Influence of spin state and electron configuration on the active site and mechanism for catalytic hydrogenation on metal cation catalysts supported on NU-1000: insights from experiments and microkinetic modeling

Shabbir, Hafeera; Pellizzeri, Steven; Ferrandon, Magali; Kim, In Soo; Vermeulen, Nicolaas A.; Farha, Omar K.; Delferro, Massimiliano; Martinson, Alex B. F.; Getman, Rachel B.

doi:10.1039/d0cy00394h

Cited by 17 publications

(16 citation statements)

References 38 publications

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“…The single site Ni 2+ , in this study, performs oligomerization; however, Ni/SiO 2 reduces to metallic (Ni 0 ) nanoparticles at temperatures higher than about 350°C, thus is not stable at the high temperature where alkane dehydrogenation is performed 48 . In addition, a recent study demonstrates that single site Ni 2+ catalysts in Zr-MOF NU1000 catalyze olefin oligomerization and hydrogenation 49,50 . Consistent with this proposal, single site Cr 3+ is catalytic for alkane dehydrogenation in the Catofin process, and olefin oligomerization, i.e., the Phillips catalyst 47,[51][52][53][54] .…”

Section: Discussionmentioning

confidence: 99%

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

Libretto

Quigley

et al. 2021

Nat Commun

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In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni2+ and Cr3+. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn2+ and Ga3+ ion sites catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni2+. The molecular weight distribution of products formed on Zn2+ is similar to Ni2+, while Ga3+ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250 °C where oligomerization is catalytically relevant. This work illuminates new chemistry for main group metal catalysts with potential for development of new oligomerization processes.

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Section: Discussionmentioning

confidence: 99%

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

Libretto

Quigley

et al. 2021

Nat Commun

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“…With regard to Zr-MOFs, the design of OHI catalysts has focused on postsynthetic modification to install active sites. For hydrogenations, metal complexes, ,− metal salts ,− and clusters, ,,, and metal nanoparticles − have been supported on the nodes and linkers or encapsulated within pores of Zr-MOFs. 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.…”

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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“…50 In addition, a recent study demonstrates that single site Ni 2+ catalysts in Zr-MOF NU1000 catalyze ole n oligomerization and hydrogenation. 51,52 Consistent with this proposal, single site Cr 3+ is catalytic for alkane dehydrogenation in the Cato n process, and ole n oligomerization, i.e., the Phillips catalyst. [53][54][55][56][57] Thus, there is evidence from heterogeneous transition metal catalysts that all three reactions are mechanistically related.…”

Section: Discussionmentioning

confidence: 62%

Olefin Oligomerization by Main Group Ga3+ and Zn2+ Single Site Catalysts

Libretto¹,

Xu²,

Quigley³

et al. 2020

Preprint

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In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni2+ and Cr3+. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn2+ and Ga3+ ions catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni2+. The molecular weight distribution of products formed on Zn2+ is similar to Ni2+; while Ga3+ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250°C where oligomerization is catalytically relevant. This work reports new chemistry for main group metal catalysts with potential for development of new olefin processes.

show abstract

Influence of spin state and electron configuration on the active site and mechanism for catalytic hydrogenation on metal cation catalysts supported on NU-1000: insights from experiments and microkinetic modeling

Abstract: Spin state is found to determine the mechanism and active site of catalytic hydrogenation on metal cation catalysts.

Cited by 17 publications

References 38 publications

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

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

Olefin Oligomerization by Main Group Ga3+ and Zn2+ Single Site Catalysts

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Influence of spin state and electron configuration on the active site and mechanism for catalytic hydrogenation on metal cation catalysts supported on NU-1000: insights from experiments and microkinetic modeling

Abstract: Spin state is found to determine the mechanism and active site of catalytic hydrogenation on metal cation catalysts.

Cited by 17 publications

References 38 publications

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

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

Olefin Oligomerization by Main Group Ga3+ and Zn2+ Single Site Catalysts

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