Project Report

East Asian Pacific Summer Institute (EAPSI) June 10th – August 7th 2011 Principle Investigator: James T. Hughes Peter A. Rock Thermochemistry Laboratory Department of Chemistry University of California at Davis Davis, CA 95616, United States Host Advisor: Professor Wen-Hua Sun, FRSC Institute of Chemistry, Chinese Academy of Science Beijing, P.R. China Background Over the six weeks research at the Institute of Chemistry Chinese Academy of Science, in Beijing Peoples Republic of China (ICCAS). Over 100 of solvothermal reactions on two different metal-organic framework (MOF) systems were performed. This resulted in the synthesis of the first isostructural lanthanide MOF series to date. The MOF construction based on combining bidentate organic "linker" molecules with "hub" atoms, in this case lanthanide metals. Each hub in these structures contains two lanthanide metal atoms that bind four adjacent linkers creating a 3D array that is analogous to a tinker toy structure. Where sticks and joints combine to form a rigid superstructure yet contains immense void space within the framework. The linker molecules chosen were 1,4 benzene dicarboxylic acid (1,4-BDC) and 3,5-pyridine dicarboxylate (3,5-PYDC) comprised the two MOF systems selected. These organic molecules were combined with the nitrate salts of all the entire lanthanide series with the exception of Promethium. Summary Understanding the material properties of the lanthanides hybrid material is an important chemical and material science concern. As such materials are analogous to materials found in radioactive storage processes. Synthesis of lanthanide frameworks from 1,4-BDC resulted in an two separate iso-crystalline structure. The first polymorph, which shows the highest crystallinity, uses the atoms Y, and Sm to Lu, to create a rigid 3D framework. The second iso-crystalline phase, spanning the atoms from La to Nd, created a yet to be identified phase. These structural series follows a well known trend of the lanthanide metals as the former framework being constructed of the atoms contained in the yttria subgroup; the latter phase is comprised of atoms found the ceria subgroup. These subgroups are due to similar atomic size of the metal cations. As a result in the interest time, efforts were shifted to scaling up the successful 1,4-BDC based reaction. Making it possible to obtain high quality material required for thermodynamic analysis. I was able to return to UC Davis with plenty of material for proper analysis. Cultural and Educational Experiences I made several close friendships with my lab mates during my summer at the ICCAS. My work scheduled followed theirs: Monday to Saturday 8 am to 10 pm, I had the chance to spend at least 80 hours a week working in close proximity with my lab mates. Every Sunday several students and myself would tour Beijing, seeing local sites, eating out and shopping, if nothing else. Overall I was pleased that during my two months in China I never rested, I spent most days with my lab mates. As they worked very hard they spend a lot of time together. I enjoyed these new friendships and cultural immersion my environment presented immensely. Despite working in my home laboratory, of which about ~40% originate from Asian countries’, living in Beijing was a totally unique experience that cannot be aptly understood unless one is there. There were so many unique events during my time there, some great, some unpleasant but overall I felt grateful to have the opportunity to observe a day to day life from a different point of view, yet still be productive. I found having an open mind was crucial, as many customs and behaviors are different or can seem strange, as one may expect. Though this does beg the question "what is it that Americans do that is weird?". Seeing a how other humans go through life lets one realize to look inward at what one considers typical and why this is so. I continue to remain in contact with several of my Chinese colleagues and this fall I have helped guide two of them through the application process to American graduate schools. Proofreading papers and giving advice on proper English style and etiquette. Training and Development This summer experience provided the principle investigator with experience designing, performing and characterizing a systematic organometallic synthetic study.

National Science Foundation (NSF)
Office of International and Integrative Activities (IIA)
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Carter Kimsey
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Hughes James T
United States
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