Synthesis and characterization of poorly-crystaline Fe-Al nano-hydroxides
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Synthesis and characterization of poorly-crystaline Fe-Al nano-
hydroxides
Crop and Soil Sciences Department & Center of Environmental Kinetics Analysis
The Pennsylvania State University
18th World Congress of Soil Science July 11, 2006
Katya Bazilevskaya, Douglas Archibald, Carmen Enid Martínez
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Why we study hydroxide nano-particles?
Form coatings: meta-stable mixtures of Fe-, Al- and Si oxides and organics, which:
Affect mobility of nutrients and contaminants
Reflect soil-forming processes
Affect mineral dissolution rates
Have large reactive surface area Create pH-dependent charge
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Slow titration rate (0.1 ml/min)
Dyalisis to remove salts and excess Al
Fe (+Al) nitrate sol-n, pH ~2
0.1 M KOH
Experimental conditions:[Fe+Al] = 10 mM;%Al: 0, 10, 25, 30, 50, 75, 100; pH = 5
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Measured by light scattering (ZetaPALS, Brookhaven Instruments)
0% Al 30% Al
AFM images of Fe-Al particles
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What methods to use?
X-ray diffraction (XRD): long range order information synchrotron XRD for poorly crystalline hydroxides only crystalline phase
Extended X-ray Absorption Fine structure spectroscopy (EXAFS) short range order (atom’s second neighbor information – bond distance, type of bond)) both crystalline and amorphous Can only probe for Fe, not Al
Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR FTIR)
short range order (bonding and reactivity of protons) both crystalline and amorphous distinct iron and Al hydroxide OH-vibrations ATR technique provide precise technique: measures nano-particles coatings on the sensor (do not
need to separate nano-particles by centrifugation and freeze-drying)
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Structure of end-membersGoethite
Gibbsite
(OH)
stretching
(OH)
bending
(OH)
deformation
Goethite 3450, 3206 1687, 1643 888, 798Gibbsite 3620, 3525 3455, 3390 1024, 975 -
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2600280030003200340036003800
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
Frequency, wavenumbers
-Log
(I/I
o)%Al
increases
600800100012001400160018000
0.005
0.01
0.015
0.02
0.025
0.03
Frequency, wavenumbers
-Log
(I/I
o)
%Al increases
Infrared spectra of Fe-Al hydroxides
with different %Al
0% Al
100% Al
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10001500200025003000350040000
0.005
0.01
0.015
0.02
0.025
Frequency, wavenumbers
-Log
(I/I
o)
10001500200025003000350040000
0.005
0.01
0.015
0.02
0.025
0.03
Frequency, wavenumbers
-Log
(I/I
o)
Change of infrared spectra of Fe-Al
hydroxides with time
0%Al
25%Al
Time = 2 days @ 50 C
Time = 0 days
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Preliminary Fe-EXAFS data (aged for 2 weeks)
Radial distribution functions for oxide suspensions of various Fe:Al ratios
Fe-Fe distances for • goethite3.0 – 3.4 Å(2.5-2.9 in R)
Fe-Al distances for • Fe3+-gibbsite2.9 Å (2.4 in R)• Epidote 2.95 Å (2.5 in R)• LiAlO2
with 1wt.%Fe3+
3.15 Å (2.6 in R)
From the Literature
Fouri
er
Tra
nsf
orm
ed X
AFS
, χ
(R)
Fe-O Fe-Fe
Fe-Al
Fe-only
Fe:Al=1:1
Distance to neighboring atom R, Å
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Connection with real life….Spodosols
Top-view
Profile-view
To monitor formation of iron coatings on quartz in situ:
placed quartz in the soil profile
recovered after 1 year
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Acknowledgments
Funding: Center of Environmental Kinetics analysis (CEKA)
XRD and EXAFS: beamlines X-16C, X-18B, X-10C, National Synchrotron Light Source, Brookhaven National Laboratory
….
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