Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Durndell, Lee J.; Parlett, Christopher M. A.; Hondow, Nicole; Isaacs, Mark A.; Wilson, Karen; Lee, Adam F.

doi:10.1038/srep09425

Cited by 116 publications

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“…The catalytic advantage of spatially segregating Pt NPs within mesopores, accessible overwhelmingly only through interconnected macropores containing Pd NPs, was explored for the cascade oxidative dehydrogenation of cinnamyl alcohol  cinnamaldehyde  cinnamic acid, the latter an important flavorant and essential oil 21,22 . Pd is highly selective for catalyzing cinnamyl alcohol oxidation to cinnamaldehyde 23,24 , but promotes decarbonylation of the resultant aldehyde product; in contrast, Pt favours undesired hydrogenation of cinnamyl alcohol (via reactively-formed surface hydrogen) to 3-phenylpropionaldehyde 25 , but is highly selective towards cinnamaldehyde oxidation to the desirable cinnamic acid product 26 . An optimal catalyst design would therefore ensure that cinnamyl alcohol was oxidized over Pd prior to encountering Pt sites, while permitting the reactively-formed cinnamaldehyde to subsequently access Pt sites for the selective production of cinnamic acid in the second oxidation step.…”

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Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

et al. 2015

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. (2016) 'Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions.', Nature materials., 15 (2). pp. 178-182.Further information on publisher's website:Publisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details.

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Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

et al. 2015

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“…We recently reported a detailed mechanistic study of the structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over fumed SiO2 and mesoporous SBA-15 supported Pt nanoparticles. 26 Kinetic mapping revealed cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency (TOF) Please do not adjust margins Please do not adjust margins independent of precursor, particle size or support architecture, while selectivity to CinnOH is highly structure sensitive. Large nanoparticles and high hydrogen pressures favored C=O over C=C hydrogenation due to molecular surface crowding, while in situ ATR-IR highlighted the role of support polarity in enhancing C=O hydrogenation.…”

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Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

2015

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Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and singlepass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.Chemoselectivity underpins 21 st century catalysis, 1, 2 permitting the targeted modification of specific functional groups within complex starting materials, 3-7 notably from biomass-derived feedstocks. 8 Catalytic hydrogenation of organic compounds possessing multiple unsaturated bonds such as α,β-unsaturated aldehydes is particularly challenging, 9-11 necessitating active sites able to discriminate and preferentially activate closely related moieties. Platinum is widely employed in heterogeneously catalysed hydrogenation of diverse functional groups including C=C, 12 C≡C, 13 C=O, 13 C≡N, 14 NO2 15 and aromatics. 15 The selective hydrogenation of allylic and benzylic aldehydes to unsaturated alcohols is a commercially important industrial process within the flavour, fragrance, agrochemical and pharmaceutical sectors, 9, 16 in which active and selective heterogeneous catalysts for such transformations are essential to circumvent the greater thermodynamic stability of C=O relative to C=C bonds. 9 The liquid phase, selective hydrogenation of cinnamaldehyde (CinnALD) to cinnamyl alcohol (CinnOH) illustrated in Scheme 1 is of significant interest due to the widespread use of this allylic alcohol in perfumes and flavourants. [16][17][18][19] Platinum is a promising catalyst for this challenging reaction, in which hydrogenation of the C=C bond is both kinetically and thermodynamically more favourable than the C=O function, 20 and hence the influence of the physicochemical properties of platinum nanoparticles is a topic of much intensive recent investigation in batch reactors. Particle size effects upon CinnOH selectivity have proved controversial, with oleic acid/oleylamine stabilised mono-and bimetallic colloidal Pt nanoparticles reported to exhibit a strong size dependence of CinnOH selectivity, with low coordination sites favoring C=C hydrogenation, 21, 22 whereas Zhu and Zaera reported that CinnOH selectivity was insensitive to the size of silica supported Pt nanoparticles albeit over a narrow size range. 23 Guo et al have shown that confinement of Pt nanoclusters within the cavity of metal-organic frameworks also promotes CinnOH selectivity; with steric constraints on CinnALD believed to hinder C=C planar adsorption with consequent preferential C=O activation. 24 Kinetics of CinnALD hydrogenation are also a function of support properties 25 and hydrogenation pressure. We recently reported a detailed mechanistic study of the structura...

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“…Thes elective hydrogenation of unsaturated carbonylc ompoundsi sac riticals tep in the synthesis of various fine chemicals, in particular, in flavor,f ragrance, andp harmaceutical chemistry. [15] Instead of the desired unsaturated alcohols, however,t he saturated aldehydes are the thermodynamically favored products because of the higherf ree reaction enthalpyo fC =O( 40 kJ mol…”

Section: Catalytic Hydrogenation With Niir 4 and Nios 4 Particlesmentioning

confidence: 99%

“…The selectiveh ydrogenation of such allylic aldehydes to unsaturateda lcohols, moreover,i sc ommerciallyr elevant in flavors and pharmaceuticals. [15] Finally,d iphenylacetylene is highly relevant for the production of (Z)-/(E)-stilbene, which is an important buildingb lock for dyes, liquid crystals, fluorescent whiteners, and organic light-emitting diodes (OLEDs). Usually,the synthesis is performed by Wittig or Heck reactions that essentially consumes toichiometric amountso fo rganicr eagents, such as base.…”

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Bimetallic Nickel‐Iridium and Nickel‐Osmium Alloy Nanoparticles and Their Catalytic Performance in Hydrogenation Reactions

et al. 2017

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Bimetallic NiIr4 and NiOs4 alloy nanoparticles are prepared and studied with regard to their performance in catalytic hydrogenation reactions. NiIr4 and NiOs4 nanoparticles are obtained by oleylamine‐driven reduction and exhibit mean diameters of (8.9±1.3) and (6.8±1.4) nm at low agglomeration. The phase composition was determined in detail by using different methods, which include high‐resolution TEM, scanning transmission electron microscopy, selected‐area electron diffraction, X‐ray diffraction, and energy‐dispersive X‐ray spectroscopy. This and results in a uniform distribution of both metals Ni‐Ir and Ni‐Os with a ratio of 1:4. The catalytic performance of the NiIr4 and NiOs4 nanoparticles for hydrogenation reactions is evaluated using three selected model substrates: 1‐octene, cinnamaldehyde, and diphenylacetylene. Similar sized Ni, Ir, and Os nanoparticles were used as references. Most remarkable are the excellent selectivity of NiOs4 in the hydrogenation of cinnamaldehyde and the promising formation of (Z)‐stilbene in terms of conversion activity and selectivity. The alloying of Ir and Os with Ni, moreover, is highly cost efficient. In general, both bimetallic alloy nanoparticles, NiIr4 and NiOs4, are shown here for the first time in terms of synthesis, composition, and catalytic hydrogenation.

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Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Cited by 116 publications

References 66 publications

Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Bimetallic Nickel‐Iridium and Nickel‐Osmium Alloy Nanoparticles and Their Catalytic Performance in Hydrogenation Reactions

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