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

无机、生物无机和有机金属化学项目以及工程、化学传输系统项目的GOALI奖支持科罗拉多州立大学Richard G. Finke教授的研究，该研究确定工业聚合物加氢和其他多用途齐格尔型8-10元素催化剂，由M(O2CR)2 / AlEt3在环己烷中形成（例如，M = Ni, Co），是目前认为的单金属均相加氢催化剂或多金属Ni(0)n和Co(0)m“Zieglernanocluster”非均相催化剂，由铝烷（含有Al-O-Al键的化合物）稳定。这项研究还旨在为工业合作伙伴KRATON Polymers提供所需的基础知识，以开发下一代提高活性、寿命和选择性的催化剂。具体目标是：(i)确定对合成可再生活性KRATON/Ziegler催化剂至关重要的关键变量；（ii）使用经过验证的方法确定KRATON/Ziegler催化剂是均相还是多相；（iii）使用各种物理方法，包括基质辅助激光解吸/电离质谱法（MALDI-MS），以确定三烷基铝衍生共催化剂的真实性质；（iv）对KRATON/Ziegler催化剂与最佳纳米团簇的催化活性、寿命、温度稳定性和选择性进行排序；(v)使用不同的铝三烷基，加上与MALDI-MS测定的组分的催化相关性，作为生产改进催化剂的合理方法；（vi）使用氘标记、气相色谱-质谱联用（GC-MS）和动力学研究来确定制备高活性催化剂的催化速率决定步骤；（七）通过博士后、研究生和本科生的实习，将主要研究成果和技术直接转让给KRATON。maldi - ms测定的增强的铝氧烷成分知识有望影响使用铝氧烷的领域，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。实习以及与KRATON Polymers的密切合作将为学生提供现实世界的工业培训。

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.