NSF-Europe Materials Collaboration: Self-Organized Nanostructured Thin Films for Catalysis in Perovskite Related Membrane Reactors (DMR-0502765) PI: Jag.

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NSF-Europe Materials Collaboration: Self-Organized Nanostructured Thin Films for Catalysis in Perovskite Related Membrane Reactors (DMR ) PI: Jag Sankar (North Carolina A&T State University) Co-PI: Nina Orlovskaya (Michigan Technological University) European Collaborator: Vladislav Kharton (University of Aveiro, Portugal) Intellectual merit Collaborative research between NC A&T SU, MTU and the University of Aveiro (Portugal) is focused on new catalytically active oxygen-permeable membrane materials for gas separation. The complete characterization of electrical, electrochemical, structural, thermal and catalytic properties of new promising (La 0.9 Sr 0.1 ) 0.95 Cr 0.85 Mg 0.1 Ni 0.05 O 3 perovskite material has been performed. Sinterability, room and high temperature crystal structure parameters, oxygen permeability, phase stability, stoichiometry, vibrational properties, and mechanical behavior have been studied. Crystal design is a key parameter in the development of catalytic membranes where the edges and surfaces are critically important to drive chemical reactions in the required directions. Polyhedral surface termination steps with a 9-fold symmetry have been discovered on the internal surfaces of orthorhombically distorted (La 0.9 Sr 0.1 ) 0.95 Cr 0.85 Mg 0.1 Ni 0.05 O 3 perovskite. The nanogons are usually formed at the corners of the grains in the (111) planes of the orthorhombic structure. The steps might appear as a result of the preferential grain growth kinetics during heating. The steps might also be the sites where twins terminate at the free surface, since these orthorhombic perovskites are heavily twinned. The primary implication of this discovery is that such step edges are potentially perfect sites for numerous catalytic reactions, facilitating syngas production, or catalytic conversion of CO 2 by splitting the C-O bond into different value added products such as CO, CH 4, methanol, or ethanol in the presence of steam. An unusual 9-fold symmetry of the polyhedral surface termination steps in (La 0.9 Sr 0.1 ) 0.95 Cr 0.85 Mg 0.1 Ni 0.05 O 3 TEM image of reduced catalyst particle

“NSF-Europe Materials Collaboration: Self-Organized Nanostructured Thin Films for Catalysis in Perovskite Related Membrane Reactors” (DMR ) (Lead: NC A&T SU Co-Lead: MTU) An unusual 9-fold symmetry of the polyhedral surface termination steps in (La 0.9 Sr 0.1 ) 0.95 Cr 0.85 Mg 0.1 Ni 0.05 O 3 N. Orlovskaya (Michigan Technological University), J. Sankar and S. Yarmolenko (NC A&T State University)

Dr. S. Yarmolenko (NCAT) visited the University of Aveiro (Portugal) to present current results and discussed plans for collaborative research. During this visit, details of development of oxygen permeability measurement setup at NCAT, technical exchange between partnering institutions, student participation and exchange were carefully planned. Research results of two graduate students Brandon Hancock and Kristofer Gordon (NCAT) were submitted to the 31st International Cocoa Beach Conference & Exposition on Advanced Ceramics and Composites for oral presentation. MTU PhD student Matthew Swanson was awarded a prestigious international 6-month fellowship at EMPA, Duebendorf, Switzerland where he works on the electrical characterization of the prospective membrane materials. Rachel Rosten, MTU undergraduate student, won 1st place and the George Kehl plaque for her poster “Surface termination steps as active catalyst sites in La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3 ” and honorable mention for her poster “9-fold symmetry of the surface termination steps of (La 0.9 Sr 0.1 ) 0.95 Cr 0.85 Mg 0.1 Ni 0.05 O 3 ” in the International Metallographic Contest held at the International Metallographic Society Conference in Chicago (August 2006). She was awarded a summer undergraduate research fellowship to support her research on the project. She also presented her results at the Gordon Research Conference on Solid State Studies in Ceramics. The results of her work have been accepted for oral presentation on MRS meeting in Boston (November 2006). Based on these results, one paper “A guide to the calculation of theoretical densities of crystal structures for SOFCs” with two other summer undergraduate participants as co-authors was accepted to the Journal of Undergraduate Materials Research and another paper is under preparation for submission to Solid State Ionics. NSF-Europe Materials Collaboration: Self-Organized Nanostructured Thin Films for Catalysis in Perovskite Related Membrane Reactors (DMR ) Broader Impact Project web-site has been developed under the umbrella of the Center for Advanced Materials and Smart Structures (NC A&T SU). This fully database driven web-site facilitates collaboration and secure data exchange between partner institutions. Student Participation / Broader Impact: Brandon Hancock and Kristofer Gordon (MS) African American minority students Matthew Swanson (PhD) Rachel Rosten (BS) – undergraduate female student Rachel Rosten discusses her results with a participant at the Gordon Research Conference (New Hampshire, August 2006)