The conversion of light olefins to heavier analogues is desirable from an industrial standpoint. Typically, olefins such as ethylene, propylene, and butene are transformed into long chain hydrocarbons by using catalytic methods such as oligomerization, metathesis, and polymerization.  Homogeneous nickel-based catalysts bearing ancillary ligands have been at the forefront for facilitating such transformations.  Shell higher olefin process (SHOP) catalysts featuring chelated nickel phosphine systems have been widely used for generating linear α-olefins in commercial settings and are exploited due to their versatility and modularity. However, due to the homogeneous nature of this catalyst, catalyst separation and regeneration are challenging. To address the limitations of these homogeneous catalysts, several studies have been performed that highlight many key advantages for developing supported catalysts for olefin conversion.  Specifically, catalysts embedded in metal-organic frameworks (MOFs) have started to provide compelling solutions to address such issues. In addition to being highly porous and crystalline, MOFs offer a predictable strategy for installing discrete active sites in a solid, high surface-area medium. In this work, we envisioned a single-site nickel catalyst that merges the modularity of SHOP based systems with the robustness of a periodic MOF support.  Starting from an organometallic precursor, a single nickel site has been grafted onto the MOF NU-1000.  Data will be presented on our synthesis and characterization (NMR spectroscopy, XAS, PXRD, and STEM-EDS) of this supported organometallic species.

Single nickel sites embedded in a metal-organic framework for olefin up-conversion

ACS Spring 2022

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