Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

Pellizzeri, Steven; Barona, Melissa; Bernales, Varinia; Miró, Pere; Liao, Peilin; Gagliardi, Laura; Snurr, Randall Q.; Getman, Rachel B.

doi:10.1016/j.cattod.2018.02.024

Cited by 21 publications

(22 citation statements)

References 63 publications

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“…Benchmark calculations indicate that PBE-D2 is suitable to describe the electronic structure of (Ru)HKUST-1 (Supplementary Table 5). We computed the ethylene dimerization via a Cossee–Arlman mechanism 15,34,35 using a ligand-engineered defective node. Figure 4c shows the model L-1 used in the simulations (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts

et al. 2019

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Production of 1-butene, a major monomer in polymer industry, is dominated by homogeneous protocols via ethylene dimerization. Homogeneous catalysts can achieve high selectivity but require large amounts of activators and solvents, and exhibit poor recyclability; in turn, heterogeneous systems are robust but lack selectivity. Here we show how the precise engineering of metal–organic frameworks (MOFs) holds promise for a sustainable process. The key to the (Ru)HKUST-1 MOF activity is the intrapore reactant condensation that enhances ethylene dimerization with high selectivity (> 99% 1-butene) and high stability (> 120 h) in the absence of activators and solvents. According to spectroscopy, kinetics, and modeling, the engineering of defective nodes via controlled thermal approaches rules the activity, while intrapore ethylene condensation accounts for selectivity and stability. The combination of well-defined actives sites with the concentration effect arising from condensation regimes paves the way toward the development of robust MOF catalysts for diverse gas-phase reactions.

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Section: Resultsmentioning

confidence: 99%

Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts

et al. 2019

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“…Therefore, as an emerging subfamily, pyrene-based MOFs have aroused interest in the last years and been investigated for several heterogeneous catalytic reactions computationally and experimentally. As yet, computational studies have focused on the study of energetic barriers, formation mechanisms and the post-synthetic modification of catalytic active sites on the Zr 6 nodes in NU-1000 for different catalytic reactions; including ethylene dimerization, 111,229,230 ethylene hydrogenation, 231 alkyne semihydrogenation, 232 alcohol dehydrogenation, 233 hydrolysis of CWAs, 234,235 and C-H bond activation. [236][237][238] In addition, computational studies have been informative about the importance of the selection of transition metals for the post-synthetic functionalization on the node, and supports for the design of heterogeneous catalyst.…”

Section: Heterogeneous Catalysismentioning

confidence: 99%

Pyrene-based metal organic frameworks: from synthesis to applications

et al. 2021

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“…Currently, single‐site catalysts are intensely discussed, also for practical applications [2] . From a conceptual point of view as well as with regard to computational modeling, two classes of single‐site catalysts come to mind: ( i ) single metal atoms on a metal or metal oxide support [2b,c,e] and ( ii ) mononuclear metal complexes on inorganic porous supports like zeolites, metal‐organic frameworks (MOFs), and metal oxides [2] . The latter class of catalysts, of concern in the present work, are applied in alkene polymerization [3] and alkene epoxidation [4] .…”

Section: Introductionmentioning

confidence: 99%

Ethene Conversion at a Zeolite‐Supported Ir(I) Complex. A Computational Perspective on a Single‐Site Catalyst System

2021

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Applying a quantum mechanics/molecular mechanics scheme involving DFT calculations, a model study of mechanisms for ethene transformations at zeolite‐supported Ir(I) complexes is presented and the results compared to those of recent experiments and previous work on the isostructural Rh(I) complexes. Starting from the 2‐ligand complex [Ir(C2H4)2]+, in the presence of H2, the ethene conversion mechanisms studied yield solely ethane while the dimerization to 1‐butene via either the Cossee‐Arlman (CA) mechanism or the metallacycle (MC) mechanism was determined to be kinetically too demanding. Therefore, turning to 3‐ligand models, the calculations showed that the diethyl complex [Ir(C2H4)(C2H5)2]+ strongly favors ethene hydrogenation over dimerization (via a CA mechanism), with crucial activation free energies of 27 kJ mol−1 and 113 kJ mol−1, respectively. The alternative route to dimerization via a MC mechanism is also not operative because the C−C coupling barrier is higher by 30 kJ mol−1 (in absolute terms) than the hydrogen activation in the CA mechanism. Thus, when Rh is substituted by Ir, the computational results allowed to rationalize the experimentally determined switching from ethene dimerization to ethane formation due to the significantly higher calculated barrier, by ∼50 kJ mol−1 relative to Rh, of C−C coupling in the Ir system. The present study illustrates the advantage of describing the active site in a single site catalysis system, yet it also highlights the potential complexity of such systems as revealed by comparing 2‐ to 3‐ligand models as well as models with different metal centers, Rh vs Ir, in the light of conversion rates via the energetic span concept.

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Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

Cited by 21 publications

References 63 publications

Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts

Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts

Pyrene-based metal organic frameworks: from synthesis to applications

Ethene Conversion at a Zeolite‐Supported Ir(I) Complex. A Computational Perspective on a Single‐Site Catalyst System

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