Effect of Particle Size on the Adsorption and

Desorption Properties of Oxide Nanoparticles

Task 425.023

Hao Wang

Chemical and Environmental Engineering

University of Arizona

April 19th, 2012

PIs:
Farhang Shadman
Dept. Chemical & Environmental Engineering, University of Arizona.

Reyes Sierra
Dept. Chemical & Environmental Engineering, University of Arizona.

Buddy Ratner
University of Washington Engineered Biomaterials (UWEB) Center, University of Washington
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 ESH Testing and Evaluation of NPs

Surface Properties: capacity, affinity, and activation energy

100 100
90 90
Moisture Retention (%)

Moisture Retention (%)

80 80
70 70
60 60
50 CeO2, 20nm 50 HfO2, 20nm
40 40
30 30
20 HfO2, 20nm
SiO2, 20nm 20 HfO2, 100nm
10 10
0 0
0 50 100 150 200 0 50 100 150 200
Time, t (min) Time, t (min)

Handy, R.D., Shaw, B.J., 2007. Toxic effects of nanoparticles and nanomaterials: Implications for public health, risk
assessment and the public perception of nanotechnology. Health Risk Society 9, 125-144.
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 Objectives and Method Approach
Objective: Characterization of the surface sites on nanoparticles that
contribute to concentration, retention, and enhanced transport of toxic
chemicals.
Method approach: Surface hydroxylation (adsorption and desorption
of contaminants).
Materials: SiO2, HfO2, and
CeO2.
Parameters: Oxide type,
particle size, temperature.

Results: Capacity and

energetics of capture and
retention of contaminants
on active sites.

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Schematic Diagram of the Experimental Setup
Voltage input
Temperature probe
FTIR
IR
chamber
beam
Detector

MFC
Purge or dilution gas Sample holder

Challenge
gas
Furnace
Moisture
UHP N2 source
MFC

APIMS CRDS
MFC MFC

Gas purifier system

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 Heating Element Design

Voltage Input Temperature

0V 25˚C
30 V 55˚C
45 V 80˚C
60 V 105˚C
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 FTIR Spectra of Moisture Adsorption on NPs
Overtone combination of SiO2, 20nm Due to hydrogen bonding,
stretching and bending for the liquid water stretch
water molecules. Wave vibration is shifted to a
number: 5200 cm-1 lower frequency. Wave
number: 3200 cm-1

The main stretching band

of water vapor. Wave
number: 3800 cm-1
Eliminate the effect of
gas phase Desorption process
SiO2, 20nm
SiO2, 20nm

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 Process Simulation: Single-Particle Domain
Adsorbent concentration in the gas phase:
𝜕𝐶𝑔𝑖𝑛 1 𝜕 2 𝜕𝐶𝑔𝑖𝑛 𝐴𝑠
= 𝐷𝑒𝑖𝑛 2 (𝑟 ) + [𝑘𝑑 𝐶𝑠𝑖𝑛 − 𝑘𝑎 𝐶𝑔𝑖𝑛 (𝑆0 − 𝐶𝑠𝑖𝑛 )]
𝜕𝑡 𝑟 𝜕𝑟 𝜕𝑟 𝑉
Diffusion term Adsorption and desorption term

Adsorbent concentration on the surface:

𝜕𝐶𝑠𝑖𝑛
= 𝑘𝑎 𝐶𝑔𝑖𝑛 (𝑆0 − 𝐶𝑠𝑖𝑛 ) − 𝑘𝑑 𝐶𝑠𝑖𝑛
𝜕𝑡
r=0 r=r0

Gas Phase
r

Substrate
Nanoparticle
Chemisorption Physisorption
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 Process Simulation: Packed-bed Domain
Adsorbent concentration in the gas phase:
𝜕𝐶𝑔𝑜𝑢𝑡 𝜕 2 𝐶𝑔𝑜𝑢𝑡 𝜕𝐶𝑔𝑖𝑛 2
= 𝐷𝑒𝑜𝑢𝑡 − 𝐷𝑒 | 𝑟=𝑟 4𝜋𝑟0 𝑁𝑣
𝜕𝑡 𝜕𝑥 2 𝑖𝑛
𝜕𝑟 0

Diffusion term in Diffusion flux from

packed-bed domain single-particle domain

Integral of absorbance peak over wavenumber:

𝜆2 𝜆2 𝐿 𝑟0
a
𝐴int = ‍𝐴𝑑𝜆 = ‍𝑎𝑑𝜆 ‍ ‍𝐶𝑠𝑖𝑛 (𝑟, 𝑥, 𝑡)𝑑𝑟𝑑𝑥.
𝜆1 𝑟0 𝜆1 0 0
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 Mechanism of Multilayer Model
Adsorption rate coefficients Desorption rate coefficients
−𝐸𝑎 −𝐸𝑑
𝑘𝑎 = 𝑘𝑎0 𝑒𝑥𝑝( ) 𝑘𝑑 = 𝑘𝑑0 𝑒𝑥𝑝( )
𝑅𝑇 𝑅𝑇

Adsorption activation energies Desorption activation energies

𝐶𝑠0 − 𝐶𝑠 𝐶𝑠 𝐶𝑠0 − 𝐶𝑠 𝐶𝑠
𝐸𝑎 = 𝐸𝑎1 + 𝐸𝑎2 𝐸𝑑 = 𝐸𝑑1 + 𝐸𝑑2 ,
𝐶𝑠0 𝐶𝑠0 𝐶𝑠0 𝐶𝑠0
1: Chemisorption 2: Physisorption

H H H H H H
OH OH OH OH OH
O O O O O O O

Si Si Si Si Si Si

O O O O O O O O O O O O

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 Numerical Method
Discretization Linearization Iteration
• Forward Euler Method • Next Time-step • Update the new value
• Crank-Nicolson Estimation for Cs, in
Method • Triangular Matrix • Update new value for
Solver ka, kd and so on

𝑚+1 𝑚
𝜕𝐶𝑔 𝐶𝑔,𝑖 − 𝐶𝑔,𝑖
=
𝜕𝑡 𝛥𝑡
2 𝑚+1 𝑚+1 𝑚+1 𝑚 𝑚 𝑚
𝜕 𝐶𝑔 1 𝐶𝑔,𝑖+1 − 2𝐶𝑔,𝑖 + 𝐶𝑔,𝑖−1 𝐶𝑔,𝑖+1 − 2𝐶𝑔,𝑖 + 𝐶𝑔,𝑖−1
= +
𝜕𝑥 2 2 Δ𝑥 2 Δ𝑥 2 𝑪𝒏𝒈,𝒐𝒖𝒕
1 𝑚+1 𝑚 𝑚
𝐶𝑔 = (𝐶𝑔,𝑖 + 𝐶𝑔,𝑖 ), 𝐶𝑠 = 𝐶𝑠,𝑖 .
2

𝑪𝒏+𝟏
𝒈,𝒊𝒏 𝑪𝒏𝒔,𝒊𝒏
𝛼Δ𝑡 𝑚+1 1 𝑚
𝛼Δ𝑡 𝑚+1
𝛼Δ𝑡 𝑚+1
𝐶 + [ (𝛿𝐶 − 𝛾)Δ𝑡 − − 1]𝐶 + 𝐶
2Δ𝑥 2 𝑔,𝑖+1 2 𝑠,𝑖
Δ𝑥 2 𝑔,𝑖
2Δ𝑥 2 𝑔,𝑖−1
𝛼Δ𝑡 𝑚 1 𝑚
𝛼Δ𝑡 𝑚
=− 2
𝐶𝑔,𝑖+1 + [− (𝛿𝐶𝑠,𝑖 − 𝛾)Δ𝑡 + 2
− 1]𝐶𝑔,𝑖
2Δ𝑥 2 Δ𝑥
𝑪𝒏+𝟏
𝒏+𝟏
𝒌𝒏+𝟏
𝒂 , 𝒌𝒅 ,
𝛼Δ𝑡 𝑚 𝑚 𝒔,𝒊𝒏
− 𝐶 − Δ𝑡𝛽𝐶𝑠,𝑖 ……
2Δ𝑥 2 𝑔,𝑖−1

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Comparison of Adsorption Profiles of NPs (I)

Sample Saturated surface Fractional Ea Ea Ed Ed

1 2 1 2
concentration coverage (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1)
CS (gmol·m-2) θ (%)
0
SiO2 (20 nm), 25˚C 2.0×10-6 67 9.0 6.0 16.0 12.5
SiO2 (20 nm), 55˚C 1.9×10-6 63 9.0 1.2 13.0 8.0
SiO2 (20 nm), 80˚C 1.5×10-6 50 9.0 0.1 7.6 5.7
SiO2 (80 nm), 25˚C 1.1×10-6 37 10.0 6.5 15.5 10.0
SiO2 (80 nm), 55˚C 1.0×10-6 33 10.0 2.0 12.5 5.5
SiO2 (80 nm), 80˚C 5.3×10-7 18 10.0 1.0 7.5 2.2

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Comparison of Adsorption Profiles of NPs (II)

Sample Saturated surface Fractiona Ea Ea Ed Ed

1 2 1 2
concentration l coverage (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1)
CS (gmol·m-2) θ (%)
0
CeO2 (20 nm), 25˚C 8.3×10-7 10.4 1.9 1.5 46 7.8
CeO2 (20 nm), 55˚C 8.2×10-7 10.3 1.9 1.2 30 8.1
CeO2 (20 nm), 105˚C 8.1×10-7 10.1 1.9 1.0 10 8.9
CeO2 (50 nm), 25˚C 5.5×10-7 6.9 3.0 0.1 19 5.3
CeO2 (50 nm), 55˚C 3.7×10-7 4.6 3.0 0.1 20 4.7
CeO2 (50 nm), 105˚C 3.6×10-8 4.5 3.0 0.1 9 5.0

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Comparison of Adsorption Profiles of NPs (III)

Sample Saturated surface Fractional Ea Ea Ed Ed

1 2 1 2
concentration coverage (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1) (kJ·gmol-1)
CS (gmol·m-2) θ (%)
0
HfO2 (20 nm), 25˚C 2.2×10-6 55 5.0 0.5 17.0 0.4
HfO2 (20 nm), 55˚C 1.5×10-6 38 5.0 2.8 23.5 0.7
HfO2 (20 nm), 80˚C 8.1×10-7 20 5.0 4.8 22.0 0.016
HfO2 (100 nm), 25˚C 4.4×10-7 11 12.5 10.5 16.5 4.6
HfO2 (100 nm), 55˚C 3.3×10-7 8.3 12.5 11.0 16.0 3.7
HfO2 (100 nm), 80˚C 3.1×10-7 7.8 12.5 12.0 11.0 2.6

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 Temperature Effect

Saturated Surface Concentration: 25˚C > 55˚C > 80˚C

*Taking HfO2, 20nm as an example

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 Temperature Effect

Adsorption energy for physisorption

Adsorption energy for chemisorption

Adsorption activation energy: 80˚C > 55˚C > 25˚C

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 Temperature Effect

Desorption activation energy: 80˚C > 55˚C > 25˚C

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 Activation Energy of Surface Processes

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 Size Effect on NP Surface Properties

• The surface retention characteristics depend on the particle size.

• Nanoparticles with smaller size will have larger density of surface sites and
larger surface retention capacity. They also have higher affinity for retention
of contaminants.

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 Size Effect on Energy of Surface Processes

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 Size Effect on Energy of Surface Processes

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 Size Effect on Energy of Surface Processes

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 Model Prediction on Desorption Time

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 Model Prediction on Desorption Time

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 Model Prediction on Desorption Time

SiO2 (20nm) ~ 90 min

HfO2 (20nm) ~ 110 min

CeO2 (20nm) ~ 8500 min

Size Effect: CeO2>SiO2>HfO2

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 Dimensionless Single NP Model
Dimensionless forms:
𝐶𝑔𝑖𝑛 𝐶𝑠𝑖𝑛 𝑟 𝑡 𝑘𝑎 𝑘𝑑
𝐶𝑔𝑖𝑛 = , 𝐶𝑠𝑖𝑛 = , 𝑟= , 𝑡= , 𝑘𝑎 = , 𝑘𝑑 =
𝐶𝑔𝑖𝑛,0 𝐶𝑠𝑖𝑛,0 𝑟0 𝑉 𝑘𝑎𝑐 𝑘𝑑𝑐
𝐴0 𝑘𝑎 𝑆0
Dimensionless governing equations:
𝜕𝐶𝑔𝑖𝑛 𝐷𝑒𝑖𝑛 𝑉 1 𝜕 2 𝜕𝐶𝑔𝑖𝑛 𝐶𝑠𝑖𝑛,0 𝑘𝑑𝑐 𝐶𝑠𝑖𝑛,0
= 2 (𝑟 )+ 𝐶 𝑘 − 𝑘𝑎 𝐶𝑔𝑖𝑛 + 𝑘 𝐶 𝐶
𝜕𝑡 𝑟0 𝐴0 𝑘𝑎𝑐 𝑆0 𝑟 2 𝜕𝑟 𝜕𝑟 𝐶𝑔𝑖𝑛,0 𝑘𝑎𝑐 𝑆0 𝑠𝑖𝑛 𝑑 𝑆0 𝑎 𝑔𝑖𝑛 𝑠𝑖𝑛

𝜕𝐶𝑠𝑖𝑛 𝐶𝑔𝑖𝑛,0 𝑉 𝐶𝑔𝑖𝑛,0 𝑉 𝑘𝑑𝑐 𝑉

= 𝑘𝑎 𝐶𝑔𝑖𝑛 − 𝑘𝑎 𝐶𝑔𝑖𝑛 𝐶𝑠𝑖𝑛 − 𝑘 𝐶
𝜕𝑡 𝐶𝑠𝑖𝑛,0 𝐴0 𝐴0 𝑆0 𝑘𝑎𝑐 𝐴0 𝑆0 𝑑 𝑠𝑖𝑛

Dimensionless groups:
𝐷𝑒𝑖𝑛 𝑉 𝐶𝑠𝑖𝑛,0 𝑘𝑑𝑐 𝐶𝑠𝑖𝑛,0
𝛼= , 𝛽= , 𝛾= ,
𝑟02 𝐴0 𝑘𝑎𝑐 𝑆0 𝐶𝑔𝑖𝑛,0 𝑘𝑎𝑐 𝑆0 𝑆0
𝐶𝑔𝑖𝑛,0 𝑉 𝐶𝑔𝑖𝑛,0 𝑉 𝑘𝑑𝑐 𝑉
𝜂= , 𝜃= , 𝜔= ,
𝐶𝑠𝑖𝑛,0 𝐴0 𝐴0 𝑆0 𝑘𝑎𝑐 𝐴0 𝑆0

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 Parametric Study

𝐷𝑒𝑖𝑛 𝑉
𝛼=
𝑟02 𝐴0 𝑘𝑎𝑐 𝑆0

𝛼 is the ratio of the characteristic time of

adsorption and characteristic time of diffusion

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 Parametric Study

𝐷𝑒𝑖𝑛 𝑉
𝛼=
𝑟02 𝐴0 𝑘𝑎𝑐 𝑆0

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 Summary and Conclusions
Hydroxylation is a powerful method for characterization of
capture and retention (adsorption/desorption) properties of
NPs.

The surface retention characteristics depend on the material as

well as on the particle size and temperature.

NPs with smaller size will have larger density of surface sites
and larger surface retention. They also have higher affinity for
retention of contaminants. Based on the size effect on energy,
smaller NPs would have higher desorption activation energy
and lower adsorption activation energy.

Purge under the higher temperature would benefit the

desorption of moisture on the NP surface.

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 Future Work

Keep on studying Parametric study Upgrade the

the surface based on the numerical model
properties of other dimensionless single and increase the
NPs NP model efficiency

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 Publications and Presentations
• Hao Wang, F. Shadman, Effect of Particle Size on the Adsorption and Desorption
Properties of Oxide Nanoparticles, Submitted to AIChE, April, 2012
• Hao Wang, J. Yao, F. Shadman, Characterization of the Surface Properties of
Nanoparticles Using Moisture Adsorption Dynamic Profiling, Chemical
Engineering Science, June 2011
• Hao Wang, Characterization of the Surface Properties of Nanoparticles Using
Moisture Adsorption Dynamic Profiling, SRC/SEMATECH Teleconference, July
2011 [PRESENTATION]
• Hao Wang, Physicochemical and Surface Characteristics Study of Nanoparticles
related to ESH Impact of Emerging Nanoparticles and Byproduct in Semiconductor
Manufacturing, SRC/SEMATECH Teleconference, November 2010
[PRESENTATION]

Acknowledgment
• SRC/SEMATECH Engineering Research Center
• Farhang Shadman, Professor of Chemical and Environmental Engineering, UA.
• Reyes Sierra, Professor of Chemical &Environmental Engineering, UA.
• Buddy Ratner, Professor of Bioengineering, UW.
• Junpin Yao, Matheson Tri-Gas Inc.
30
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