SusChEM:CAREER:Using unique synthesis techniques and reaction kinetics to quantify and manipulate catalytically active sites in metal-reducible oxide systems

SusChEM：职业：使用独特的合成技术和反应动力学来量化和操纵金属可还原氧化物系统中的催化活性位点

• 批准号: 1653935
• 负责人: Steven Crossley
• 金额: $ 54.88万
• 依托单位: University of Oklahoma Norman Campus
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-03-01 至 2023-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1653935&HistoricalAwards=false
• 关键词: SusChEM; CAREER; Using; unique; synthesis

The project will provide detailed understanding of the active sites and atom transfer processes involved in catalytic conversion of various bio oil molecules derived from lignocellulosic biomass. Identification of highly active metal sites on reducible oxide supports will enable design of catalysts with optimized composition and site location. The catalyst structure-function relationships thus obtained will provide design guidance for converting a broad range of oxygenated organic compounds to high-value fuels and chemicals. The research will be integrated with educational and outreach programs targeting American Indian students, while also emphasizing the importance of safety in chemical processes.Biomass conversion processes typically create a broad range of oxygenated intermediates that are treated further by catalytic processes to remove the excess oxygen and build longer chain hydrocarbons attractive as fuel components and chemical intermediates. Efficient conversion requires multifunctional catalysts - typically composed of metal and metal oxide active sites - capable of several simultaneous or sequential reaction steps. While it is well understood that different types of active sites are required for the different reactions, the exact nature of those sites and their ideal proximity is not known. This study will examine those factors by decoupling metal sites from reducible metal oxide sites using carbon nanotube (CNT) bridges as hydrogen shuttles. By eliminating direct contact between the metal and metal oxide components, and by varying the metal-metal oxide spacing along the CNTs, the study will provide an opportunity to examine independently two important aspects of bifunctional catalysis on reducible metal oxides: metal-support interactions and hydrogen spillover from the metal to the metal oxide support. The study will also investigate how the metal-support and hydrogen spillover effects vary with different types of molecules common to biomass deconstruction processes. More broadly, the study will provide catalyst design guidance that can be used to improve the technoeconomic viability of a broad range of chemical reactions including those of importance in natural gas processing. The PI is a faculty mentor for the American Indian Science and Engineering Society at the University of Oklahoma, and plans to use the project as an opportunity to expand his on-going efforts to recruit Native American students at all levels via outreach camps that emphasize the importance of sustainable energy while generating excitement towards engineering degrees amongst American Indian and other underrepresented groups.

该项目将详细了解来自木质纤维素生物质的各种生物油分子催化转化的活性位点和原子转移过程。识别可还原氧化物载体上的高活性金属位点将使催化剂的设计具有优化的组成和位点。由此获得的催化剂结构-功能关系将为将广泛的含氧有机化合物转化为高价值燃料和化学品提供设计指导。这项研究将与针对美国印第安学生的教育和推广项目结合起来，同时也强调化学过程中安全的重要性。生物质转化过程通常会产生广泛的含氧中间体，这些中间体通过催化过程进一步处理以去除多余的氧，并生成具有吸引力的用作燃料成分和化学中间体的长链碳氢化合物。有效的转化需要多功能催化剂-通常由金属和金属氧化物活性位点组成-能够同时或连续进行几个反应步骤。众所周知，不同的反应需要不同类型的活性位点，但这些位点的确切性质及其理想距离尚不清楚。本研究将利用碳纳米管（CNT）桥作为氢载体，通过将金属位点与可还原金属氧化物位点解耦来考察这些因素。通过消除金属和金属氧化物组分之间的直接接触，以及改变金属-金属氧化物沿碳纳米管的间距，该研究将为独立研究可还原金属氧化物双功能催化的两个重要方面提供机会：金属-载体相互作用和氢从金属向金属氧化物载体的溢出。该研究还将探讨金属支持和氢溢出效应如何随生物质解构过程中常见的不同类型分子而变化。更广泛地说，该研究将提供催化剂设计指导，可用于提高广泛化学反应的技术经济可行性，包括天然气加工中的重要化学反应。PI是俄克拉何马大学美国印第安人科学与工程协会的教师导师，他计划利用这个项目作为一个机会，扩大他正在进行的努力，通过外展营来招募各个层次的美国原住民学生，这些营地强调可持续能源的重要性，同时在美国印第安人和其他代表性不足的群体中激发对工程学位的兴趣。

项目成果

Stabilization of furanics to cyclic ketone building blocks in the vapor phase

• DOI: 10.1016/j.apcatb.2019.04.079
• 发表时间: 2019-10
• 期刊: Applied Catalysis B: Environmental
• 作者: Taiwo Omotoso;Leidy V. Herrera;Tyler Vann;Nicholas M. Briggs;L. A. Gomez;L. Barrett;Donald G. Jones;T. Pham;Bin Wang;S. Crossley

Polystyrene and poly(methyl methacrylate) interfaces reinforced with diblock carbon nanotubes

二嵌段碳纳米管增强聚苯乙烯和聚甲基丙烯酸甲酯界面

• DOI: 10.1002/pen.25665
• 发表时间: 2021
• 期刊: Polymer Engineering & Science
• 影响因子: 3.2
• 作者: Seyni, Fatoumata Ide;Barrett, Lawrence;Crossley, Steven;Grady, Brian P.
• 通讯作者: Grady, Brian P.

Shifts in catalyst deactivation mechanisms as a function of surface coverage during Friedel-Crafts acylation in zeolites

沸石傅克酰化过程中催化剂失活机制随表面覆盖度的变化

• DOI: 10.1016/j.jcat.2023.07.009
• 发表时间: 2023
• 期刊: Journal of Catalysis
• 影响因子: 7.3
• 作者: Alalq, Ismaeel;Nguyen-Phu, Huy;Crossley, Steven
• 通讯作者: Crossley, Steven

Anisotropically Functionalized Nanotube Anchors for Improving the Mechanical Strength of Immiscible Polymer Composites

用于提高不混溶聚合物复合材料机械强度的各向异性功能化纳米管锚

• DOI: 10.1021/acsanm.0c02886
• 发表时间: 2021
• 期刊: ACS Applied Nano Materials
• 影响因子: 5.9
• 作者: Barrett, Lawrence;Ide Seyni, Fatoumata;Komarneni, Mallikharjuna Rao;Zapata-Hincapie, John A.;Glatzhofer, Daniel T.;Grady, Brian P.;Crossley, Steven
• 通讯作者: Crossley, Steven