GOALI: 'Ziegler-Nanocluster' Industrial Catalysts Stabilized by Alumoxanes

目标：由铝氧烷稳定的“齐格勒纳米簇”工业催化剂

• 批准号: 0611588
• 负责人: Richard Finke
• 金额: $ 42.2万
• 依托单位: Colorado State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0611588&HistoricalAwards=false
• 关键词: GOALI; Ziegler; Nanocluster; Industrial; Catalysts

This GOALI award in the Inorganic, Bioinorganic and Organometallic Chemistry program and in the Division of Engineering, Chemical Transport Systems program supports research by Professor Richard G. Finke at Colorado State University determine whether industrial polymer hydrogenation and other, multi-use Zielger-type group 8-10 element catalysts, formed from M(O2CR)2 / AlEt3 in cyclohexane (e.g., M = Ni, Co), are single metal homogeneous hydrogenation catalysts as presently believed or multimetallic Ni(0)n and Co(0)m "Zieglernanocluster" heterogeneous catalysts stabilized by alumoxanes (compounds containing Al-O-Al linkages). This research also aims to provide fundamental knowledge needed by the industrial partner, KRATON Polymers, to develop the next generation of improved activity, lifetime and selectivity catalysts. The specific objectives are to: (i) establish the key variables crucial to the synthesis of reproducible activity KRATON/Ziegler catalysts; (ii) determine whether the KRATON/Ziegler catalysts are homogeneous or heterogeneous using proven methods; (iii) use a variety of physical methods, including matrix-assisted laser desporption/ionization mass spectrometry (MALDI-MS), to identify the true nature of the aluminum trialkyl-derived co-catalyst; (iv) rank the catalytic activity, lifetime, temperature stability and selectivity of the KRATON/Ziegler catalyst vs the best available nanoclusters; (v) use different aluminium trialkyls, plus correlations of catalysis with MALDI-MS determined compositions, as a rational method to yield improved catalysts; (vi) use deuterium labeling and gas chromatography-mass spectrometry (GC-MS) plus kinetic studies to identify the catalytic rate-determining step en route to higher activity catalysts; and (vii) transfer the key findings and technology directly to KRATON via internships for a postdoc, graduate student and an undergraduate. The MALDI-MS-determined enhanced compositional knowledge of alumoxanes promises to impact areas that utilize alumoxanes, including: catalysis, polymerization, fuel cells, cathode materials, nanocomposites, inorganic membranes, ceramics, and synthetic bone materials. Internships and the close partnership with KRATON Polymers will provide real-world, industrial training for students.

这个GOALI奖在无机，生物无机和有机化学计划和工程，化学运输系统计划支持教授理查德G。科罗拉多州立大学的Finke确定工业聚合物氢化和其他多用途的Zielger型8-10族元素催化剂，由环己烷中的M（O2 CR）2 /AlEt 3形成（例如，M = Ni，Co）是目前认为的单金属均相氢化催化剂或由铝氧烷（含有Al-O-Al键的化合物）稳定的多金属Ni（0）n和Co（0）m“齐格勒纳米簇”非均相催化剂。 这项研究还旨在提供工业合作伙伴KRATON Polymers所需的基础知识，以开发下一代改进活性，寿命和选择性的催化剂。 具体目标是：（i）建立对合成可再现活性的KRATON/齐格勒催化剂至关重要的关键变量;（ii）使用经证实的方法确定KRATON/齐格勒催化剂是均相还是非均相的;（iii）使用各种物理方法，包括基质辅助激光解吸/电离质谱法（iv）将KRATON/齐格勒催化剂的催化活性、寿命、温度稳定性和选择性与最佳可得纳米团簇进行排序;（vi）使用氘标记和气相色谱-质谱（GC-MS）加上动力学研究来鉴定在获得更高活性催化剂的过程中的催化速率决定步骤;以及（vii）通过博士后、研究生和本科生的实习将关键发现和技术直接转移到KRATON。MALDI-MS确定的增强的铝氧烷组成知识有望影响利用铝氧烷的领域，包括：催化，聚合，燃料电池，阴极材料，纳米复合材料，无机膜，陶瓷和合成骨材料。 实习和与KRATON Polymers的密切合作将为学生提供真实世界的工业培训。