organic and macromolecular synthesis facility the molecular foundry lawrence berkeley national...
TRANSCRIPT
Organic and Macromolecular Synthesis Facility
The Molecular FoundryLawrence Berkeley National laboratory
Berkeley, United States
Boston, MA
2010 Nuclear Fuel Resources Workshop
Innovative Functionalized Polymers for Efficient Collection of Uranium from Seawater
Organic and Macromolecular Synthesis Facility
Innovative Functionalized Polymers for Efficient Collection of Uranium from Seawater
Identified Uranium Resources(<$130/kgU) Demand Uranium in Seawater
Worldwide U.S. U.S. in 2007 Concentration Resource
5,469,000 540,000 12,000 3.3 ppb 4.5 109
The Identified Resource base would be sufficient for 40-80 years of reactor supply worldwide. However, the projections for the United States are less optimistic. To secure our energy supply in the future, more uranium exploration is important and necessary.
Shortcomings of the Japanese braid:1. Hydrophobic polyethylene base slow sorption kinetics.2. Amidoxime functional group: poor stability and selectivity low efficiency and high cost.
Uranium Resource and Demand (tU)
Method for uranium collection from seawater developed in Japan ($300-400/kgU):
Organic and Macromolecular Synthesis Facility
O
O
O OO
O
mn
+Benzyl peroxide
isopropanolCyclohexane
b. Resin synthesis
Synthesis of Glycidyl Functionalized Adsorbent Base Materials
O
O
O
Free radical initiationO
O
OO
O
O
n
a. Cellulose modification
(GMA)Cellulose Cellulose
Fe2+ + H2O2 Fe3+ OH- OH+ +
Fenton reaction
Ceric Ammonium nitrate (CAN)
Free Radical Initiation
or
(grafting)
(copolymerization)
Organic and Macromolecular Synthesis Facility
Polymer
OO
O
OO
O
OHS
Polymer
OO
HO
O
S
OO
HO
O
S
N
COOH
COOH
Ligand
Ligand Ligand
Ligand POC8H17
O
OC8H17
PC8H17
O
C8H17
, ,
Ligand Immobilization and Screening
Glycidyl methacrylate (GMA)Higher hydrophilicity, easy modification
Organic and Macromolecular Synthesis Facility
K. Raymond JACS 1992
J. Rebek Chemical Science 2010 J. Rebek JACS 2010
• Coordination geometry — linear vs. spherical, octahedral coordination, auxiliary binding to oxygen.• High affinity — only 3 ppb in sea water. (vs Amidoxime?)• Selectivity — in competition with alkaline and alkaline earth metal ions in sea water.• Can be modified – easiness for attachment to adsorbent.
New Ligand Design
R NH2
NOH
R NH2
NNH2
Organic and Macromolecular Synthesis Facility
Consideration of polymer backbone conformation
Foldamer to reinforce cooperative multivalency
Tripodal ligands
QuickTime™ and a decompressor
are needed to see this picture.
O
O
NH
NH
O
O
HN
NH
O
O
NH
HN