Advancing understanding of aqueous chemistry for plutonium is important because it impacts energy production,environmental management,and national security.Unfortunately,plutonium’s aqueous chemistry remains poorly c...Advancing understanding of aqueous chemistry for plutonium is important because it impacts energy production,environmental management,and national security.Unfortunately,plutonium’s aqueous chemistry remains poorly characterized.We addressed this problem by characterizing Pu_((IV))redox and coordination chemistry in aqueous solutions as a function of hydrochloric acid concentration using X-ray absorption spectroscopy,ultraviolet-visible near-infrared spectroscopy,and electrochemistry.The impact of Pu-Cl vs.Pu-OH_(2)O bonding was correlated with the stability of different plutonium oxidation states.We discovered that anionic Cl^(1-)ligands stabilized electron-deficient Pu_((IV))over Pu_((III))and neutral H_(2)O ligands stabilized Pu_((III))over Pu_((IV)).These findings offer a way to control plutonium electron transfer chemistry and imply that selective stabilization of Pu_((IV))or Pu_((III))may be achieved through tuning the electron donating ability of the ligand.Overall,this work advances predictive capabilities for aqueous plutonium chemistry,particularly within nuclear application spaces.展开更多
基金Department of Energy,Office of Science,Office of Basic Energy Sciences,Heavy Element Chemistry program(2020LANLE372)for funding the majority of this worksupport came from LANL’s LDRD projects(20220054DR)+2 种基金the US Department of Energy,National Nuclear Security Association(NNSA),Plutonium Modernization Program(NA-191)the Los Alamos National Laboratory Directors(Rice)and Harold Agnew National Security(Piedmonte)fellowships,and the Glenn T.Seaborg Institute(Gilhula,Klouda,Marshall-Roth)affirmative action/equal opportunity employer managed by Triad National Security,LLC,for the National Nuclear Security Administration of the U.S.DOE.Use of the Stanford Synchrotron Radiation Lightsource,SLAC National Accelerator Laboratory,was supported by the US DOE,Office of Science,Office of Basic Energy Sciences under contract no.DE-AC02-76SF00515。
文摘Advancing understanding of aqueous chemistry for plutonium is important because it impacts energy production,environmental management,and national security.Unfortunately,plutonium’s aqueous chemistry remains poorly characterized.We addressed this problem by characterizing Pu_((IV))redox and coordination chemistry in aqueous solutions as a function of hydrochloric acid concentration using X-ray absorption spectroscopy,ultraviolet-visible near-infrared spectroscopy,and electrochemistry.The impact of Pu-Cl vs.Pu-OH_(2)O bonding was correlated with the stability of different plutonium oxidation states.We discovered that anionic Cl^(1-)ligands stabilized electron-deficient Pu_((IV))over Pu_((III))and neutral H_(2)O ligands stabilized Pu_((III))over Pu_((IV)).These findings offer a way to control plutonium electron transfer chemistry and imply that selective stabilization of Pu_((IV))or Pu_((III))may be achieved through tuning the electron donating ability of the ligand.Overall,this work advances predictive capabilities for aqueous plutonium chemistry,particularly within nuclear application spaces.
