This document summarizes research into using hydrogenase enzymes and glycerol to produce hydrogen as an alternative energy source. It discusses different biological and photolytic methods for hydrogen production and their limitations. The document focuses on using hydrogenase enzymes directly as electrocatalysts for fuel cells, looking at improving their stability and activity when integrated into electrode materials. Overall the research aims to develop hydrogenase-based technologies as alternatives to platinum in fuel cells and electrolysis.

1. Reviewed by Holden Ranz
ChE 391: Independent Study
Advised by Professor Piergiovanni

2. Original Interest
 Alternative energy  Algae
 What can be done to make
algae fuel more sustainable?
 Biodiesel processing
generates residual glycerol
 Certain unicellular organisms
can produce H2
○ Glycerol be used as substrate
for H2 production?

3. Fermentative Hydrogen
 Dark Fermentation
 glycerol 
1,3-propanediol
+ hydrogen
 Biological limitations
 Require carbohydrates
 Low yields of energy
 Specific T, P, pH requirements
Enterobacter
Clostridium

4. Fermentative Hydrogen
 Photofermentation
 photosynthetic bacteria
(purple non-sulfur)
Rhodopseudomonas Rhodobacter

5. Biophotolysis
 Light-driven decomposition
of water
 Direct Biophotolysis
 green algae, cyanobacteria
 Advantages:
○ High solar energy conversion
 Disadvantages:
○ O2 inhibition

6. Biophotolysis
 Indirect Biophotolysis
 cyanobacteria
 Advantages:
○ Able to fix N2 from atmosphere
 Disadvantages:
○ Lower efficiency than direct

7. Biohydrogen Downfalls
 Low yields
 Inhibition of hydrogen production
 Requires low levels of H2, O2
 Gas separation needed
 Biological sensitivity
 Metabolic pathways for alcohol
formation

8. Evolved Interest
 Hydrogenase enzymes
 Catalyzes redox: 2H+  H2
 Can hydrogenases be used as electrocatalysts for fuel
cell applications?
Surprising
amount of
development in
FC technology
and enzymes!

9. Hydrogenase Enzymes
 Serve function that is closely related to needs
for technological systems
 Can be used in multiple alternative energy
applications

10. Active Site
 Nature uses nickel, iron, and sulfur for H2
production/activation
 Fe-Fe (Clostridium)
 Ni-Fe
 Hydrophobic channels

11. Enzyme Electrodes
 Anodes
 Cathodes
 Stability/structure
 Adsorption to carbon
support
○ PGE, GCE, carbon felt
 Encapsulation in polymeric
porous gels
○ Si-O-Si network

12. Progress of Enzyme Electrodes
 CO poisoning not an issue
 Energy conversion of enzyme electrode
comparable to noble metal based
commercial fuel electrode
 Alternative for fuel cells and electrolysis

13. Continuing Research
 Improving electrode
stability and activity
 Doping of sol-gel
○ Methyl viologen
○ Carbon nanotubes
 Integration of
photosystem
 Porphyrin - TiO2
colloidal system

14. References
 Adhikari, Sushil, Sandun Fernando, and Agus Haryanto. "Hydrogen Production from
Glycerin by Steam Reforming over Nickel Catalysts." Renewable Energy 33 (2008):
1097-100. Web.
 Demirbas, Ayhan. "Progress and Recent Trends in Biofuels." Progress in Energy and
Combustion Science 33 (2007): 1-18. Web.
 Ito, Takeshi, Yutaka Nakashimada, Koichiro Senba, Tomoaki Matsui, and Naomichi
Nishio.
 "Hydrogen and Ethanol Production from Glycerol-Containing Wastes Discharged after
Biodiesel Manufacturing Process." Journal of Bioscience and Bioengineering 100.3
(2005): 260-65. Web.
 Liu, Fei, and Baishan Fang. "Optimization of Bio-hydrogen Production from Biodiesel
Wastes by Klebsiella Pneumoniae." Biotechnology Journal 2 (2007): 374-80. Web.
 Yang, Zhiman, Rongbo Guo, Xiaohui Xu, Xiaolei Fan, and Shengjun Luo.
"Fermentative Hydrogen Production from Lipid-extracted Microalgal Biomass
Residues." Applied Energy 88.10 (2011): 3468-472. Print.
 Yu, J., and P. Takahashi. "Biophotolysis-based Hydrogen Production by Cyanobacteria
and Green Microalgae." Http://www.formatex.org/microbio/pdf/Pages79-89.pdf. 2007.
Web. 19 Feb. 2012.
 "Improvement of Fermentative Hydrogen Production: Various Approaches." Web.
 http://www.fao.org/docrep/w7241e/w7241e06.htm
 http://www.bw2e.com/images/dia2.gif
 http://www.hielscher.com/image/biodiesel_process_chart_p0500.gif
 http://www.theprofessionalgroup.com/Enterobacter.html
 http://world.edu/wp-content/uploads/2011/12/cyanobacteria1.jpg
 http://www.microscopy-uk.org.uk/mag/indexmag.html?http://www.microscopy-
uk.org.uk/mag/wimsmall/green.html

15. Questions?