Carbon-Carbon Bond Formation and Related Reactions on Metal Oxides: Surface Science and Catalysis

金属氧化物上碳-碳键的形成及相关反应：表面科学与催化

• 批准号: 9410965
• 负责人: Mark Barteau
• 金额: $ 44.5万
• 依托单位: University of Delaware
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1994
• 资助国家: 美国
• 起止时间: 1994-07-01 至 1997-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9410965&HistoricalAwards=false
• 关键词: Carbon; Bond; Formation; Related; Reactions

ABSTRACT Mark Barteau CTS-9410965 This is an investigation of two carbon-carbon bond-forming reactions that occur on metal-oxide surfaces: reductive carbonyl coupling and alkyne cyclotrimerization. It has been demonstrated that both reactions can be run as gas-solid reactions on titania single crystals even in ultrahigh vacuum. This research defines the mechanisms of these surface reactions in order to test analogies with liquid-phase organometallic reactions, and applies the understanding gained to the invention of new heterogeneous catalysts for novel surface organic syntheses. The program includes spectroscopic investigations of carbon-carbon bond-forming reactions on reduced titania single crystals, steady-state and temperature-programmed flow reactor studies on oxide powders at atmospheric pressure (to demonstrate the "scale-up" from ultrahigh vacuum to normal industrial catalytic operations), and scanning probe microscopy experiments to probe active sites and adsorbed intermediates at the molecular level and to test the ability to manipulate these factors. This effort is the centerpiece of a program to enable the transfer of traditionally esoteric surface chemistry to industrial practice through a series of "scale-up" stages, and thus rationalize the introduction of new catalytic chemistry into industrial technology. ***

摘要Mark Barteau CTS-9410965 这是一个调查的两个碳-碳键形成反应，发生在金属氧化物表面：还原羰基偶联和炔环三聚。 结果表明，这两种反应都可以在二氧化钛单晶上进行，即使在高真空下也可以进行。 本研究定义了这些表面反应的机制，以测试与液相有机金属反应的类比，并将所获得的理解应用于新型表面有机合成的新型多相催化剂的发明。 该计划包括在还原的二氧化钛单晶上的碳-碳键形成反应的光谱研究，在常压下氧化物粉末的稳态和程序升温流动反应器研究（为了证明从超真空到正常工业催化操作的“按比例放大”），和扫描探针显微镜实验，以探测在分子水平上的活性位点和吸附的中间体，并测试操纵这些因素的能力。 这一努力是一个计划的核心，该计划通过一系列“放大”阶段将传统深奥的表面化学转移到工业实践中，从而使新的催化化学引入工业技术合理化。 ***