Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

Nikoshvili, Linda Zh.; Быков, А. А.; Khudyakova, Tatiana E.; LaGrange, Thomas; Héroguel, Florent; Luterbacher, Jeremy S.; Matveeva, Valentina G.; Sulman, Esther M.; Dyson, Paul J.; Kiwi‐Minsker, Lioubov

doi:10.1021/acs.iecr.7b01612

Cited by 16 publications

(10 citation statements)

References 31 publications

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“…It is noteworthy that all the initial samples were unreduced and contained Pd(II). As it was supposed in one of our previous publications [27] and also shown in the work of Hu K.-J. et al [28], formation of Pd NPs occurs effectively in situ in the presence of the substrate.…”

Section: Resultssupporting

confidence: 72%

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

et al. 2022

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This work is addressing the selective hydrogenation of alkynols over hybrid catalysts containing Pd-nanoparticles, within newly synthesized hyper-cross-linked polystyrenes (HPS). Alkynols containing C5, C10, and C20 with a terminal triple bond, which are structural analogues or direct semi-products of fragrant substances and fat-soluble vitamins, have been studied. Selective hydrogenation was carried out in a batch mode (ambient hydrogen pressure, at 90 °C, in toluene solvent), using hybrid Pd catalysts with low metal content (less than 0.2 wt.%). The microporous and mesoporous HPS were both synthesized and used as supports in order to address the influence of porosity. Synthesized catalysts were shown to be active and selective: in the case of C5, hydrogenation selectivity to the target product was more than 95%, at close to complete alkynol conversion. Mesoporous catalysts have shown some advantages in hydrogenation of long-chain alkynols.

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Section: Resultssupporting

confidence: 72%

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

et al. 2022

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“…The standard industrial synthesis route has involved the hydrogenation of alkynols over Pd catalysts . The existing literature on alkynol hydrogenation has focused on tertiary alkynols, notably 2-methyl-3-butyn-2-ol . The only reported transformation of secondary alkynols involved liquid-phase conversion of 3-butyn-2-ol using Pd/Al 2 O 3 in pressurized (oscillatory baffled vs stirred tank) reactors. , We have recently reported the formation of 2-butanol and 2-butanone as by-products in the continuous hydrogenation of 3-butyn-2-ol over a commercial Pd/Al 2 O 3 catalyst .…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Catalytic Hydrogenation/Isomerization in the Transformation of 3-Butyn-2-ol over Pd-Ni/Al₂O₃

2021

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The continuous gas-phase (P = 1 atm; T = 373 K) hydrogenation of 3butyn-2-ol has been investigated over Pd/Al 2 O 3 and Ni/Al 2 O 3 prepared by incipient wetness impregnation and Pd−Ni/Al 2 O 3 (Pd/Ni mol ratio = 1:1) synthesized by coimpregnation. A physical mixture (Pd/Al 2 O 3 + Ni/Al 2 O 3 ; Pd/Ni = 1:1) is also considered for comparison purposes. H 2 temperature-programmed reduction (TPR) results are consistent with a lower temperature requirement for the reduction of palladium and nickel in the bimetallic catalyst relative to the monometallic counterparts. The Pd/Al 2 O 3 catalyst exhibits a narrow metal particle size distribution (mean = 20 nm) while Ni/Al 2 O 3 and Pd−Ni/Al 2 O 3 bore larger particles (mean = 28 ± 2 nm). TEM−EDX, XRD, and XPS measurements are consistent with a palladium surface-enriched Pd−Ni bimetallic phase. Ni/Al 2 O 3 promoted exclusive −CC− group hydrogenation to generate 3-buten-2-ol (partial reduction) and 2-butanol (complete reduction). Pd/Al 2 O 3 exhibited a greater H 2 uptake and delivered a higher 3-butyn-2-ol transformation rate, yielding 3-buten-2-ol, 2-butanol, and 2-butanone through hydrogenation and double bond migration. An equivalent H 2 uptake, rate, and product distribution were delivered by Pd/Al 2 O 3 and the Pd/Al 2 O 3 + Ni/Al 2 O 3 system, where the catalytic response was controlled by the palladium component. In contrast, we recorded a higher hydrogen chemisorption on Pd−Ni/Al 2 O 3 (vs Pd/Al 2 O 3 ) and catalytic activity with an enhanced selectivity to 3-buten-2-ol (up to 95%). We linked the distinct response over Pd−Ni/Al 2 O 3 to the formation of bimetallic Pd−Ni as proven by TPR, XRD, TEM−EDX, and XPS analyses. A parallel/stepwise kinetic model has been used to quantify the catalytic hydrogenation response.

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“…These results suggest that Pd NPs were mostly formed (during H 2 liquid-phase reduction of Pd/MN270-NaW at conditions of MBY hydrogenation) and probably are responsible for observed catalytic activity. Recently, we have found that the presence of alkali metals strongly influences the behavior (activity and selectivity) of hydrogenation catalysts synthesized while using chloridecontaining Pd salt [10]. Moreover, the sample treatments after impregnation with sodium carbonate accelerates precursor decomposition rendering Pd oxide and Pd NPs (see the results of XPS data).…”

Section: Suzuki Cross-coupling Results Of Catalytic Testing Of Pd/ Mmentioning

confidence: 99%

“…Pd-containing catalyst with calculated metal loading 1.5 wt.% was synthesized via conventional wet impregnation according to the procedure, which we described earlier elsewhere [9][10][11][12]. In a typical experiment, 1 g of pretreated (washed with distilled water and then with acetone), dried, and crushed (<70 μm) granules of HPS was impregnated with 2.7 mL of the Pd(CH 3 COO) 2 THF solution (concentration 0.058 mol/L).…”

Section: Catalyst Synthesis Hps-basedmentioning

confidence: 99%

“…Among numerous supports, rigid nanostructured polymers such as hypercrosslinked polystyrene (HPS) can be considered the most promising. Recently, we have shown that the HPS of MN100 type bearing amino groups can be used as a support for palladium NPs and clusters to catalyze effectively Suzuki reaction [9] and selective hydrogenation of triple bond in alkynols [10].…”

Section: Introductionmentioning

confidence: 99%

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Pd Nanoparticles Stabilized by Hypercrosslinked Polystyrene Catalyze Selective Triple C-C Bond Hydrogenation and Suzuki Cross-Coupling

Nikoshvili

Nemygina

Khudyakova

et al. 2019

Journal of Nanomaterials

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This paper describes the synthesis of Pd-containing catalysts based on nonfunctionalized hypercrosslinked polystyrene via impregnation with Pd acetate. Developed Pd nanoparticulate catalyst allowed achieving conversion of aryl halide up to 90% in Suzuki cross-coupling reaction under mild conditions and at the absence of phase-transfer agents. During the selective hydrogenation of triple C-C bond of 2-methyl-3-butyn-2-ol, up to 96% selectivity with respect to corresponding olefinic alcohol was found at 95% conversion. The influences of the procedure of catalyst synthesis like precursor decomposition and reductive activation method on Pd nanoparticle formation are discussed.

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Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

Cited by 16 publications

References 31 publications

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

Gas-Phase Catalytic Hydrogenation/Isomerization in the Transformation of 3-Butyn-2-ol over Pd-Ni/Al₂O₃

Pd Nanoparticles Stabilized by Hypercrosslinked Polystyrene Catalyze Selective Triple C-C Bond Hydrogenation and Suzuki Cross-Coupling

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Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

Cited by 16 publications

References 31 publications

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

Hybrid Pd-Nanoparticles within Polymeric Network in Selective Hydrogenation of Alkynols: Influence of Support Porosity

Gas-Phase Catalytic Hydrogenation/Isomerization in the Transformation of 3-Butyn-2-ol over Pd-Ni/Al2O3

Pd Nanoparticles Stabilized by Hypercrosslinked Polystyrene Catalyze Selective Triple C-C Bond Hydrogenation and Suzuki Cross-Coupling

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Gas-Phase Catalytic Hydrogenation/Isomerization in the Transformation of 3-Butyn-2-ol over Pd-Ni/Al₂O₃