of other metals, the team found something unexpected. In POM complexes with other metals, such as cerium, hafnium, and thorium, the metal ions arrange themselves in parallel. Surprisingly, plutonium complexes arranged themselves perpendicularly to each other. The researchers attribute this arrangement to why plutonium has defied simple models and behaves like a wild card among other elements. The research also shows that the approach can be useful in isolating other challenging elements in the periodic table and studying them in greater detail. The research findings were published in the journal Inorganic Chemistry.
Inorganic Chemistry Keggin Cages Keggin Ion Plutonium Plutonium-POM Polyoxometalates
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