1. HYDROGEN STORAGE ON CARBONIZED CHICKEN FEATHER FIBERS
Erman Senoz, Richard P. Wool
Department of Chemical Engineering
University of Delaware
12th Annual Green Chemistry & Engineering Conference, June 25, 2008

2. OUTLINE Introduction Experimental Results Conclusions
Hydrogen
Objectives
Storage Problem
Structure of Chicken Feather Fibers (CFF)
Experimental Results
Surface Analyses
Hydrogen Adsorption Device (Sievert’s Apparatus)
Hydrogen Storage Results
Conclusions
Future Research Plans

3. Hydrogen as Energy Carrier
Why hydrogen?
Clean source, no CO2 emission, only product is H2O for fuel cell application
Energy density is ~3 times larger than gasoline1
Fuel cells are at least 2 times more efficient than combustion engines2
Production and storage of H2 are main bottlenecks for using it as a fuel
Hydrogen Powered UD Bus3
1 Louis Schlapbach, MRS Bull., 2002
2 Jesse L. C. Rowsell and Omar M. Yaghi, Angew. Chem. Int. 2005,44,
3 UDaily Archive April 9, 2007

4. OBJECTIVES for future H2 powered technologies.
To find the best process to obtain H2 storage material from waste materials, chicken feather fibers (CFF).
To fulfill Department of Energy’s (DOE) 2010 H2 storage targets which are
Gravimetric Capacity= 6 wt% H (light)
Volumetric Capacity= 45 g H2/l (compact)
System Storage Cost= $4 /kWh (cheap)
for future H2 powered technologies.

5. How to reach 300 miles range?
DOE Target
Hydrogen’s extreme low density requires huge tanks!
Relatively high wt% H2 storage values has to be achieved!
Material has to be as cheap as possible!
Required adsorbent mass and CCFF tank volume to build a car with 300 miles range

6. Status of hydrogen storage vs. system targets as of 20071
Background
Physisorption (∆Hads= ~4 kJ/mol)
Graphite
Carbon Nanofibers
Carbon Nanotubes
Metal Organic Frameworks (MOF)
Activated Carbon
Chemisorption
(∆Hads = ~ kJ/mol)
Metal Hydrides
Complex Hydrides
Status of hydrogen storage vs. system targets as of 20071
1 Annual Progress Report, DOE Hydrogen Program, 2007

7. Chicken Feather Fiber (CFF) Properties
Agricultural waste
Very cheap!
6 μm diameter1
92% Keratin2
Hollow tubes1
Low density
SEM image of CFF, 1000X magnification
α-helix Keratin
Structure
Feather Fiber Structure3
1 Hong, Chang K and Richard P. Wool “Development of a Bio-based Composite Material from Soybean Oil and Keratin Fibers” 2005
2 Farner, Donald S. et al. Avian Biology. vol 6. Academic Press, New York: 1982.
3 Martinez-Hernandez A. L., Velasco-Santos C., de Icaza M., and Castano V. M, Int. J. Env. Pol, Vol. 23, No 2, 2005

8. Specific Surface Area: 300-450 m2/g
CARBONIZATION OF CFF
Images of surface of untreated and carbonized chicken feather fibers (CCFF)
Specific Surface Area: m2/g
Average Pore Size: 5-10 Å
230 oC
Temperature (oC)
Differential Scanning Calorimetry (DSC) Curve
Thermal Gravimetric Analysis (TGA) Curve1
1 C. W. J. McChalicher’s Thesis, Chemical Engineering, University of Delaware

9. XPS ANALYSIS OF PYROLYSIS OF CFF
Fatty Acid
Protein Matrix
Elemental Keratin Composition
Carbon: 59.4 %
Oxygen: 22.4 %
Nitrogen: 17.9 %
C-(C,H)
C-(C,H) C
Carbon
50.0 %
Oxygen
31.3 %
Nitrogen
18.6 %
Carbon
79.2 %
Oxygen
14.6 %
Nitrogen
6.3 %
C-(O,N)
Keratin Fiber Surface Model1
C=O C
C-(C,H)
C-(C,H)
Carbon
66.5 %
Oxygen
22.2 %
Nitrogen
11.3 %
Carbon
86.4 %
Oxygen
9.4 %
Nitrogen
4.1 %
C-(O,N)
C=O
C=O
O-C=O
1 Negri, P., N. and Cornell H., Textile Res. J. 63(2), (1993)

10. H2 STORAGE (SIEVERT’S) APPARATUS
reservoir
pressure transducer
sample
holder

11. H2 STORAGE RESULTS CCFF-CycleA: Heating CFF at 420 0C for 1 hr
CCFF-CycleB:
Heating CFF at 420 0C for 1.5 hr
CCFF-CycleC:
Heating CFF at 420 0C for 2 hr
SSA CCFFs= m2/g SSA Activated Carbon= 1500 m2/g
SSA: Specific Surface Area

12. Hydrogen adsorption isotherms at room temperature and 77 K for CCFF
H2 STORAGE RESULTS
T=77 K
T=298 K
Hydrogen adsorption isotherms at room temperature and 77 K with Henry type and Langmuir type equation for purified SWCNTs1
Hydrogen adsorption isotherms at room temperature and 77 K for CCFF
1 B. Panella et al., Carbon 43 (2005)

13. CONCLUSIONS
Surface of the fibers is not completely keratin, carbonization doesn’t increase the carbon content.
2 wt% H2 storage capacity at 77 K
H2 storage capacity of CCFF is as high as that of purified SWCNTs1
CNT: ~ $1.2 million
Metal Hydride: ~ $30 000
CCFF: ~ $200
200 kg
1 B. Panella et al., Carbon 43 (2005)

14. FUTURE RESEARCH PLANS
Continue searching for better pyrolysis paths especially to obtain higher surface are materials
Optimize the average pore size for high storage capacities
Increase the accuracy of the Sievert’s apparatus
Use Thermogravimetric Analysis (TGA) with mass spectrometer

15. FUTURE RESEARCH PLANS
Investigate the effect of dispersion of various metals on hydrogen storage
SEM image of 10% Ag on CCFF taken in National Institute of Aerospace in Virginia
Spillover Mechanism1
1 Lachawiec A. J. et al., Langmuir 2005, 21,

16. ACKNOWLEDGEMENTS
This project was supported by the National Research Initiative of the USDA Cooperative State Research, Education and Extension Service, grant number
Anne Dillon - National Renewable Energy Laboratory
The Wool Research Group
The Lobo Group
George Whitmyre- Colburn Lab Manager

17. Background Chemisorption Physisorption (∆Hads= ~4 kJ/mol)
Binding Energy
Methane C-H bonds (~400 kJ/mol)
Chemisorption
(∆Hads = ~ kJ/mol)
Metal Hydrides
Complex Hydrides
Physisorption (∆Hads= ~4 kJ/mol)
Graphite
Carbon Nanofibers
Carbon Nanotubes
Metal Organic Frameworks (MOF)
Activated Carbon
Status of hydrogen storage vs. system targets as of 20071
1 Annual Progress Report, DOE Hydrogen Program, 2007