Selective hydrogenation of terminal alkynes over palladium nanoparticles within the pores of amino-modified porous aromatic frameworks

Караханов, Э. А.; Maximov, A. L.; Terenina, M. V.; Винокуров, В. А.; Куликов, Л. А.; Makeeva, D. A.; Glotov, Aleksandr

doi:10.1016/j.cattod.2019.05.028

Cited by 23 publications

(12 citation statements)

References 45 publications

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“…9,74 However, some catalytic properties (such as: type of support, surface acidity, particle size, dispersion, and type of active sites among others) can influence undesired processes, like the overhydrogenation or isomerization reactions of alkenes. 6,9,75,76 Scheme 1 summarizes the proposed interaction between palladium precursor with the different supports used in the synthesis of the catalysts. Initially, the chloride palladium precursor [PdCl 4 ] 2− at pH = 1 was impregnated over different supports that offer different physicochemical characteristics.…”

Section: Catalytic Tests Hydrogenation Of Pure 1-heptyne and 1-pentynementioning

confidence: 99%

Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

Cordoba

Betti

Bovier

et al. 2021

J of Chemical Tech & Biotech

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BACKGROUND: Pd nanoparticles over different supports were evaluated during the alkyne selective hydrogenation of medium chain (C 7 and C 5 ) and the 1-pentene purification at mild operational conditions (150 kPa and 303 K). The role of support and chloride was investigated; γ-Al 2 O 3 , γ-Al 2 O 3 modified with Mg, CaCO 3 and activated carbon were used as supports, and PdCl 2 as precursor salt. The classical Lindlar catalyst was used as reference.RESULTS: Surface acidity of supports, active sites dispersion and surface species (MgO, Pd x Cl y O z and/or functional groups) can favor or disfavor the desorption of 1-alkene during the purification of 1-pentene stream. The smallest particle sizes (3.8-10.0 nm) favor the dissociative adsorption of hydrogen over Pd°active sites, promoting good catalytic behavior. The best synthesized catalysts are Pd/Al-Mg and Pd/Ca, and their high selectivity (≥90%) is favored by the presence of superficial acidic Lewis sites. On the contrary, lower selectivity (74-80%) is assessed on catalysts with Brönsted acidic sites (Pd/Al and Pd/RX3) that favored the undesired overhydrogenation or isomerization reactions. CONCLUSION:The geometric and electronic properties of the support have a major influence on the activity and selectivity of the catalysts. Low loaded Pd catalysts supported on Al 2 O 3 -Mg and CaCO 3 (Pd/Al-Mg, Pd/Ca) can be used for the purification of medium or large terminal alkenes at mild reaction conditions as an alternative to the toxic Lindlar commercial catalyst.

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Section: Catalytic Tests Hydrogenation Of Pure 1-heptyne and 1-pentynementioning

confidence: 99%

Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

Cordoba

Betti

Bovier

et al. 2021

J of Chemical Tech & Biotech

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“…The latter (otherwise called porous aromatic frameworks) are three-dimensional polymers, who’s rigid, diamond-like structure, consisting of tetrahedral node atoms connected with polyphenylene edges ( Figure 19 ), provides high specific surface area and thermal stability [ 375 , 376 , 377 , 378 ]. Earlier it was demonstrated that Pd nanoparticles, immobilized on polyaromatic frameworks, functionalized with amino groups, appeared noticeably inferior to those based on unmodified PAFs, as catalysts for hydrogenation of various unsaturated compounds (phenylacetylene and styrene, linear alkenes, alkynes, and dienes) [ 379 ]. Nonetheless, this Pd/PAF-NH 2 catalyst exhibited excellent stability, maintaining a conversion of about 30% in the hydrogenation of phenylacetylene during 6 cycles [ 379 ].…”

Section: Covalent Immobilization On Heterogeneous Supportsmentioning

confidence: 99%

“…Earlier it was demonstrated that Pd nanoparticles, immobilized on polyaromatic frameworks, functionalized with amino groups, appeared noticeably inferior to those based on unmodified PAFs, as catalysts for hydrogenation of various unsaturated compounds (phenylacetylene and styrene, linear alkenes, alkynes, and dienes) [ 379 ]. Nonetheless, this Pd/PAF-NH 2 catalyst exhibited excellent stability, maintaining a conversion of about 30% in the hydrogenation of phenylacetylene during 6 cycles [ 379 ]. Herein, amino groups attached to polyphenylene edges of PAFs can be considered as G0 dendrons.…”

Section: Covalent Immobilization On Heterogeneous Supportsmentioning

confidence: 99%

Heterogeneous Dendrimer-Based Catalysts

2022

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The present review compiles the advances in the dendritic catalysis within the last two decades, in particular concerning heterogeneous dendrimer-based catalysts and their and application in various processes, such as hydrogenation, oxidation, cross-coupling reactions, etc. There are considered three main approaches to the synthesis of immobilized heterogeneous dendrimer-based catalysts: (1) impregnation/adsorption on silica or carbon carriers; (2) dendrimer covalent grafting to various supports (silica, polystyrene, carbon nanotubes, porous aromatic frameworks, etc.), which may be performed in a divergent (as a gradual dendron growth on the support) or convergent way (as a grafting of whole dendrimer to the support); and (3) dendrimer cross-linking, using transition metal ions (resulting in coordination polymer networks) or bifunctional organic linkers, whose size, polarity, and rigidity define the properties of the resulted material. Additionally, magnetically separable dendritic catalysts, which can be synthesized using the three above-mentioned approaches, are also considered. Dendritic catalysts, synthesized in such ways, can be stored as powders and be easily separated from the reaction medium by filtration/centrifugation as traditional heterogeneous catalysts, maintaining efficiency as for homogeneous dendritic catalysts.

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“…At the same time, metal NPs tend to agglomerate and are easily oxidized in air, resulting in a loss of their catalytic activity. Thus, the development of cost-effective materials with limited aggregation and leaching of noble metal NPs is of high importance [ 2 ]. In recent years, porous organic polymers with a high surface area have attracted great attention.…”

Section: Introductionmentioning

confidence: 99%

Mono- and Bimetallic Nanoparticles Stabilized by an Aromatic Polymeric Network for a Suzuki Cross-Coupling Reaction

et al. 2021

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This work addresses the Suzuki cross-coupling between 4-bromoanisole (BrAn) and phenylboronic acid (PBA) in an environmentally benign ethanol–water solvent catalysed by mono- (Pd) and bimetallic (PdAu, PdCu, PdZn) nanoparticles (NPs) stabilised within hyper-cross-linked polystyrene (HPS) bearing tertiary amino groups. Small Pd NPs of about 2 nm in diameters were formed and stabilized by HPS independently in the presence of other metals. High catalytic activity and complete conversion of BrAn was attained at low Pd loading. Introduction of Zn to the catalyst composition resulted in the formation of Pd/Zn/ZnO NPs, which demonstrated nearly double activity as compared to Pd/HPS. Bimetallic core-shell PdAu/HPS samples were 3-fold more active as compared to Pd/HPS. Both Pd/HPS and PdAu/HPS samples revealed promising stability confirmed by catalyst recycling in repeated reaction runs.

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Selective hydrogenation of terminal alkynes over palladium nanoparticles within the pores of amino-modified porous aromatic frameworks

Cited by 23 publications

References 45 publications

Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

Role of the support and chloride during the purification of 1‐pentene in alkyne/alkene streams over Pd catalysts

Heterogeneous Dendrimer-Based Catalysts

Mono- and Bimetallic Nanoparticles Stabilized by an Aromatic Polymeric Network for a Suzuki Cross-Coupling Reaction

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