Palladium-nanoparticles on end-functionalized poly(lactic acid)-based stereocomplexes for the chemoselective cinnamaldehyde hydrogenation: Effect of the end-group

Oberhauser, Werner; Evangelisti, Claudio; Jumde, Ravindra P.; Petrucci, Giorgio; Bartoli, Mattia; Frediani, Marco; Mannini, Matteo; Capozzoli, Laura; Passaglia, Elisa; Rosi, Luca

doi:10.1016/j.jcat.2015.07.012

Cited by 26 publications

(19 citation statements)

References 49 publications

(60 reference statements)

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“…Like HRTEM, also EXAFSd ata analysisa tt he Pd K-edge showedt he presence of small fcc Pd nanoparticles having contracted interatomic distances [38,39] in the case of the bimetallic sample and that both the monometallic and the bimetallic cat- alysts have af irst shell Pd-O contribution. [38] As recently found using XPS investigations of MVS-derived samples, [40] ,P da toms are mainly present in aP d 0 phase, but small amountsc an be in aP d 2 + one. Owing to the rather small dimensions of the Pdbased nanoparticles, the Pd atoms on the surface of the nanoparticles can be easily oxidized to form thin surface layers of PdO when treated in air atmosphere.…”

Section: Resultsmentioning

confidence: 61%

Characterization of a Poly‐4‐Vinylpyridine‐Supported CuPd Bimetallic Catalyst for Sonogashira Coupling Reactions

et al. 2017

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CuPd bimetallic solvated metal atoms (SMA) synthesized by metal vapor synthesis (MVS) technique and supported on poly-4-vinylpyridine (PVPy) resin, showed significantly higher catalytic activity in Sonogashira-type carbon-carbon coupling reactions than the corresponding monometallic Cu and Pd systems as well as their physical mixture. The analysis of the bimetallic catalyst combining transmission electron microscopy techniques and X-ray absorption fine structure (XAFS) spectroscopy revealed the presence of small Pd nanoparticles (d =2.5 nm) while the analysis of the X-ray absorption data, at the Cu K-edge suggests the formation of thin and incomplete Cu oxide layers around the Pd-rich cores.

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Section: Resultsmentioning

confidence: 61%

Characterization of a Poly‐4‐Vinylpyridine‐Supported CuPd Bimetallic Catalyst for Sonogashira Coupling Reactions

et al. 2017

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“…Transmission electron microscopic (TEM) analyses carried out on Pd-NPs supported onto PLA-stereocomplexes clearly confirmed the influence of the synthetic procedure on the size of NPs and their distribution and the effect of the nitrogen-containing functional groups on the dispersion of Pd-NPs on the polymer-based support as shown in Figure 4. The thermal gravimetric analysis (TGA) of L 11/12 and Pd@L 11/12 showed that the presence of Pd-Np strongly affected the thermal stability of stereocomplex structures [30] as shown in Figure 5. The decomposition process of L 11/12 started at 552 K instead of Pd@L 11/12 that did not show a meaningful loss of weight up to 575 K. So, not only PLA-stereocomplexes prevent the aggregation of Pd-NPs but the latter increase the thermal stability of the stereocomplex structure.…”

Section: Pd-nps Supported Onto Pla Stereocomplexes: Synthesis and Chamentioning

confidence: 99%

“…Pd-NPs synthesized by the MVS-technique and stabilized by differently end-functionalized PLA-stereocomplexes (i.e., L 1/2 , L 7/8 , L 9/10 , and L 11/12 ) with pyridine, BipyOH, Bn, and OH-end groups, respectively ( Table 1) were tested in the chemoselective C═C double bond cinnamaldehyde in Tetrahydrofuran (THF) [30]. As a result, the following order of decreasing catalytic activity as well as chemoselectivity was found: L 7/8 > L 1/2 >L 9/10 > L 11/12 ( Table 3), which is in line with the decreasing Pd-NPs' dispersion on the polymer surface.…”

Section: Hydrogenation Of C-c Double and Triple Bondsmentioning

confidence: 99%

“…Functionalized PLA stereocomplexes show high resistance against hydrolysis and thermal degradation and in addition, a poor solubility in all organic solvents. This latter property was exploited by Petrucci et al [29] and Oberhauser et al [30] for catalytic purposes to easily separate PLA-stereocomplex-based catalysts from catalytic solution.…”

Section: Introductionmentioning

confidence: 99%

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Palladium‐Based Catalysts‐Supported onto End‐Functionalized Poly(lactide) for C–C Double and Triple Bond Hydrogenation Reactions

Frediani¹,

Oberhauser²,

Rosi³

et al. 2017

New Advances in Hydrogenation Processes - Fundamentals and Applications

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Poly(lactide) (PLA), which is the polymer that will be discussed in this chapter, was functionalized with nitrogen containing aromatic groups by means ring opening polymerization (ROP) reactions. The obtained macroligands were successfully employed to coordinate Pd(II), which chemoselectively hydrogenated αβ-unsaturated carbonyl compounds to give the saturated counterparts as main product. The catalyst could be easily recycled upon a simple filtration process. End-functionalized isotactic PLA chains were used to generate stereocomplexes, featured by a higher thermal and hydrolytic resistance. The chemical nature of the nitrogen ligand introduced at the chain end of PLA was exploited to stabilize Pdnanoparticles (Pd-NP s) by interactions of the aromatic or nitrogen functionality with the NP s-surface. The polymer-anchored Pd-NP s were generated by a classical approach which comprised the coordination of Pd(II) by the functional group followed by reduction with hydrogen or by the metal vapor synthesis technique. The polymersupported Pd-NP s were successfully applied to catalyze the selective hydrogenation of alkynes to the corresponding alkene and cinnamylalcohol to the corresponding saturated aldehyde. In this book chapter the synthesis and structure-performance relationship of the new hydrogenation catalysts will be discussed.

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“…The catalytic system showed the same time advantages of a homogenous catalyst and the easy recyclability of a heterogeneous one. The use of Pd containing poly(lactic acid) systems is a well-established practice for selective hydrogenation of carbon-carbon double bonds [23][24][25], achieving great results for its selectivity and reusability.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Performances of Platinum Containing PLLA Macrocomplex in the Hydrogenation of α,β-Unsaturated Carbonyl Compounds

et al. 2019

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The synthesis of a bipyridine poly(lactic acid) carboxylic end-capped macroligand coordinated to a platinum center was reported. The reaction between the metal ion and the polymeric ligand was run in a very efficient way through a one-step synthesis and the complex was tested for selective hydrogenation of α,β-carbonyl compounds. High selectivity was proven for double bond hydrogenation of 2-cyclohexen-1-one (up to 99%) and the production of 1-butanol from (E)-but-2-enal. Moreover, the catalytic system was still active after three catalytic cycles.

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Palladium-nanoparticles on end-functionalized poly(lactic acid)-based stereocomplexes for the chemoselective cinnamaldehyde hydrogenation: Effect of the end-group

Cited by 26 publications

References 49 publications

Characterization of a Poly‐4‐Vinylpyridine‐Supported CuPd Bimetallic Catalyst for Sonogashira Coupling Reactions

Characterization of a Poly‐4‐Vinylpyridine‐Supported CuPd Bimetallic Catalyst for Sonogashira Coupling Reactions

Palladium‐Based Catalysts‐Supported onto End‐Functionalized Poly(lactide) for C–C Double and Triple Bond Hydrogenation Reactions

Catalytic Performances of Platinum Containing PLLA Macrocomplex in the Hydrogenation of α,β-Unsaturated Carbonyl Compounds

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