Supported Cobalt Catalysts for Acceptorless Alcohol Dehydrogenation

Kaźmierczak, Kamila; Pinel, Catherine; Loridant, S.; Бессон, М.; Michel, Carine; Perret, Noémie

doi:10.1002/cplu.202000359

Cited by 17 publications

(22 citation statements)

References 49 publications

(71 reference statements)

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“…Supported cobalt catalysts were shown to be active in the dehydrogenation of secondary alcohols, including 2-octanol. 20,21 However, the reactions were not completely selective to 2-octanone and H 2 due to the formation of small amounts of C16 byproducts, resulting from aldol condensation/ dehydration reactions, followed by subsequent hydrogenation. 20 On the other hand, shape-controlled unsupported Co NPs were highly selective in the former reaction.…”

Section: Introductionmentioning

confidence: 99%

Influence of Capping Ligands on the Catalytic Performances of Cobalt Nanoparticles Prepared with the Organometallic Route

Kaźmierczak

Jaud

et al. 2021

J. Phys. Chem. C

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Cobalt nanorods and cobalt nanoplatelets, prepared by the same organometallic route with two different metal precursors, were tested for the first time in the acceptor-less dehydrogenation of 2-octanol. The nature of the metal precursor determines not only nanoparticle morphology but also their surface chemistry. While cobalt nanorods showed high conversions (up to 85% after 24 h) and complete selectivity toward 2-octanone with concomitant molecular hydrogen production, cobalt nanoplatelets were practically inactive. Here, we show that this striking difference in the catalytic properties is not associated with facet-dependent differences in reactivity, but rather with different surface chemistry. The activity critically depends on the coordinating ability of the adsorbed species under catalytic reaction conditions and to a smaller degree on their concentration, as evidenced by ligand exchange experiments at room temperature as well as by direct addition of ligands in the reaction during catalysis by cobalt nanorods. This study shows that to optimize performances with unsupported metal nanocatalysts, the capping ligands should be selected by considering their ability to reversibly dissociate from the metal surface during catalysis.

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Section: Introductionmentioning

confidence: 99%

Influence of Capping Ligands on the Catalytic Performances of Cobalt Nanoparticles Prepared with the Organometallic Route

Kaźmierczak

Jaud

et al. 2021

J. Phys. Chem. C

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“…These compounds originate from aldol condensation and further hydrogenation processes. 49,50 This also explains why the octan-1-ol conversion (55 %) is much higher than the yield of H 2 (29 % after 24 h, see Figure 9a); with an acceptorless mechanism, two similar values are expected. To explain our results, it is assumed that H 2 generated by dehydrogenation of alcohols is next used to hydrogenate aldol condensation products following a reaction pathway that has been proposed previously with Cu/ZrO 2 catalyst.…”

Section: Catalytic Acceptorless Dehydrogenation Of Alcoholsmentioning

confidence: 65%

“…Very interestingly, unsupported Co 50 Ru 50 nanoalloys are found to be much more active than heterogeneous catalysts corresponding to Co, or Ru supported on various supports tested under identical conditions. 49,50 An octan-1-ol conversion of 55 % was found after 24 h at 145 °C for the nanoalloys, to be compared to 10 % obtained with Co/TiO 2 49 or 8 % with Ru/TiO 2 , 50 tested under the same conditions.…”

Section: Catalytic Acceptorless Dehydrogenation Of Alcoholsmentioning

confidence: 97%

Facile soft-chemistry synthesis of Co-Ru nanoalloys: influence of the composition on the catalytic activity for the acceptorless dehydrogenation of alcohols.

Azeredo

Ghzaiel

Huang

et al. 2022

Preprint

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The synthesis of Co-Ru bimetallic nanoparticles was performed by co-reduction of Co(II) and Ru(III) salts in octan-1-ol, acting both as a solvent and a mild reducing agent. The metal composition was varied in the entire range, from pure Co to pure Ru. Although Co and Ru are miscible in the bulk, the formation of nanoalloys is not straightforward and requires selecting carefully reaction parameters such as the nature of the solvent and that of the metal precursors. The formation of nanoalloys was unambiguously evidenced by HAADF STEM–EDX analyses. The particle size and the size dispersity were found to decrease with increasing Ru amount, yielding very small and monodisperse particles for the richest compositions in Ru. The unsupported particles were tested for the acceptorless alcohol dehydrogenation using (±)-octan-2-ol and octan-1-ol as model substrates. The results clearly show a synergetic effect since the bimetallic particles exhibit better performances than their monometallic counterparts.

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“…The only by‐product, hydrogen, is a sustainable energy carrier due to its high energy capacity [8–9] . It is worth noting that high selectivity of aldehydes or ketones can be achieved in this approach owing to the absence of oxidants [10–32] …”

Section: Introductionmentioning

confidence: 99%

“…Alcohol splitting is an uphill reaction (endothermic), implying that energy is required to drive this reaction [10–32] . Conventional alcohol splitting reactions are usually conducted at equal or above 90 °C [10–24] . Alcohol splitting by electrolysis has also been reported, but an electrolyte and a complicated apparatus are needed [25] .…”

Section: Introductionmentioning

confidence: 99%

Light‐Driven Alcohol Splitting by Heterogeneous Photocatalysis: Recent Advances, Mechanism and Prospects

Chai

2021

Chemistry An Asian Journal

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Splitting of alcohols into hydrogen and corresponding carbonyl compounds, also called acceptorless alcohol dehydrogenation, is of great significance for both synthetic chemistry and hydrogen production. Light‐Driven Alcohol Splitting (LDAS) by heterogeneous photocatalysis is a promising route to achieve such transformations, and it possesses advantages including high selectivity of the carbonyl compounds, extremely mild reaction conditions (room temperature and irradiation of visible light) and easy separation of the photocatalysts from the reaction mixtures. Because a variety of alcohols can be derived from biomass, LDAS can also be regarded as one of the most sustainable approaches for hydrogen production. In this Review, recent advances in the LDAS catalyzed by the heterogeneous photocatalysts are summarized, focusing on the mechanistic insights for the LDAS and aspects that influence the performance of the photocatalysts from viewpoints of metallic co‐catalysts, semiconductors, and metal/semiconductor interfaces. In addition, challenges and prospects have been discussed in order to present a complete picture of this field.

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Supported Cobalt Catalysts for Acceptorless Alcohol Dehydrogenation

Abstract: Supporting information for this article is given via a link at the end of the document.

Cited by 17 publications

References 49 publications

Influence of Capping Ligands on the Catalytic Performances of Cobalt Nanoparticles Prepared with the Organometallic Route

Influence of Capping Ligands on the Catalytic Performances of Cobalt Nanoparticles Prepared with the Organometallic Route

Facile soft-chemistry synthesis of Co-Ru nanoalloys: influence of the composition on the catalytic activity for the acceptorless dehydrogenation of alcohols.

Light‐Driven Alcohol Splitting by Heterogeneous Photocatalysis: Recent Advances, Mechanism and Prospects

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