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Pacific Northwest National LaboratoryU.S. Department of Energy
Nanomaterials for Nanomaterials for Environmental RemediationEnvironmental Remediation
Glen E. Glen E. FryxellFryxellPacific Northwest Pacific Northwest
National LaboratoryNational LaboratoryRichland, WARichland, WA
[email protected]@pnl.gov
Advantages of nanomaterials
High surface area (capacity)Well defined structureHigh reactivityEasy dispersabilityReadily tailored for application in different environmentsChemistry/materials developed for remediation processes are readily tailored to sensing/detection
Nanomaterials provide:
SAMMS: Self-Assembled Monolayers on Mesoporous
Supports
20 nm20 nm
A. Self-assembled monolayers
B. Ordered mesoporous oxide+
First reported in:
Science 1997, 276, 923-926.
POC: Glen Fryxell
SAMMS in a Nutshell
Extremely high surface area = high capacityRigid, open pore structure provides for fast sorption kineticsChemical specificity dictated by monolayer interfaceEasily modified for new target speciesSequestration can be driven either by metal/ligand affinity or by adduct insolubilityGood chemical and thermal stability Easily regenerated/recycled
“Designing Surface Chemistry in Mesoporous Silica” in “Adsorption on Silica Surfaces”; pp. 665-687, Marcel-Dekker, 2000.
POC: Glen Fryxell
Tailoring SAMMS interfacial chemistry to the periodic table
H HeLi Be B C N O F NeNa Mg Al Si P S Cl ArK Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I XeCs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At RnFr Ra Ac Rf Db Sg Bh Hs Mt Uun Uuu Uub 113 Uuq 115 117
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb LuTh Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Chemistry of Materials 1999, 11, 2148-2154J. Physical. Chem. B. 2001, 105, 6337-6346.J. Synchrotron Radiation, 2001, 8, 922-924
Cu-EDA
OOSi
SH
OOSi
SH
HO OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OHOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
HO OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
OOSi
SH
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SH
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SH
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OHOSi
SH
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OHOSi
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Science, 1997, 276, 923-926.J. Synchrotron Radiation, 1999, 6, 633-635Sep. Sci. & Technol. 1999, 3411, 2329-2345Mat. Tech. Adv. Perf. Mat. 1999, 14, 183-193Surf. Sci. & Catalysis, 2000, 105, 729-738.
thiol
SiO2
Si
O
O O
NHO
PHO
OHO
SiO2
Si
O
O O
NHO
NHO
O
3,2 HOPO
CH3
HOPO Prop-Phos
Cu-FC-EDA Cs
Env. Sci. & Tech. 2001, 35, 3962-3966.
Chem. Comm. 2002, 1374-1375.
Radiochimica Act2003, 91, 539-545
….all by varying the monolayer ligand field.
Functional Nanomaterials for analytical preconcentration
20 nm20 nm
Self-assembled monolayers•Dense surface coverage
•Chemical specificity
Mesoporous materials•High surface area
•Rapid sorption kinetics
High-performance preconcentrators
E-chem
UV-Vis
XRF
RadiocountingIRGC
“Self-Assembled Monolayers on Mesoporous Supports (SAMMS): Environmental Clean-up and Enhanced Sensing Capability” Encyclopedia of Nanoscience and Nanotechnology,
Marcel-Dekker, 2004
POC: Shane Addleman
Functionalized TiO2 Nanoparticlesfor Subsurface Injection
TiNano40TM CharacteristicsSurface Area (BET) 51.2 m2/gParticle Density 3.88 g/cm3Particle Size 40 – 60 nmTiO2 99.8%Impurities 0.2%(ZrO2, SiO2,Cl, P2O5, ZnO)Crystalline Phase Anatase
Tc-99 Adsorption ExperimentAdsorbent: Cu-EDA anatase nanoparticlesContact Solution: Hanford GW spiked with 49.5 pCi/ml of Tc-99Hanford Ground Water (mg/l)Ca 49.5 NO3 8.6Mg 14.6SO4 64.7K 1.7Si 16.5Na 13.2CO3 60.8Cl 16.4pH 8.3 (SU)EC 0.47 mS/cmSolution:Solid Ratio (ml/g) :25, 50, 100, 500, 100, 5000, 10000
Anatase Nanoparticle Injection TestsAn aqueous suspension of anatase (ammonium carboxylate ~ 2 wt %) was successfully injected in to a 100 cm long, 20 – 30 mesh sand column (~35% porosity).
The inlet pressure after injection of 3 pore volumes of suspension remained low (<14 psi).
An average of 4 wt % of anatase was uniformly distributed throughout the sand column.
POC: Shas Mattigod
Tc-99 Sequestration by Functionalized TiO2 Nanoparticles
y = 3.0072x2.9643
R2 = 0.95370.0E+00
2.0E+04
4.0E+04
6.0E+04
8.0E+04
1.0E+05
1.2E+05
1.4E+05
1.6E+05
0.0 10.0 20.0 30.0 40.0
Tc-99 Equilibrium Activity (pCi/ml)
Tc-9
9 ad
sorb
ed (p
Ci/g
)
y = 26.084x0.5453
R2 = 0.97320.0E+00
1.0E+03
2.0E+03
3.0E+03
4.0E+03
5.0E+03
10.0 100.0 1000.0 10000.0
Solution:Solid Ratio (ml/g)
Dis
tribu
tion
Coe
ffici
ent (
Kd m
l/g)
02468
10121416
0 1 2 3
# of Pore Volumes Injected
Inle
t Pre
ssur
e (p
si)
Inlet Pressure Change as a Function of Pore Volume
SummaryAnatase nanoparticles were successfully functionalized with Cu-EDA monolayers.
Cu-EDA anatase selectively adsorbed Tc-99 from spiked Hanford ground water.
Successful injection of an aqueous suspension of anatase nanoparticles into a sand medium was demonstrated.
Tc-99 Adsorption ExperimentsMaximum Tc-99 loading: ~1.3 x 105 pCi/g.Tc-99 Kd: 1.5 x 102 – 4.0 x 103 ml/g.
POC: Shas Mattigod