Selective hydrogenation of 2-methyl-3-butyn-2-ol over Pd-nanoparticles stabilized in hypercrosslinked polystyrene: Solvent effect

Nikoshvili, Linda Zh.; Shimanskaya, E. I.; Быков, А. А.; Yuranov, Igor; Kiwi‐Minsker, Lioubov; Sulman, Esther M.

doi:10.1016/j.cattod.2014.01.045

Cited by 43 publications

(39 citation statements)

References 34 publications

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“…For the 0.7%-Pd/MN100-Na catalyst the mean diameter of the Pd NPs is 4.7 ± 1.0 nm (Figure 7a,b), which is essentially the same size as the Pd NPs in a previously reported 0.7%-Pd/MN100 catalyst (4.5 ± 0.9 nm 18 ). In contrast, the 0.7%-Pd/MN100-R catalyst contains Pd NPs with a much larger mean diameter of 13.2 ± 4.8 nm (Figure 7c,d).…”

Section: Industrial and Engineering Chemistry Researchsupporting

confidence: 52%

“…Testing of the catalysts in the selective hydrogenation of MBY to MBE ( Figure 2) was performed at 90°C in a 60 mL isothermal glass batch reactor connected to a gasometrical buret for online monitoring of hydrogen consumption, and installed in a shaker for vigorous mixing (more than 800 twosided shaking per minute), which excludes external diffusion limitations. 18 The internal diffusion limitations were also excluded via powdering of HPS to <63 μm. 18,19 Toluene was used as a solvent.…”

Section: Articlementioning

confidence: 99%

“…18 The internal diffusion limitations were also excluded via powdering of HPS to <63 μm. 18,19 Toluene was used as a solvent. A recirculating bath (LOIP LT 100, SaintPetersburg, Russia) was used to stabilize the reaction temperature within ±1°C using water as the thermal medium.…”

Section: Articlementioning

confidence: 99%

“…The choice of solvent and reaction temperature was based on previous studies. 18,19 At the beginning of each experiment, the temperature was set to 90°C, and allowed to stabilize (ca. 30 min).…”

Section: Articlementioning

confidence: 99%

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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

Nikoshvili

Быков

Khudyakova

et al. 2017

Ind. Eng. Chem. Res.

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Postimpregnation of Pd nanoparticles (NPs) stabilized within hyper-cross-linked polystyrene with sodium or potassium hydroxides of optimal concentration was found to significantly increase the catalytic activity for the partial hydrogenation of the C−C triple bond in 2-methyl-3-butyn-2-ol at ambient hydrogen pressure. The alkali metal hydroxide accelerates the transformation of the residual Pd(II) salt into Pd(0) NPs and diminishes the reaction induction period. In addition, the selectivity to the desired 2-methyl-3-buten-2-ol increases with the K-and Na-doped catalysts from 97.0 up to 99.5%. This effect was assigned to interactions of the alkali metal ions with the Pd NPs surfaces resulting in the sites' separation and a change of reactants adsorption.

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Section: Industrial and Engineering Chemistry Researchsupporting

confidence: 52%

Section: Articlementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

Section: Articlementioning

confidence: 99%

See 2 more Smart Citations

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

Nikoshvili

Быков

Khudyakova

et al. 2017

Ind. Eng. Chem. Res.

Self Cite

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“…Solvent effects may also play a role in the change in the selectivity, however, the literature data indicate that the solvent mainly affects the reaction rates [63]. The literature data on the solvent effects in MBY semihydrogenation over the Pd nanoparticles suggest that the solvent effects should result in a minor increase in MBE selectivity (0.5-1.0%) in alcohol as compared to water solvent [64]. Therefore, the increasing selectivity in the diluted solution is likely associated with the decrease in the substrate concentration rather than the solvent effect.…”

Section: Effect Of Liquid Flow Ratesmentioning

confidence: 99%

Process Intensification of Alkynol Semihydrogenation in a Tube Reactor Coated with a Pd/ZnO Catalyst

2017

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Semihydrogenation of 2-methyl-3-butyn-2-ol (MBY) was studied in a 5 m tube reactor wall-coated with a 5 wt % Pd/ZnO catalyst. The system allowed for the excellent selectivity towards the intermediate alkene of 97.8 ± 0.2% at an ambient H 2 pressure and a MBY conversion below 90%. The maximum alkene yield reached 94.6% under solvent-free conditions and 96.0% in a 30 vol % MBY aqueous solution. The reactor stability was studied for 80 h on stream with a deactivation rate of only 0.07% per hour. Such a low deactivation rate provides a continuous operation of one month with only a two-fold decrease in catalyst activity and a metal leaching below 1 parts per billion (ppb). The excellent turn-over numbers (TON) of above 10 5 illustrates a very efficient utilisation of the noble metal inside catalyst-coated tube reactors. When compared to batch operation at 70 • C, the reaction rate in flow reactor can be increased by eight times at a higher reaction temperature, keeping the same product decomposition of about 1% in both cases.

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Cyclodextrin‐Grafted Silica‐Supported Pd Nanoparticles: An Efficient and Versatile Catalyst for Ligand‐Free C−C Coupling and Hydrogenation

et al. 2016

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Silica is an extremely versatile support, which is capable of hosting metal nanoparticles (NPs) and enhancing their stability and reactivity. In this study, a novel cyclodextrin/silica support for Pd NPs, which we have denoted Pd/Si‐CD, has been prepared. The highly efficient and homogeneous impregnation of small palladium nanoparticles on this support has been carried out under conventional conditions, and ultrasound irradiation has been shown to have a beneficial effect on catalyst preparation. The catalyst exhibited excellent activity in ligand‐free C−C Suzuki and Heck couplings with a large number of aryl iodide and bromides, in which microwave irradiation use cuts down reaction time. Pd/Si‐CD have shown high activity and selectivity in the hydrogenation reaction, and the semihydrogenation of phenyl acetylene was also studied with excellent results.

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Selective hydrogenation of 2-methyl-3-butyn-2-ol over Pd-nanoparticles stabilized in hypercrosslinked polystyrene: Solvent effect

Cited by 43 publications

References 34 publications

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

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

Process Intensification of Alkynol Semihydrogenation in a Tube Reactor Coated with a Pd/ZnO Catalyst

Cyclodextrin‐Grafted Silica‐Supported Pd Nanoparticles: An Efficient and Versatile Catalyst for Ligand‐Free C−C Coupling and Hydrogenation

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