Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Zhang, Guanghui; Yang, Ce; Miller, Jeffrey T.

doi:10.1002/cctc.201701815

Cited by 40 publications

(31 citation statements)

References 44 publications

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“…This suggests that any catalyst that is active for one reaction should also be active for the other two if they are structurally stable under all reaction conditions. 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 .…”

Section: Discussionmentioning

confidence: 77%

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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: 77%

“…Single site Ga/SiO 2 and Zn/SiO 2 were prepared following the procedures previously reported in literature, using standard catalyst synthesis techniques, and compared to a Ni/SiO 2 control 22,23,48 .…”

Section: Methodsmentioning

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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“…However, SACs do not find broad application in high temperature (> 500 °C) light alkane dehydrogenation reactions. Although single-site Zn(II) 33 , Co(III) 34 , Ni(II) 35 , and Ga(III) 36 on silica have been developed as selective PDH catalysts, these active sites suffer from low activity compared to metallic sites. To the best of our knowledge, high stability and selectivity have not been achieved for the PDH reaction with the use of single-atom Pt catalysts.…”

Section: Introductionmentioning

confidence: 99%

Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation

et al. 2018

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Noble-metal alloys are widely used as heterogeneous catalysts. However, due to the existence of scaling properties of adsorption energies on transition metal surfaces, the enhancement of catalytic activity is frequently accompanied by side reactions leading to a reduction in selectivity for the target product. Herein, we describe an approach to breaking the scaling relationship for propane dehydrogenation, an industrially important reaction, by assembling single atom alloys (SAAs), to achieve simultaneous enhancement of propylene selectivity and propane conversion. We synthesize γ-alumina-supported platinum/copper SAA catalysts by incipient wetness co-impregnation method with a high copper to platinum ratio. Single platinum atoms dispersed on copper nanoparticles dramatically enhance the desorption of surface-bounded propylene and prohibit its further dehydrogenation, resulting in high propylene selectivity (~90%). Unlike previous reported SAA applications at low temperatures (<400 °C), Pt/Cu SAA shows excellent stability of more than 120 h of operation under atmospheric pressure at 520 °C.

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“…alkane dehydrogenation is performed. 50 In addition, a recent study demonstrates that single site Ni 2+…”

Section: Discussionmentioning

confidence: 99%

“…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. 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.…”

Section: Discussionmentioning

confidence: 99%

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

Tetrahedral Nickel(II) Phosphosilicate Single‐Site Selective Propane Dehydrogenation Catalyst

Cited by 40 publications

References 44 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

Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation

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

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