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

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

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, 4670-4679 3 UDaily Archive April 9, 2007

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% H2 (light) Volumetric Capacity= 45 g H2/l (compact) System Storage Cost= $4 /kWh (cheap) for future H2 powered technologies.

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

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 = ~50-100 kJ/mol) Metal Hydrides Complex Hydrides Status of hydrogen storage vs. system targets as of 20071 1 Annual Progress Report, DOE Hydrogen Program, 2007

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

Specific Surface Area: 300-450 m2/g CARBONIZATION OF CFF Images of surface of untreated and carbonized chicken feather fibers (CCFF) Specific Surface Area: 300-450 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

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) 400-450 0C 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 210-220 0C 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), 109-115 (1993)

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

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= 300-450 m2/g SSA Activated Carbon= 1500 m2/g SSA: Specific Surface Area

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) 2209-2214

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) 2209-2214

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

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, 11418-11424

ACKNOWLEDGEMENTS This project was supported by the National Research Initiative of the USDA Cooperative State Research, Education and Extension Service, grant number 2005-35504-16137. Anne Dillon - National Renewable Energy Laboratory The Wool Research Group The Lobo Group George Whitmyre- Colburn Lab Manager

Background Chemisorption Physisorption (∆Hads= ~4 kJ/mol) Binding Energy Methane C-H bonds (~400 kJ/mol) Chemisorption (∆Hads = ~50-100 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