For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C(1) building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO(2), ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.

Numerous homogeneous catalyst‐initiator systems are known and utilized in industrial scale to conduct various autoxidation processes. The reaction mechanism and kinetic details of homogeneous liquid phase autoxidation have been extensively investigated. This article presents an overview on the state of the art of heterogeneous catalyst‐initiator systems in the liquid phase oxidation of hydrocarbons. Mechanistic insights and limitations of the heterogeneous catalyst‐initiator systems are discussed. The potentials and challenges towards an industrial application are evaluated.

High throughput experimentation (HTE) approaches and the choice of the design of experiment (DoE) tools are discussed with regard to their convenience and applicability in homogeneous and heterogeneous catalysis as a concerted workflow. Much attention is given to diverse methodologies and strategies, which are fundamental for the experimental planning. For two target reactions in two case studies presented in this chapter, HTE methods were applied to create and evaluate catalyst libraries. A homogeneous catalyst case study is illustrated first, which deals with parallel synthesis and screening of organometallic catalysts in the polymerisation of ethylene. The second case study (heterogeneous catalysis) focuses on coherent synthesis and testing of dopant effects on the performance of oxidation catalysts in a reaction of transformation of n-butane to maleic anhydride. Supporting examples from the literature described here show that careful planning of libraries and test conditions is vital in high throughput experimentation in order to deliver meaningful results leading to performance improvements or disruptive new findings.

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