From ethene to propene (ETP) on tailored silica–alumina supports with isolated Ni(<scp>ii</scp>) sites: uncovering the importance of surface nickel aluminate sites and the carbon-pool mechanism

Chen, Zixuan; Docherty, Scott R.; Florian, Pierre; Kierzkowska, Agnieszka M.; Moroz, Ilia B.; Abdala, Paula M.; Copéret, Christophe; Müller, Christoph R.; Fedorov, Alexey

doi:10.1039/d2cy01272c

Cited by 4 publications

(6 citation statements)

References 42 publications

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“…This structural variation leads to a decreasing abundance of strong Brønsted acid sites (BAS) with increasing thickness of the deposited layer. Such model AlO x /SiO 2 supports allowed us to identify the role of strong BAS in the aromatization of ethylene and its oligomers for Ni-based ethene-to-propene catalysts …”

Section: Introductionmentioning

confidence: 99%

“…Such model AlO x / SiO 2 supports allowed us to identify the role of strong BAS in the aromatization of ethylene and its oligomers for Ni-based ethene-to-propene catalysts. 25 While reports on ALD-derived gallia films have utilized mostly flat substrates (Si-wafers, fused silica, or polyimide supports), 26−30 studies on the deposition of GaO x on powder substrates are limited. 31,32 For instance, it has been demonstrated that the use of trimethylgallium (TMG) in combination with ozone is efficient for the growth of amorphous gallia films onto Si(100) or fused SiO 2 .…”

Section: ■ Introductionmentioning

confidence: 99%

“…Such model AlO x /SiO 2 supports allowed us to identify the role of strong BAS in the aromatization of ethylene and its oligomers for Ni-based ethene-to-propene catalysts. 25 …”

Section: Introductionmentioning

confidence: 99%

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Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Chen,

Zimmerli,

Zubair

et al. 2023

Chem. Mater.

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Gallia-based shells with a thickness varying from a submonolayer to ca. 2.5 nm were prepared by atomic layer deposition (ALD) using trimethylgallium, ozone, and partially dehydroxylated silica, followed by calcination at 500 °C. Insight into the atomic-scale structure of these shells was obtained by high-field 71 Ga solid-state nuclear magnetic resonance (NMR) experiments and the modeling of X-ray differential pair distribution function data, complemented by Ga K-edge X-ray absorption spectroscopy and 29 Si dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) studies. When applying one ALD cycle, the grown submonolayer contains mostly tetracoordinate Ga sites with Si atoms in the second coordination sphere ( [4] Ga (Si) ) and, according to 15 N DNP SENS using pyridine as the probe molecule, both strong Lewis acid sites (LAS) and strong Brønsted acid sites (BAS), consistent with the formation of gallosilicate Ga–O–Si and Ga–μ 2 -OH–Si species. The shells obtained using five and ten ALD cycles display characteristics of amorphous gallia (GaO x ), i.e., an increased relative fraction of pentacoordinate sites ( [5] Ga (Ga) ), the presence of mild LAS, and a decreased relative abundance of strong BAS. The prepared Ga1-, Ga5-, and Ga10-SiO 2–500 materials catalyze the dehydrogenation of isobutane to isobutene, and their catalytic performance correlates with the relative abundance and strength of LAS and BAS, viz., Ga1-SiO 2–500 , a material with a higher relative fraction of strong LAS, is more active and stable compared to Ga5- and Ga10-SiO 2–500 . In contrast, related ALD-derived Al1-, Al5-, and Al10-SiO 2–500 materials do not catalyze the dehydrogenation of isobutane and this correlates with the lack of strong LAS in these materials that instead feature abundant strong BAS formed via the atomic-scale mixing of Al sites with silica, leading to Al–μ 2 -OH–Si sites. Our results suggest that [4] Ga (Si) sites provide strong Lewis acidity and drive the dehydrogenation activity, while the appearance of [5] Ga (Ga) sites with mild Lewis activity is associated with catalyst deactivation through coking. Overall, the atomic-level insights into the structure of the GaO x -based materials prepared in this work provide a guide to design active Ga-based catalysts by a rational tailoring of Lewis and Brønsted acidity (nature, strength, and abundance).

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Chen,

Zimmerli,

Zubair

et al. 2023

Chem. Mater.

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“…1). 8 The SAC concept therefore implies no (or weak) influence of other atoms in the first coordination sphere of grafted metal atom beyond the metal to surface bonds (such as M-O or M-C bonds at oxide or carbon surface respectively), while typically at least one coordinated organic molecule, which is absent in SAC systems, directly influences the electronic and/or steric properties of the grafted metal complex in SOMC or macroligand strategies though M-X bonds where X = C, O, N, P, S. Therefore the SAC systems, as well as the similarly ligand free catalysts that can be obtained by the thermolytic molecular precursor method, 41,42 are beyond the scope of this review, and will only be sporadically mentioned if they lead to performing materials against whose performance the performance of the SOMC or macroligand-based materials can be compared and contrasted.…”

Section: Je ´Ro ˆMe Canivetmentioning

confidence: 99%

Heterogenization of molecular catalysts within porous solids: the case of Ni-catalyzed ethylene oligomerization from zeolites to metal–organic frameworks

Rajapaksha,

Samanta,

Quadrelli

et al. 2023

Chem. Soc. Rev.

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“…Further, a controlled engineering of the metal/support interface will benefit the elucidation of robust structure–activity relationships . In this context, atomic layer deposition (ALD) can be a method of choice and has been used in the preparation of heterogeneous catalysis, e.g., by forming an overcoat of controlled thickness (e.g., a metal oxide) onto a support or a catalyst. , In particular, ALD enables a high conformality of the grown films and their tunable composition and thickness down to the sub-nm scale. , In addition, ALD allows to manipulate in a controlled fashion the relative abundance and distribution of Brønsted and Lewis (strong and weak) acid sites. – Yet, the use of ALD to create heterogeneous catalysts with well-defined metal/support interfaces remains relatively underexplored. – …”

Section: Introductionmentioning

confidence: 99%

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

Zhou,

Docherty,

Phongprueksathat

et al. 2023

JACS Au

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The direct synthesis of methanol via the hydrogenation of CO2, if performed efficiently and selectively, is potentially a powerful technology for CO2 mitigation. Here, we develop an active and selective Cu–Zn/SiO2 catalyst for the hydrogenation of CO2 by introducing copper and zinc onto dehydroxylated silica via surface organometallic chemistry and atomic layer deposition, respectively. At 230 °C and 25 bar, the optimized catalyst shows an intrinsic methanol formation rate of 4.3 g h–1 gCu –1 and selectivity to methanol of 83%, with a space-time yield of 0.073 g h–1 gcat –1 at a contact time of 0.06 s g mL–1. X-ray absorption spectroscopy at the Cu and Zn K-edges and X-ray photoelectron spectroscopy studies reveal that the CuZn alloy displays reactive metal support interactions; that is, it is stable under H2 atmosphere and unstable under conditions of CO2 hydrogenation, indicating that the dealloyed structure contains the sites promoting methanol synthesis. While solid-state nuclear magnetic resonance studies identify methoxy species as the main stable surface adsorbate, transient operando diffuse reflectance infrared Fourier transform spectroscopy indicates that μ-HCOO*(ZnO x ) species that form on the Cu–Zn/SiO2 catalyst are hydrogenated to methanol faster than the μ-HCOO*(Cu) species that are found in the Zn-free Cu/SiO2 catalyst, supporting the role of Zn in providing a higher activity in the Cu–Zn system.

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From ethene to propene (ETP) on tailored silica–alumina supports with isolated Ni(ii) sites: uncovering the importance of surface nickel aluminate sites and the carbon-pool mechanism

Abstract: The ethene-to-propene reaction on Ni catalysts correlates with the formation of alkylated aromatic species. The deactivation of surface Ni aluminate sites can be reversed by calcination, while the deactivation of Ni silicate sites is irreversible.

Cited by 4 publications

References 42 publications

Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Heterogenization of molecular catalysts within porous solids: the case of Ni-catalyzed ethylene oligomerization from zeolites to metal–organic frameworks

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol

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From ethene to propene (ETP) on tailored silica–alumina supports with isolated Ni(ii) sites: uncovering the importance of surface nickel aluminate sites and the carbon-pool mechanism

Abstract: The ethene-to-propene reaction on Ni catalysts correlates with the formation of alkylated aromatic species. The deactivation of surface Ni aluminate sites can be reversed by calcination, while the deactivation of Ni silicate sites is irreversible.

Cited by 4 publications

References 42 publications

Nature of GaOx Shells Grown on Silica by Atomic Layer Deposition

Nature of GaOx Shells Grown on Silica by Atomic Layer Deposition

Heterogenization of molecular catalysts within porous solids: the case of Ni-catalyzed ethylene oligomerization from zeolites to metal–organic frameworks

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO2 Catalysts for the Hydrogenation of CO2 to Methanol

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Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Nature of GaO_x Shells Grown on Silica by Atomic Layer Deposition

Combining Atomic Layer Deposition with Surface Organometallic Chemistry to Enhance Atomic-Scale Interactions and Improve the Activity and Selectivity of Cu–Zn/SiO₂ Catalysts for the Hydrogenation of CO₂ to Methanol