Intellectual Merit: Electrolysis of water is an electrochemical process that generates hydrogen from water. Hydrogen is a key energy source and chemical, widely used in a number of important industrial processes. One of the drawbacks with this process is that it is energy intensive. In this proposal, we describe an approach that uses the chemical energy of a biofuel, a renewable source of energy - its processing leads to no net CO2 emissions - to run water electrolysis using solid oxide electrolyzers (SOEs). Biofuel-assisted SOEs are solid-state electrolyzers that, in principle, can electro-oxidize any oxygenated hydrocarbon (i.e. a biofuel) at the anode, and utilize its chemical energy internally to drive the electrochemical water splitting at the cathode. Our preliminary results show that the main challenges with SOEs operating with biofuels such as ethanol are: (i) the high overpotential losses at the cathode induced by the high activation energy barrier required to split water on the conventional cathode materials and (ii) the poor stability of the conventional anode materials due to carbon poisoning. The PI's long-term research goal is to develop robust SOE electrode (anode and cathode) materials that can efficiently generate pure H2 from water using the chemical energy of any biofuel source. In this two year BRIGE proposal, the overall objective is to identify robust SOE anode and cathode materials for ethanol-assisted SOEs. We will initially focus on ethanol, since it represents a reasonable model biofuel, containing both C-O and C-C bonds, characteristic of any biofuel molecule. It is our central hypothesis that modifying conventional monometallic SOE electrode materials (such as Ni, Co at the cathode and Ni at the anode) via alloying with another element (such as Ru, Rh at the cathode and Sn, Au, Ag at the anode) will induce geometric and electronic changes to the parent metal surface that will impact the chemistry on these surfaces and lead to improved performance. We propose to employ a combined experimental/theoretical approach to unearth the surface chemistry that governs (i) the process of electrochemical water splitting on cathode materials (such as Ni, Co, Ni/Ru, Ni/Rh, Co/Ru and Co/Rh alloy) and (ii) the stability of the anode materials (such as Ni and Ni/Sn, Ni/Ag and Ni/Au alloy). This information will allow us to identify the electrode materials with the outmost activity and stability. We expect that this work will lead to the development of robust SOEs systems that use the chemical energy of ethanol to drive the production of clean H2 from water. In addition, it will provide significant fundamental insights that can be utilized (i) to achieve the PI's long-term research goal and (ii) to develop other electrochemical systems that involve similar chemistries. Broader Impact: The proposed research has broader impact in terms of science and engineering, training and education. The fundamental insights obtained in this project have the potential to move the field of SOEs significantly forward by (i) determining the surface chemistry that governs the electrochemical reactions at the SOE electrodes and (ii) developing improved SOE electrode materials. In addition, these insights can be used to develop other systems that involve similar chemistries such as fuel cells and low temperature electrolyzers. This work will also contribute to the enhancement of the undergraduate and graduate curriculum at WSU. The PI plans to use the fundamental electrochemical insights obtained from this project to design a course, for senior undergraduate and graduate students, titled "Fundamentals of Electrochemistry'. In addition, the PI has arranged for undergraduate students from underrepresented minorities at WSU to work in the lab this summer through the Initiative for Maximizing Student Development (IMSD) and The Michigan-Louis Stokes Alliance for Minority Participation (LSAMP) Programs. The PI is establishing partnerships with the broader community and local high schools in the area to educate and inspire students from traditionally underrepresented minorities to pursue a career in science and engineering. More specifically, the PI is arranging field trips and demonstration experiments for 11th and 12th graders from the Pontiac and Bethune Alternative Academy High Schools in Pontiac, Michigan. In addition, she plans to recruit two senior high school students to work in her laboratory as a summer internship.
