TY - JOUR
T1 - Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene
AU - Pellizzeri, Steven
AU - Barona, Melissa
AU - Bernales, Varinia
AU - Miró, Pere
AU - Liao, Peilin
AU - Gagliardi, Laura
AU - Snurr, Randall Q.
AU - Getman, Rachel B.
N1 - Funding Information:
This work was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award DE-SC0012702. S.P. and R.B.G. would like to thank the Palmetto Supercomputer Cluster, which is maintained by the Cyberinfrastructure Technology Integration Group at Clemson University for generous allotment of computing time on the Palmetto cluster. M.B., P.M., and P.L. would like to thank the Quest High Performance Computing Cluster, which is maintained by the Northwestern University Information Technology, and the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. V.B. performed her calculations at the Minnesota Supercomputing Institute.
Publisher Copyright:
© 2018 Elsevier B.V.
PY - 2018/8/15
Y1 - 2018/8/15
N2 - Six first-row transition metal cations (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) were evaluated as catalysts for ethene dimerization to 1-butene. This is an important reaction in the chemistry of C–C bond formation and in the conversion of natural gas to higher hydrocarbons. Two related classes of transition metal cation catalysts were investigated: 1) single transition metal cations supported on zirconium oxide nodes of the metal–organic framework NU-1000 and 2) small metal hydroxide clusters with two metal atoms (M2) that could be grown by atomic layer deposition on a support exhibiting isolated hydroxyl groups. Using scaling relations, the free energies of co-adsorbed hydrogen and ethene (i.e., (H/C2H4)*) and adsorbed ethyl (i.e., C2H5*) were identified as descriptors for ethene dimerization catalysis. Using degree of rate control analysis, it was determined that the rate controlling steps are either ethene insertion (C–C bond forming) or β-hydride elimination (C–H bond breaking), depending on the metal. Using degree of catalyst control analysis, it was determined that activity on all the catalysts studied could be improved by tuning the free energy of C2H5*.
AB - Six first-row transition metal cations (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) were evaluated as catalysts for ethene dimerization to 1-butene. This is an important reaction in the chemistry of C–C bond formation and in the conversion of natural gas to higher hydrocarbons. Two related classes of transition metal cation catalysts were investigated: 1) single transition metal cations supported on zirconium oxide nodes of the metal–organic framework NU-1000 and 2) small metal hydroxide clusters with two metal atoms (M2) that could be grown by atomic layer deposition on a support exhibiting isolated hydroxyl groups. Using scaling relations, the free energies of co-adsorbed hydrogen and ethene (i.e., (H/C2H4)*) and adsorbed ethyl (i.e., C2H5*) were identified as descriptors for ethene dimerization catalysis. Using degree of rate control analysis, it was determined that the rate controlling steps are either ethene insertion (C–C bond forming) or β-hydride elimination (C–H bond breaking), depending on the metal. Using degree of catalyst control analysis, it was determined that activity on all the catalysts studied could be improved by tuning the free energy of C2H5*.
KW - Atomically dispersed catalyst
KW - Computational catalysis
KW - Hydrocarbon chemistry
KW - Metal-organic framework
KW - Microkinetic modeling
KW - Single atom catalyst
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U2 - 10.1016/j.cattod.2018.02.024
DO - 10.1016/j.cattod.2018.02.024
M3 - Article
AN - SCOPUS:85042438459
SN - 0920-5861
VL - 312
SP - 149
EP - 157
JO - Catalysis Today
JF - Catalysis Today
ER -