Creation of highly stable monomeric Pd(II) species in an anion-exchangeable hydroxy double salt interlayer: Application to aerobic alcohol oxidation under an air atmosphere

Hara, Takayoshi; Ishikawa, Masakazu; Sawada, Junya; Ichikuni, Nobuyuki; Shimazu, Shogo

doi:10.1039/b918350g

Cited by 52 publications

(28 citation statements)

References 45 publications

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“…In contrast, there will be of great advantages if a reaction could be performed in water other than organic solvents. For example, the oxidations in water could be much cheaper and safer than those performed in organic solvents, and products can be isolated by simple procedures, enabling catalysts to be readily recovered and reused [9,10]. However, the catalytic aerobic alcohol oxidation in water was only scarcely explored.…”

Section: Introductionmentioning

confidence: 99%

Diverse copper(II) complexes with simple nitrogen ligands: Structural characterization and applications in aerobic alcohol oxidations in water

Zhang

et al. 2016

Polyhedron

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Section: Introductionmentioning

confidence: 99%

Diverse copper(II) complexes with simple nitrogen ligands: Structural characterization and applications in aerobic alcohol oxidations in water

Zhang

et al. 2016

Polyhedron

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“…Detailed kinetic investigations, alongside in situ [8], [9] and [10] and operando studies [11], [12], [13] and [14] have provided conclusive evidence that allylic alcohol oxidation occurs via a redox mechanism, catalysed by electron deficient, surface Pd(II) species present as PdO. Kumar et al [15], Scott et al [16] and Hara et al [17] have likewise reported a heterogeneous Pd(II) active species responsible for aerobic alcohol selox, while homogeneous Pd(II) complexes are well known to catalyse such alcohol oxidations [18], [19] and [20]. Interestingly, surface PtO2 has also been recently reported as the active phase in the analogous Pt catalysed aerobic selox of allylic alcohols [21].…”

Section: Introductionmentioning

confidence: 99%

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2O3 catalysts

Parlett

Durndell

Wilson

et al. 2014

Catalysis Communications

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Highly ordered mesoporous alumina was prepared via evaporation induced self-assembly and was impregnated to afford a family of Pd/meso-Al 2 O 3 catalysts for the aerobic selective oxidation (selox) of allylic alcohols under mild reaction conditions. CO chemisorption and XPS identify the presence of highly dispersed (0.9 2 nm) nanoparticles comprising heavily oxidised PdO surfaces, evidencing a strong palladium-alumina interaction. Surface PdO is confirmed as the catalytically active phase responsible for allylic alcohol selox, with initial rates for Pd/meso-Al 2 O 3 far exceeding those achievable for palladium over either amorphous alumina or mesoporous silica supports. Pd/meso-Al 2 O 3 is exceptionally active for the atom efficient selox of diverse allylic alcohols, with activity inversely proportional to alcohol mass.

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“…In recent years, an array of ex-situ and in-situ analytical techniques and parallel kinetic profiling has identified electron deficient Pd 2+ , present as PdO at the surface of nanoparticles, as the active species participating in palladium catalysed allylic alcohol selox. Pd 2+ species are proposed to play a critical role in aerobic alcohol oxidations over AuPd core-shell nanoparticles [12] and intercalated Pd/NiZn layered double hydroxides [13], while Pd 2+ complexes are ubiquitous in homogeneously catalysed selox chemistry [14,15].…”

Section: Introductionmentioning

confidence: 99%

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

et al. 2014

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eprints@whiterose.ac.uk https://eprints.whiterose.ac.uk/ Reuse Unless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. Operando, liquid phase XAS highlights the interplay between dissolved oxygen and the oxidation state of palladium nanoparticles dispersed over Al-SBA-15 towards on-stream reduction: ambient pressures of flowing oxygen are sufficient to hinder palladium oxide reduction to metal, enabling a high selox activity to be maintained, whereas rapid PdO reduction and concomitant catalyst deactivation occurs under static oxygen.Selectivity to the desired cinnamaldehyde product mirrors these trends in activity, with flowing oxygen minimising C-O cleavage of the cinnamyl alcohol reactant to trans--methylstyrene, and of cinnamaldehyde decarbonylation to styrene. Highlights: An ultrathin alumina coating has been grafted onto a SBA-15 mesoporous silica architecture. Pd impregnated Al-SBA-15 materials are superior catalysts for the aerobic selox of allylic alcohols to aldehydes compared to pure silica or alumina supports.  Operando XAS confirms cinnamyl alcohol selox occurs over a PdO active species, which is prone to on-stream reduction and associated catalyst deactivation under static oxygen. [20,21] have highlighted PdO reduction to metallic palladium as a potential deactivation pathway, and hence the importance of generating highly dispersed nanoparticles which favour an oxide phase [20,[22][23][24]. KeywordsTemperature-programmed desorption and XPS of crotyl alcohol (but-2-en-1-ol) and crotonaldehyde (but-2-en-1-al) over Pd(111) and palladium-rich Au/Pd surface alloys suggest deactivation arises from crotonaldehyde decarbonylation and subsequent site-blocking by strongly adsorbed propylidyne and CO [20,21]. Computational modelling predicts Pd(111) can also drive propanoic acid decarbonylation [25]. Vapour phase studies of crotyl alcohol oxidation show that such in-situ palladium reduction is reversible under oxidising environments [17,19], enabling selox to be maintained, however the ability of dissolved oxygen to preserve palladium as PdO during liquid phase selox is unknown. Experimental Catalyst synthesisThe parent SBA-15 silica framework was synthesised following the method of Zhao et al [30]. Pluronic P123 (10 g) was dissolved in water (75.5 ...

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Creation of highly stable monomeric Pd(II) species in an anion-exchangeable hydroxy double salt interlayer: Application to aerobic alcohol oxidation under an air atmosphere

Cited by 52 publications

References 45 publications

Diverse copper(II) complexes with simple nitrogen ligands: Structural characterization and applications in aerobic alcohol oxidations in water

Diverse copper(II) complexes with simple nitrogen ligands: Structural characterization and applications in aerobic alcohol oxidations in water

Selective oxidation of allylic alcohols over highly ordered Pd/meso-Al2O3 catalysts

Alumina-grafted SBA-15 as a high performance support for Pd-catalysed cinnamyl alcohol selective oxidation

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