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Title: U(IV) Aqueous Speciation from the Monomer to UO 2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Energy Frontier Research Center, Materials Science of Actinides Department of Chemistry, Oregon State University, Gilbert Hall, Corvallis, Oregon 97331, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388899
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 56; Journal Issue: 11; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
Language:
English
Subject:
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Falaise, Clément, Neal, Harrison A., and Nyman, May. U(IV) Aqueous Speciation from the Monomer to UO2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b00616.
Falaise, Clément, Neal, Harrison A., & Nyman, May. U(IV) Aqueous Speciation from the Monomer to UO2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands. United States. doi:10.1021/acs.inorgchem.7b00616.
Falaise, Clément, Neal, Harrison A., and Nyman, May. Tue . "U(IV) Aqueous Speciation from the Monomer to UO2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands". United States. doi:10.1021/acs.inorgchem.7b00616.
@article{osti_1388899,
title = {U(IV) Aqueous Speciation from the Monomer to UO2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands},
author = {Falaise, Clément and Neal, Harrison A. and Nyman, May},
abstractNote = {},
doi = {10.1021/acs.inorgchem.7b00616},
journal = {Inorganic Chemistry},
number = 11,
volume = 56,
place = {United States},
year = {Tue May 16 00:00:00 EDT 2017},
month = {Tue May 16 00:00:00 EDT 2017}
}
  • A new caesium uranyl molybdate belonging to the M{sub 6}U{sub 2}Mo{sub 4}O{sub 21} family has been synthesized by solid-state reaction and its structure determined from single-crystal X-ray diffraction data. Contrary to the other alkali uranyl molybdates of this family (A=Na, K, Rb) where molybdenum atoms adopt only tetrahedral coordination and which can be formulated A{sub 6}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}], the caesium compound Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 21} should be written Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] with molybdenum atoms in tetrahedral and square pyramidal environments. Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] crystallizes in the triclinic symmetry withmore » space group P1-bar and a=10.4275(14) A, b=15.075(2) A, c=17.806(2) A, {alpha}=70.72(1){sup o}, {beta}=80.38(1){sup o} and {gamma}=86.39(1){sup o}, V=2604.7(6) A{sup 3}, Z=4, {rho}{sub mes}=5.02(2) g/cm{sup 3} and {rho}{sub cal}=5.08(3) g/cm{sup 3}. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R{sub 1}=0.0464 and wR{sub 2}=0.0950 for 596 parameters with 6964 independent reflections with I{>=}2{sigma}(I) collected on a BRUKER AXS diffractometer with Mo(K{alpha}) radiation and a CCD detector. The crystal structure of Cs compound is characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} parallels chains built from U{sub 2}O{sub 13} dimeric units, MoO{sub 4} tetrahedra and MoO{sub 5} square pyramids, whereas, Na, K and Rb compounds are characterized by {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}O(MoO{sub 4}){sub 4}]{sup 6-} parallel chains formulated simply of U{sub 2}O{sub 13} units and MoO{sub 4} tetrahedra. Infrared spectroscopy measurements using powdered samples synthesized by solid-state reaction, confirm the structural results. The thermal stability and the electrical conductivity are also studied. The four compounds decompose at low temperature (between 540 and 610 {sup o}C). -- Graphical abstract: The staking of {sub {infinity}}{sup 1}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})]{sup 6-} infinite uranyl molybdate ribbons in the Cs{sub 6}[(UO{sub 2}){sub 2}(MoO{sub 4}){sub 3}(MoO{sub 5})] structure. Display Omitted Highlights: {yields} Cs{sub 6}U{sub 2}Mo{sub 4}O{sub 2} a new compound with bidimensional crystal structure, characterized by infinite uranyl molybdate chains. {yields} Crystal structure similar to these of the compounds containing Na, K, Rb. {yields} Molybdenum atoms surrounded by five oxygen atoms to form an original and strongly distorted MoO{sub 5} environment. {yields} The chains arrangement illustrates the key role of the alkaline ionic radius, in the crystal structure distortion for Cs compound.« less
  • Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less
  • Uranium is commonly associated in natural waters with O-containing ligands both in the aqueous and the solid phases. Phosphate is present in most of these systems; however, the thermodynamics of the U(VI)-H[sub 3]PO[sub 4] system are poorly known, particularly in the pH range of interest 6 to 9. Hence, the effect of phosphate on the migration of uranium in natural waters is not well understood. We have investigated the solubility of a well-characterized U(VI)-phoshpate phase in the pH range 3 to 9: (UO[sub 2])[sub 3](PO[sub 4])[sub 2][center dot]4H[sub 2]O(s). Analysis of these data indicates the formation of the predominant speciesmore » UO[sub 2]HPO[sub 4](aq) and UO[sub 2]PO[sub 4] in the pH range 4-9. Their formation constants as well as the solubility constant of (UO[sub 2])[sub 3](PO[sub 4])[sub 2][center dot]4H[sub 2]O(s) have been determined. From the same experiments we have established the equilibrium constant of the hydroxide complex UO[sub 2](OH)[sub 3][sup [minus]]. A discussion of the hydrolysis of U(VI) is also reported. The effect of phosphate on the mobility of U in natural waters is assessed in the light of these new data. They indicate that in the pH range of most natural waters, 6 to 9, U(VI) will be associated to aqueous phosphate complexes when the total concentration ratio [PO[sup 3[minus]][sub 4]]T/CO[sup 2[minus]][sub 3]T is greater than 10[sup [minus]1].« less
  • ABS>The system UO/sub 3/- SO/sub 3/- H/sub 2/O at high temperature is characterized by a range of compositions in which liquid-liquid immiscibility occurs. Some equilibrium compositions of the two liquid phases with vapor present in this system and its D/sub 2/O analogus were determined from 280 to 350 deg . The nature of the equilibrium is unusual since at 350 deg in certain parts of the systems the light-liquid phase, 0.02 to 0.1 molal in SO/sub 3/, is in equilibrium with a heavy-liquid phase, 9 molal in SO/sub 3/. The light-liquid phases contain an excess of free H/sub 2/SO/sub 4/more » whereas the heavy-liquid phases either are stoicheiometric in UO/sub 2/SO/sub 4/ or contain a small excess of free H/sub 2/SO/sub 4/ or UO/sub 3/. Comparative liquid-phase compositions in the analogous D/sub 2/O system showed little difference in composition in the heavy-liquid phases but indicated approximately 10 per cent lower saturation molal ratios, m/sub uo3/ m/sub so3/, for the light-liquid phases. (auth)« less
  • Thermolysis of Cp[sup *]Zr(COT)R(Cp[sup *] = [eta][sup 5]-C[sub 5]Me[sub 5], COT = [eta][sup 8]-C[sub 8]H[sub 8], R = CH[sub 2]SiMe[sub 3],Me) proceeds via a double hydrogen abstraction from a cyclooctatetraene ligand to give RH and Cp[sup *]Zr([mu]-[eta][sup 8]:[eta][sup 2]-C[sub 8]H[sub 6])ZrCp[sup *]([eta][sup 4]-C[sub 8]H[sub 8]) as the kinetic product. Cp[sup *]Zr([mu]-[eta][sup *]:[eta][sup 2]-C[sub 8]H[sub 6])ZrCp[sup *]([eta][sup 4]-C[sub 8]H[sub 8]) undergoes a thermally induced hydrogen transfer from the pentamethylcyclopentadienyl ligands to the cyclooctatetraenediyl ligand to give the thermodynamic product FvZrCOT (Fv = [eta][sup 6]-C[sub 5]Me[sub 4]CH[sub 2]). For Cp[sup *]Zr(COT)R (R = CH[sub 2]Ph) a different thermolysis reaction was observed, inmore » which FvZrCOT was the major product at low temperatures, together with some Cp[sup *]Zr([mu]-[eta][sup 8]:[eta][sup 2]-C[sub 8]H[sub 6])-ZrCp[sup *]([eta][sup 4]-C[sub 8]H[sub 8]). The latter does not convert into the thermodynamic product at the temperature of thermolysis, indicating an alternative, direct, thermal decomposition pathway to FvZrCOT for R = CH[sub 2]Ph, with preferred hydrogen abstraction from the sp[sup 3] carbon of the pentamethylcyclopentadienyl ligand. Cp[sup *]Zr([mu]-[eta][sup 8]:[eta][sup 2]-C[sub 8]H[sub 6])ZrCp[sup *]([eta][sup 4]-C[sub 8]H[sub 8]) crystallizes in the monoclinic space group P2[sub 1]/n. The molecular structure shows an unprecedented cyclooctatrienyne ligand, bridged asymmetrically between the Zr atoms. The formulation as a cyclooctatrienyne complex is formal; the actual bonding of the ligand is as a dimetalated [eta][sup 8]-cyclooctatetraene-1,2-diyl. 40 refs., 1 fig., 3 tabs.« less