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Semiconductor Metal Oxide Nanoparticles for Visible Light
Photocatalysis
NSF NIRT Grant No. 0210284
University of Delaware
S. Ismat Shah Materials Science and EngineeringPhysics and
AstronomyC.P. HuangCivil and Environmental EngineeringJ. G.
ChenChemical EngineeringD. DorenChemistry and BiochemistryM.
BarteauChemical
Engineeringhttp://www.physics.udel.edu/~ismat/NIRT.htm
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Students and Post-DocsM. Barakat:Materials Science and
Engineering (Post-Doc)S. Rayko: Chemical Engineering (Post-Doc)S.
Lin: Graduate Student, Civil and Environmental Engin.Y. Wang:
Graduate Student, Chemistry and BiochemistryS. Chan: Graduate
Student, Chemical EngineeringJ. McCormick: Graduate Student,
Chemical EngineeringW. Li: Graduate Student, Materials Science and
Engin.S. Buzby: Graduate Student, Materials Science and Engin.Greg
Hayes: Undergraduate Student, Mechanical Engin.Holly Sheaffers:
Undergraduate Student, Chemical Engin.
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ObjectivesTo develop an understanding of the chemical and
photochemical properties of pure and modified TiO2 in nanostructure
form. Modification involves the selective decoration and doping of
nanoparticle surfaces. To utilize unique physical and chemical
vapor deposition processes to obtain TiO2 nanoparticles. To modify
TiO2 nanoparticles to induce visible light photocatalysis. To
characterize the nanoparticles for structural, chemical and
optoelectronic properties. To utilize first-principles calculations
to acquire an atomistic understanding of nanoparticle
properties.
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TiO2TiO2 is desirable for photocatalysis due to its inertness,
stability, and low cost. It is also self regenerating and
recyclable. Its redox potential of the H2O/*OH couple (-2.8 eV)
lies within the band gap.However, its large band gap (Eg=3.2 eV)
only allows absorption the UV of solar spectrum. An absorber in the
visible range is desired.Absorption in the visible range can be
improved by dye sensitization, doping , particle size modification,
and surface modification by noble metals.
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Why nano-TiO2?Considerations:Volumetric RecombinationSurface
RecombinationQuantum Confinement effectsReduction Reactionhn
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MethodologyStudy Size EffectsStudy Doping EffectsCharacterize
Photocatalytic Properties
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Schematic of MOCVD System for TiO2 Synthesis
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Split Cathode Magnetron
Sputtering gases inlet
Nanoparticle collector
Split Cathodes
Transformer
Water-cooled copper coil for electromagnet
AC Power Supply
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TEM Characterization of TiO2 NanoparticlesThe structure of all
as-grown samples is anatase.The particle sizes from TEM range
between 15 and 25 nm.(b) bright field image(a) dark field image(c)
diffraction patterns(d) lattice image20nm(d) Lattice Image
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XRD of TiO2 Nanoparticles as a Function of Deposition
Temperature
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TiO2 Phase Transformation: Effect of Particle size 20nmXRD
patterns from as-deposited samples and samples annealed at 700,
750, and 800 oC. The phase compositions were calculated based on
formula
Particle sizes were calculated.
A. A. Gribb and J. F. Banfield, Am. Mineral. 82, 717 (1997).
(*)
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Activation Energy Calculation AR=A0Exp(-Ea/KT), A0=0.884AA+AR Ea
is anatase to rutile transformation activation energy. The
activation energy decreases with the particle size and 12-nm sample
has the lowest activation energy of 180.28 kJ/mol. Bulk TiO2 has
activation energy of 450 kJ/mol.(*)(*) H. Zhang and J. F. Banfield,
Am. Mineral. 84, 528 (1999).
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The Effect of Dopants on Photocatalytic Kinetics:
Degradation of 2-chlorophenolTiO2 = 10 mg, C0(2-CP) = 50 mg/L,
Volume= 1 L, pH = 9.5, Temperature = 22 oC, P uv lamp = 100
Watts.
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Apparent Quantum Yields for Doped and Undoped
TiO2 Nanoparticles
Table I. Estimations of initial photodegradation rate, UV photon
flux, and apparent
quantum yield for aqueous solutions of 2CP with doped and
undoped TiO2 nanoparticles
in the reactor.
Catalysts
Initial rate
(mol/min)
Photon flux
(Einstein/min)
Quantum yield
TiO2 (Nd3+)
29.2 ( 0.25
4.42
6.61 ( 0.06
TiO2 (Pd3+)
17.6 ( 0.82
4.42
3.98 ( 0.19
TiO2 (Pt4+)
12.9 ( 0.47
4.42
2.92 ( 0.11
TiO2 (Fe3+)
3.74 ( 0.64
4.42
0.84 ( 0.14
Pure TiO2
9.72 ( 0.82
4.42
2.20 ( 0.19
Degussa P25
11.7 ( 0.25
4.42
2.65 ( 0.06
_1062245448.unknown
_1062497726.unknown
_1062245419.unknown
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Ionic Radii of the Dopants
Ions
Ti4+
Pt4+
Fe3+
Pd2+
Nd3+
Ionic radii ()
0.605
0.625
0.645
0.86
0.983
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Band Gap Calculation from Light Absorptiona: Nd=0%b: Nd=0.6%c:
Nd=1%d: Nd=1.5%
]Chart2
3.18
2.83
2.5
2.3
Nd Concentration (at.%)
Band Gap (eV)
]Sheet1
03.18
0.62.83
12.5
1.52.3
]Sheet1
Nd Concentration (at.%)
Band Gap (eV)
]Sheet2
]Sheet3
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-NEXAFS reveals LUMO and HOMO states (related to Eg) of TiO2 are
modified Review on NEXAFS: Chen, Monograph in Surface Science
Reports, Vol. 30 (1997)Characterizing TiO2 Nanoparticles Using
Near-Edge X-ray Absorption Fine Structure (NEXAFS)
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Theoretical Calculation of Band Gap(d) lattice image20nmDensity
functional theory calculations using the generalized gradient
approximation with the linearized augmented plane wave method are
used to interpret the band gap narrowing.Some electronic states are
introduced into the band gap of TiO2 by substitutional Nd 4f
electrons, to form the new LUMO band.The absorption edge transition
for the doped material can be from O 2p to Nd 4f instead of Ti 3d,
as in pure TiO2.
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Short Term ProgramOptimization of the doping
concentrationCombined nanosize and doping effectsNd: Substitutional
or interstitial? NEXAFS and EXAFS analyses.Theoretical calculations
of bandgap variation with the doping type and
concentrations.Degradation kinetics, intermediates, etc.
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Long Term ProgramPhotocatalysis with visible light Anion doping:
C,O,NSurface decoration with Pt-group metals nanoparticles for
charge transfer enhancementDLTS characterization for dopant level
Transient absorption spectroscopy to study the carrier life time in
nanoparticles.
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Outreach ActivitiesVacuum on wheels: A demonstration unit for
area middle schools showing the affects and uses of
vacuum.Nanotechnology and Society: A lecture series being developed
for local school and junior colleges.Minority recruitment
activities for participation in the NIRT program.Visit our web
site:http://www.physics.udel.edu/~ismat/NIRT.htm
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XRD ResultOnly anatase phase is detected for all (0.6%, 1%, and
1.5% Nd) doped and undoped samples.These diffraction patterns are
from 1% Nd doped TiO2.Part III: Structural, Optical, Photocatalytic
Properties of Nd3+ Doped TiO2 Nanoparticles
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Visible Light Photocatalysis of TiO2 NanoparticlesPart III:
Structural, Optical, Photocatalytic Properties of Nd3+ Doped TiO2
NanoparticlesDegradation of 2-chlorophenol: TiO2 = 5 mg,
C0(2-CP)=20 mg/L, Volume=0.5 L, pH = 9.5, Temperature = 22 oC,
PVisible Lamp = 100 Watts.
Chart1
111
0.95990099010.99950.976
0.94455445540.9980.9689
0.92920792080.9970.9589
0.89257425740.99250.9446
0.85643564360.98550.9252
0.81683168320.9830.9112
TiO2(Nd1%)
No TiO2
TiO2(pure)
Reaction Time (min)
Relative Concentration (C/C0)
Sheet1
0120201191.5011960120001
100.9599009901193.9100.9117493473174.6101.0454081633204.9100.9995199.9100.976
200.9445544554190.8200.8428198433161.4201.0285714286201.6200.998199.6200.9689
300.9292079208187.7300.87154047166.9300.9964285714195.3300.997199.4300.9589
500.8925742574180.3500.8156657963156.250500.9925198.5500.9446
700.8564356436173700.7775456919148.9700.9494897959186.1700.9855197.1700.9252
900.8168316832165900.7347258486140.7900.9005102041176.5900.983196.6900.9112
1200.6767624021129.61300.8295918367162.6
Sheet1
000
000
000
000
000
000
000
0
TiO2(Nd1)
Vis-Only
TiO2(pure)
Reaction Time (min)
Relative Concentration (C/C0)
Sheet2
Sheet3
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Conclusions
Doped and undoped TiO2 nanoparticles were synthesized by MOCVD
method.The effect of growth temperature on particle size and size
distribution was investigated. Results showed that particles
deposited at 600 oC had the smallest size and narrowest size
distribution.Some transition metal ions were selected to study the
dopant effect on the photocatalytic efficiency and Nd3+ was found
to have the highest enhancement.The absorption range of TiO2
nanoparticles was extended into visible light region by Nd
doping.The positions of Nd in the TiO2 lattice are being
studied.Measurements of electric current and photocatalysis under
irradiation of visible light are being carried out.
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Acknowledgements We would like to thank NSF - NIRT for financial
support of this project.
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TEM bright field images, diffraction patterns and particle size
distributions of undoped TiO2 nanoparticles as a function of the
growth temperature.The doped TiO2 has the similar results.TEM
ResultsPart I: Structure and Size Distribution of TiO2
Nanoparticles
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DLS Study of TiO2 Particle Size DistributionPart I: Structure
and Size Distribution of TiO2 Nanoparticles
EMBED Origin50.Graph
_1033135056.bin
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Effect of Growth Temperature on Size of TiO2 Part I: Structure
and Size Distribution of TiO2 Nanoparticles
EMBED Origin50.Graph
_1063551617.bin
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Size Dependence of Structural, Optical,
and Photocatalytical Properties of TiO2 Nanoparticles W. Li1, C.
Ni1, H. Lin3, C.P. Huang3, S. Ismat Shah1,2 1. Department of
Materials Science and Engineering 2. Department of Physics and
Astronomy 3. Department of Civil and Environmental Engineering
University of Delaware, Newark, DE 19716.
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MotivationAnatase TiO2 is desirable for photocatalysis due to
its inertness, stability, and low cost. It is also self
regenerating and recyclable. Its redox potential of the H2O/*OH
couple (-2.8 eV) lies within the band gap.It is crucial to 1.
design and controllably manipulate TiO2 phase types and
concentrations for more efficient photocatalysis. 2. determine the
optimal size for highest photoreactivity.So, we would like to study
the effect of particle size on the phase thermal stability,
optical, and photoreactivity of TiO2 nanoparticles.
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Schematic of MOCVD System for TiO2 Synthesis Chemical reaction
in the chamberTi[OCH(CH3)2]4 + 18O2 TiO2 + 12CO2 +14H2O
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Experimental Conditions (1)
Carrier gas Ar: 3 sccm.Reactant gas O2: 10 Torr. 20, 25, and 35
sccm flow rates of O2 were used to obtain different size of TiO2
nanoparticles. Ti precursor: Titanium Tetraisopropoxide
Ti[OCH(CH3)2]4 (TTIP).TTIP bath temperature=220 oC (B.P.=232
oC)Growth temperature: 600 oC.
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Experimental Conditions (2)Annealing conditions: Isochronal
annealings were carried out with temperatures 700, 750, and 800 oC
for 1 hr in the air.
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X-ray Diffraction Patterns for TiO2 with Different Particle
Sizes Effect of O2 gas flow rate on particle size.
All peaks belong to the anatase phase and no other phase is
detected within the X-ray detection limit
The measured average particle sizes were 12 2, 17 2, and 23 2 nm
for the three samples.
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BET Surface Area Measurements
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Transmission Electron Microscopy Study of TiO2 Phase
Transformation (1)As-deposited700 oC800 oCTEM diffraction patterns
for annealed and as-deposited 12-nm sample.
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Transmission Electron Microscopy Study of TiO2 Phase
Transformation (2)As-deposited700 oC800 oCTEM bright field images
for annealed and as-deposited 12-nm sample.
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X-ray Diffraction Study of TiO2 Phase Transformation (1) (d)
lattice image20nmXRD patterns from as-deposited samples and samples
annealed at 700, 750, and 800 oC. The phase compositions were
calculated based on formula
Particle sizes were calculated.
A. A. Gribb and J. F. Banfield, Am. Mineral. 82, 717 (1997).
(*)
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Activation Energy Calculation AR=A0Exp(-Ea/KT), A0=0.884AA+AR Ea
is anatase to rutile transformation activation energy. The
activation energy decreases with the particle size and 12-nm sample
has the lowest activation energy of 180.28 kJ/mol. Bulk TiO2 has
activation energy of 450 kJ/mol.(*)(*) H. Zhang and J. F. Banfield,
Am. Mineral. 84, 528 (1999).
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Mechanism of Phase Transformation Interface boundary atomic
migration is the primary source for phase growth. This has been
previously reported by other researchers. [A, B] TiO2 nanoparticles
have smaller activation energy. It is easier to overcome the energy
barrier to new phase. Smaller particles have lower activation
energy.
References: [A] T. C. Chou and T. G. Nieh, Thin Solid Films 221,
89 (1992). [B] P. I. Gouma, P. K. Dutta, and M. J. Mills,
NanoStruct. Mater. 11, 1231 (1999).
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Size Dependence of Light Absorption 17 nm sample has the largest
red shift. Comparison of band gaps B17nm < B12nm < B23nm
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Size Dependence of Photoreactivity
Photodegradation of 2-chlorophenol solutions with different size
samples. 17 nm sample has the highest photoreactivity.
Chart2
111
0.9980582520.9848076920.992376112
0.9555339810.9346153850.926483935
0.735922330.5903846150.774913777
0.5584466020.3638461540.65347613
0.3943689320.1850.550009076
0.2155339810.0653846150.371755309
0.0848543690.0128846150.237611182
12 nm
17 nm
23 nm
Reaction Time (min)
Relative Concentration (C/C0)
Sheet1
12 nm17 nm23 nmP25
01111
50.9980582520.9848076920.9923761120.987191561
100.9555339810.9346153850.9264839350.937841401
200.735922330.5903846150.7749137770.787907327
300.5584466020.3638461540.653476130.640045206
400.3943689320.1850.5500090760.525334338
600.2155339810.0653846150.3717553090.169523451
900.0848543690.0128846150.2376111820.033716331
Sheet1
000
000
000
000
000
000
000
000
12 nm
17 nm
23 nm
Reaction Time (min)
Relative Concentration (C/C0)
Sheet2
Sheet3
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The Optimal Size17 nm sample has the highest photoreactivity
compared with 12 nm and 23 nm samples.The optimal size is
determined by several aspects of TiO2 including surface area, light
absorption efficiency, and charge carrier recombination rate.
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Conclusions
TiO2 nanoparticles with different sizes were synthesized by
MOCVD.
The particle size role in the anatase to rutile phase
transformation was studied. The activation energies for particles
were calculated to be 180.28, 236.38, and 298.85 kJ/mol for 12, 17,
and 23 nm samples, respectively.
The 17 nm sample had the smallest band gap and highest
photoreactivity compared with the other samples.
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Acknowledgements We would like to thank NSF - NIRT for the
funding of this project.