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Deposition of small metal-oxide clusters on the Zr-based nodes of a metal-organic framework has been demonstrated to provide access to a variety of single-site catalysts. Well-defined catalytic active sites are amenable to detailed computational studies of potential catalytic pathways, and they invite screening a wide range of metals to assess their expected activity. Here we report the application of density functional theory to a variety of transition metals (in particular TiIV, VII, VIV, CrII, CrIII, MnII, MnIV, FeII, FeIII, NiII, CoII, CoIII, CuII, CuIII, PdII, MoII, and WII) supported on NU-1000 inorganometallic nodes to evaluate their activity for ethylene dimerization. We found that the rate-determining step varies between different catalysts, which illustrates the importance of considering more than a single step when comparing catalytic cycles across a variety of metals. Our calculations are consistent with the known good activity of supported NiII for ethylene dimerization, and they predict that CrII and PdII are also potentially useful catalysts for this process. We also screen modifications to the organic linker of NiII-NU-1000 by considering the addition of Me, iPr, tBu, CF3 and NH2 groups to study the influence of sterically demanding and, the case of CF3 and NH2, respectively, electron-donating and -withdrawing, substituents on the activity for ethylene dimerization; we predict no improvements in activity or selectivity (for 1-butene) with such substitutions.
Bibliographical noteFunding Information:
We thank Aaron League for helpful discussions. This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE , Office of Basic Energy Sciences ( DE -SC0012702). The computations were performed at the Minnesota Supercomputing Institute.
We thank Aaron League for helpful discussions. This work was supported as part of the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DE-SC0012702). The computations were performed at the Minnesota Supercomputing Institute.
© 2017 Elsevier Inc.
- Density functional theory
- Ethylene dimerization
- Linker functionalization
- Metal-organic framework
- Transition metal catalysts