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

Colorado State University, Fort Collins CO

Investigators

Abstract

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.