This award is funded under the American Recovery and Reinvestment Act of 2009 (Public Law 111-5).
The International Research Fellowship Program enables U.S. scientists and engineers to conduct nine to twenty-four months of research abroad. The program's awards provide opportunities for joint research, and the use of unique or complementary facilities, expertise and experimental conditions abroad.
This award will support a twenty-four-month research fellowship by Dr. Joseph J. Zakzeski to work with Dr. Bert M. Weckhuysen at Utrecht University in the Netherlands.
The conversion of biomass, such as wood, agricultural crops, and agricultural wastes, into transportation fuels and other valuable chemicals is becoming increasingly important as a way to transition energy consumption away from fossil fuels. Lignin is an important fraction of biomass, which has received little attention to date in the field of renewable catalysis, and its valorization for fuel and chemical applications is in its infancy. The relevant issues that arise during catalytic development include structure-reactivity relationships, active site design by tuning the ligand characteristics, and routes to catalyst deactivation and poisoning. Rational catalyst design requires a detailed understanding of these issues, which strongly depend on reaction conditions, catalyst composition, and solvent characteristics. Fortunately, the development of a wide range of characterization techniques has provided important new insight into many of these issues, which has subsequently allowed improvements in catalyst design with wide-spread industrial implications. The most pertinent spectroscopic information is obtained in-situ because it concerns the study of the catalyst material in its active form, where structure and electronic considerations dictate catalytic performance. The objective of this work is to test the hypothesis that rational alterations of structural and electronic properties of transition metal complexes, monitored by in-situ spectroscopic techniques, and appropriate choice of solvent system can allow low-temperature (<100°C) and low-pressure (<10 bar) biomass valorization processes with high catalytic activity and selectivity. In order to achieve these ambitious goals, various in-situ spectroscopic analytical techniques, including UV-visible, Raman, ATR-IR, and XAFS spectroscopy, are being used to correlate changes in catalyst properties to catalyst performance in a wide range of solvents ranging from water to ionic liquids. The successful development of these in-situ techniques provides critical information necessary for rational catalyst design and important structural/activity relationships for the production of a wide-range of industrially important chemicals from lignin.
This work contributes to the understanding of structure-reactivity relationships, ligand characteristics, conditions and factors that cause catalyst deactivation including poisoning, and catalyst re-usability for biomass valorization processes. The development of in-situ techniques for characterizing first-row transition metals provides strategies for the design of industrial catalytic systems, especially those that involve strongly adsorbing solvent systems. Results from this work contribute to the production of transportation fuels and other useful chemicals from biomass, a resource of which the United States has ample supply, and diversifies fuel production away from fossil fuels. In addition, this work benefits society through sustainable energy production, safer process operation using milder conditions, and fewer undesirable byproducts and greenhouse gas emissions.
