To mitigate many of the potentially deleterious environmental and agricultural consequences associated with current landbased-biofuel feedstocks, we advocate the use of biofuels derived from aquatic microbial oxygenic photoautotrophs (AMOPs), more commonly known as algae, cyanobacteria and diatoms. Our research on AMOPs addresses:
- Demonstrated productivity in mass culturing and future potential as biomass energy crops
- Use as cell factories for production of gaseous fuels (H2, CH4)
- Fundamental photosynthetic physiology and mechanisms
- Genetic transformants for understanding mechanisms and improving fuel production.
We develop selective and robust catalysts that electrochemically convert carbon dioxide (CO2) into sustainable chemical feedstocks and could ultimately be coupled to the recycling of environmental CO2. The catalysts employed are transition metal phosphides and their doped derivatives that form distinct crystalline structure types, enabling selection of chemical reactivity towards desired products including high molecular weight solid polymers. Selecting the catalyst’s elemental composition and crystal structure allows for tuning of the chemical, physical, and electrical properties to achieve the best match with desired product and application.
Transition metal phosphides are efficient hydrogen evolution catalysts due to their ability to abstract protons from water and transfer electrons to them, forming adsorbed hydrides. Since CO2 reduction also requires multiple transfers of adsorbed hydrogen and electrons, these catalysts are also effective for the reduction of CO2. Additionally, these catalysts bind CO2 relatively strongly, allowing for the formation of C3, C4 and Cn products at ambient conditions and aqueous solution. It is also our belief that when utilizing iron and nickel phosphides, the reaction proceeds through hydride transfer, and therefore carbon monoxide is not an intermediate. This opens up a new reaction pathway with minimal overpotential requirements.
Selective CO 2 Reduction to C 3 and C 4 Oxyhydrocarbons on Nickel Phosphides at Overpotentials as Low as 10 MV.
Calvinho, Karin U. D., Anders B. Laursen, Kyra M. K. Yap, Timothy A. Goetjen, Shinjae Hwang, Bryan Mejia-Sosa, Alexander Lubarski, et al. 2018. “Selective CO 2 Reduction to C 3 and C 4 Oxyhydrocarbons on Nickel Phosphides at Overpotentials as Low as 10 MV.” Energy & Environmental Science. The Royal Society of Chemistry. doi:10.1039/C8EE00936H.
Climbing the Volcano of Electrocatalytic Activity While Avoiding Catalyst Corrosion: Ni3P, a Hydrogen Evolution Electrocatalyst Stable in Both Acid and Alkali.
Laursen, A.B., R.B. Wexler, M.J. Whitaker, E.J. Izett, K.U.D. Calvinho, S. Hwang, R. Rucker, et al. 2018. “Climbing the Volcano of Electrocatalytic Activity While Avoiding Catalyst Corrosion: Ni3P, a Hydrogen Evolution Electrocatalyst Stable in Both Acid and Alkali.” ACS Catalysis 8 (5): 4408–4419. doi:10.1021/acscatal.7b04466.
Thin Film Catalysts: Ni5P4 (Cathodic) and LiCoO2 (Anodic) for Electrolysis of Water.
Hwang, S.; Porter, S. H.; Gardner, G.; Laursen, A. B.; Wang, H.; Li, M.; Amarasinghe, V.; Taghaddos, E.; Safari, A.; Garfunkel, E.; Greenblatt, M.; Dismukes, G. C. 2016. Thin Film Catalysts: Ni5P4 (Cathodic) and LiCoO2 (Anodic) for Electrolysis of Water. ECS Trans, 72(23), 31–51.
Optimizing “Artificial Leaf” Photoanode-Photocathode-Catalyst Interface Systems for Solar Water Splitting.
Porter, S. H.; Hwang, S.; Amarasinghe, V.; Taghaddos, E.; Manichev, V.; Li, M.; Gardner, G.; Safari, A.; Garfunkel, E.; Greenblatt, M.; Dismukes, G. C. 2016. Optimizing “Artificial Leaf” Photoanode-Photocathode-Catalyst Interface Systems for Solar Water Splitting. ECS Trans., 72 (37), 1–19.
Dr. G. Charles Dismukes
G. Charles Dismukes is a Distinguished Professor at Rutgers University on the faculties of the Chemistry & Chemical Biology Department and the Waksman Institute of Microbiology. He is a member of the executive committee of the Institute for Advanced Materials and Device Nanotechnology (IAMDN), the Rutgers Energy Institute (REI), and the graduate training faculty in Microbiology and Biochemistry.
The Dismukes research group investigates the science of catalysis particularly photo- and electro-catalysis, using an integrated theoretical-experimental approach that incorporates knowledge from biology, chemistry and physics to understand the fundamental principles and translate that knowledge into proof of principle devices and solutions. They study systems extending from natural photosynthetic organisms and isolated enzymes to artificial photosynthetic constructs and solar fuel cells.
Topics include water splitting, carbon dioxide capture and reduction to chemicals, carbon metabolism in phototrophs, dinitrogen capture and reduction.