Isomerization of 1-Butene to 2-Butene Catalyzed by Metal–Organic Frameworks

Sheng, Donghai; Zhang, Ying; Song, Qingxiang; Xu, Guang; Peng, Dandan; Hou, Heqian; Xie, Ren; Shan, Dongming; Li, Xiuting

doi:10.1021/acs.organomet.9b00599

Cited by 7 publications

(5 citation statements)

References 40 publications

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“…In all cases, it has been proposed that the zirconium framework has improved catalytic activity through physical means, such as site isolation, , nanoparticle size control, ,, and shape selectivity. , However, to the best of our knowledge, no work has shown olefin hydrogenation activity intrinsic to the Zr-MOFs themselves. Fewer studies have focused on olefin isomerization in MOFs, , and for Zr-MOFs, olefin isomerization has only been reported on sulfated nodes, which possess strong Brønsted acid sites. , Collectively, the current MOF catalyst literature suggests that the unmodified metal-oxide nodes of Zr-MOFs are spectators or inactive in catalytic olefin transformations such as OHI.…”

Section: Introductionmentioning

confidence: 99%

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

et al. 2020

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Zirconium-based metal–organic frameworks (Zr-MOFs) have been increasingly studied over the past two decades as heterogeneous catalysts due to their synthetic tunability, well-defined nature, and chemical stability. In contrast to traditional zirconia-based heterogeneous catalysts, the community has assumed that Zr-MOFs are inert catalyst supports that do not participate directly in hydrocarbon transformations, such as olefin hydrogenation and isomerization. Here, we report that the Zr-MOF NU-1000 is capable of catalyzing olefin hydrogenation and isomerization, without any postsynthetic modifications, under a hydrogen atmosphere. We probe H2 activation over the nodes of NU-1000 via spectroscopic and computational techniques revealing that H2 dissociation can occur heterolytically across coordinatively unsaturated Zr sites and proximal hydroxide and μ3-oxo ligands. These results, along with catalytic experiments, suggest that H2 activation results in node-supported zirconium hydrides capable of the hydrogenation and isomerization of 1-butene. When examining rate dependence on the partial pressure of H2, we observe first-order dependence for hydrogenation and half-order dependence for isomerization. Half-order H2 rate dependence is consistent with a mechanism where both fragments of cleaved H2 are active for 1-butene isomerization, suggesting that heterolytic cleavage generates acidic protons resulting in parallel, acid-, and hydride-catalyzed isomerization pathways. This work shows that Zr-MOFs have more diverse reactivity than the current literature may suggest and opens possibilities for ways in which Zr-MOFs can be used as heterogeneous catalysts and supports.

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Section: Introductionmentioning

confidence: 99%

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

et al. 2020

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“…The isomerization of primary B1 to secondary B2 has practical importance as it influences the distribution of final products. This process has attracted extensive study from both commercial and fundamental perspectives. − However, precisely identifying the isomerization pathway within the context of BD hydrogenation poses technical challenges. The main difficulty lies in determining whether B2 forms directly from BD hydrogenation or via B1 isomerization.…”

Section: Introductionmentioning

confidence: 99%

The Role of Adsorbed Species in 1-Butene Isomerization: Parahydrogen-Induced Polarization NMR of Pd–Au Catalyzed Butadiene Hydrogenation

Wang,

Lewis,

et al. 2024

ACS Catal.

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Isomerization of 1-butene critically influences product distributions in 1,3-butadiene hydrogenation. However, distinguishing between the isomerization and hydrogenation pathways is challenging. Here, we employ parahydrogen-induced polarization (PHIP) NMR spectroscopy to determine the extent of the isomerization pathway when using Pd−Au bimetallic nanoparticles synthesized via a colloidal protocol in the presence or absence of a polyvinylpyrrolidone (PVP) stabilizing ligand and immobilized on TiO 2 . Residual additives, in particular, sulfur, are observed to considerably influence the pairwise hydrogenation and 1-butene isomerization pathways. PHIP NMR analysis reveals that the PVP ligand can induce strong polarized signals, likely due to restricted proton migration, but minimally impact 1-butene isomerization. In contrast, removing surface sulfur species introduced during catalyst synthesis profoundly enhances 1-butene isomerization by reducing the hydrogen concentration at the nanoparticle surface. This work elucidates how residual species can modulate key reaction pathways such as isomerization during 1,3-butadiene hydrogenation, with implications for rational catalyst design.

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“…Strategies to synthesize single-site catalysts include the surface organometallic chemistry (SOMC) approach and the use of metal–organic and covalent organic frameworks (MOFs and COFs, respectively), and both have had limited success with alkene isomerization. Estes demonstrated that an alumina-supported platinum-hydride is effective at 1-hexene isomerization (Figure b, bottom right), and a handful of examples of MOFs show activity for 1-butene isomerization and E / Z isomerization. − While these advancements demonstrate the potential of single-site catalysts in alkene isomerization, their substrate scopes are highly limited and often utilize precious metals as the active site.…”

Section: Introductionmentioning

confidence: 99%

Alkene Isomerization Using a Heterogeneous Nickel-Hydride Catalyst

Chang,

Kascoutas,

Valentine

et al. 2024

J. Am. Chem. Soc.

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Transition metal-catalyzed alkene isomerization is an enabling technology used to install an alkene distal to its original site. Due to their well-defined structure, homogeneous catalysts can be fine-tuned to optimize reactivity, stereoselectivity, and positional selectivity, but they often suffer from instability and nonrecyclability. Heterogeneous catalysts are generally highly robust but continue to lack active-site specificity and are challenging to rationally improve through structural modification. Known single-site heterogeneous catalysts for alkene isomerization utilize precious metals and bespoke, expensive, and synthetically intense supports. Additionally, they generally have mediocre reactivity, inspiring us to develop a heterogeneous catalyst with an active site made from readily available compounds made of Earth-abundant elements. Previous work demonstrated that a very active homogeneous catalyst is formed upon protonation of Ni[P(OEt)3]4 by H2SO4, generating a [Ni–H]+ active site. This catalyst is incredibly active, but also decomposes readily, which severely limits its utility. Herein we show that by using a solid acid (sulfated zirconia, SZO300), not only is this decomposition prevented, but high activity is maintained, improved selectivity is achieved, and a broader scope of functional groups is tolerated. Preliminary mechanistic experiments suggest that the catalytic reaction likely goes through an intermolecular, two-electron pathway. A detailed kinetic study comparing the state-of-the-art Ni and Pd isomerization catalysts reveals that the highest activity and selectivity is seen with the Ni/SZO300 system. The reactivity of Ni/SZO300, is not limited to alkene isomerization; it is also a competent catalyst for hydroalkenylation, hydroboration, and hydrosilylation, demonstrating the broad application of this heterogeneous catalyst.

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Isomerization of 1-Butene to 2-Butene Catalyzed by Metal–Organic Frameworks

Cited by 7 publications

References 40 publications

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

The Role of Adsorbed Species in 1-Butene Isomerization: Parahydrogen-Induced Polarization NMR of Pd–Au Catalyzed Butadiene Hydrogenation

Alkene Isomerization Using a Heterogeneous Nickel-Hydride Catalyst

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Isomerization of 1-Butene to 2-Butene Catalyzed by Metal–Organic Frameworks

Cited by 7 publications

References 40 publications

Zr6O8 Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

Zr6O8 Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

The Role of Adsorbed Species in 1-Butene Isomerization: Parahydrogen-Induced Polarization NMR of Pd–Au Catalyzed Butadiene Hydrogenation

Alkene Isomerization Using a Heterogeneous Nickel-Hydride Catalyst

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Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

Zr₆O₈ Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000