International Research Fellowship Progr.: Development of In-situ Spectroscopic Characterization Techniques to Understand & Optimize Catalytic Conversion Routes for Biomass Va

0856754 Zakzeski该奖项是根据2009年美国复苏和再投资法案（公法111-5）资助的。国际研究奖学金计划使美国科学家和工程师能够在国外进行9到24个月的研究。 该计划的奖项提供了联合研究的机会，以及使用独特或互补的设施，专业知识和国外的实验条件。该奖项将支持由博士约瑟夫J. Zakzeski二十四个月的研究奖学金与博士伯特M。将木材、农作物和农业废弃物等生物质转化为运输燃料和其他有价值的化学品，作为能源消费从化石燃料转变的一种方式，正变得越来越重要。 木质素是生物质的重要组成部分，其迄今在可再生催化领域中很少受到关注，并且其用于燃料和化学应用的价值正在起步阶段。 在催化剂开发过程中出现的相关问题包括结构-反应性关系、通过调整配体特性进行的活性位点设计以及催化剂失活和中毒的途径。合理的催化剂设计需要对这些问题有详细的了解，这些问题在很大程度上取决于反应条件、催化剂组成和溶剂特性。 幸运的是，广泛的表征技术的发展为许多这些问题提供了重要的新见解，这随后允许改进催化剂设计，具有广泛的工业影响。 最相关的光谱信息是在原位获得的，因为它涉及到活性形式的催化剂材料的研究，其中结构和电子因素决定了催化性能。 这项工作的目的是测试的假设，过渡金属配合物的结构和电子性质的合理改变，监测原位光谱技术，和适当的溶剂系统的选择可以允许低温（100°C）和低压（10巴）的生物质稳定过程具有高催化活性和选择性。为了实现这些雄心勃勃的目标，各种原位光谱分析技术，包括UV-可见光，拉曼，ATR-IR和XAFS光谱，正在被用来关联催化剂性能的变化，催化剂在从水到离子液体的各种溶剂中的性能。这些原位技术的成功开发为合理的催化剂设计和重要的结构/活性关系提供了必要的关键信息，用于从木质素生产广泛的工业重要化学品。这项工作有助于理解结构-反应性关系，配体特征，导致催化剂失活的条件和因素，包括中毒，和催化剂的可重复使用性。第一行过渡金属原位表征技术的发展为工业催化体系的设计提供了策略，特别是那些涉及强吸附溶剂体系的催化体系。 这项工作的成果有助于从生物质生产运输燃料和其他有用的化学品，美国有充足的供应，并使燃料生产多样化，远离化石燃料。此外，这项工作通过可持续的能源生产、使用更温和的条件进行更安全的工艺操作以及更少的不良副产品和温室气体排放来造福社会。

0856754ZakzeskiThis 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.