Supported catalysts based on Pd–In nanoparticles for the liquid- phase hydrogenation of terminal and internal alkynes: 2. catalytic properties

Марков, П. В.; Брагина, Г. О.; Баева, Г. Н.; Машковский, И. С.; Рассолов, А. В.; Yakushev, I. A.; Варгафтик, М. Н.; Stakheev, A. Yu.

doi:10.1134/s0023158416050141

Cited by 17 publications

(7 citation statements)

References 22 publications

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“…While precious transition metals like palladium (Pd) and platinum (Pt) are widely used in catalytic reactions due to their outstanding chemical and physical properties, they are generally less selective toward forming desired products. − More selective catalytic processes require less reactants, dispense with subsequent separation procedures, and produce fewer byproducts. − So from economical and environmental perspectives, improving selectivity of industrial heterogeneous catalysts is vital. For example, highly selective removal of trace amounts of acetylene impurities in the ethylene feed is a crucial step for industrial production of polyethylene. − Pd is highly active for this process, but it always exhibits low ethylene selectivity, generating undesired ethane. − Hence, developing effective strategies for improving the selectivity of Pd catalysts has attracted broad interests.…”

Section: Introductionmentioning

confidence: 99%

Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes

et al. 2017

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Improving the catalytic selectivity of Pd catalysts is of key importance for various industrial processes and remains a challenge so far. Given the unique properties of single-atom catalysts, isolating contiguous Pd atoms into a single-Pd site with another metal to form intermetallic structures is an effective way to endow Pd with high catalytic selectivity and to stabilize the single site with the intermetallic structures. Based on density functional theory modeling, we demonstrate that the (110) surface of Pm3̅m PdIn with single-atom Pd sites shows high selectivity for semihydrogenation of acetylene, whereas the (111) surface of P4/mmm PdIn with Pd trimer sites shows low selectivity. This idea has been further validated by experimental results that intermetallic PdIn nanocrystals mainly exposing the (110) surface exhibit much higher selectivity for acetylene hydrogenation than PdIn nanocrystals mainly exposing the (111) surface (92% vs 21% ethylene selectivity at 90 °C). This work provides insight for rational design of bimetallic metal catalysts with specific catalytic properties.

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Section: Introductionmentioning

confidence: 99%

Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes

et al. 2017

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“…The effect of this modification can be generally classified as an ensemble effect, , caused by the dilution of active sites, and a ligand effect, − caused by electronic perturbation related to the second metal. With respect to controlling the nature of active sites, intermetallic compounds are attractive candidates for drastically changing the electronic and geometric states of active metals, typically rendering a considerably enhanced catalytic performance compared with those of pure metals in various reactions, including the selective hydrogenation of alkynes, − nitroarenes, and α,β-unsaturated aldehydes . These unique catalytic properties of intermetallic compounds can be attributed to their specific crystal and electronic structures, that is, well-structured bimetallic surface atomic arrangements and electronically modified active sites.…”

Section: Introductionmentioning

confidence: 99%

Surface Modification of PdZn Nanoparticles via Galvanic Replacement for the Selective Hydrogenation of Terminal Alkynes

Miyazaki

Furukawa

Takayama

et al. 2019

ACS Appl. Nano Mater.

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In this study, a novel intermetallic compound-derived trimetallic surface site in nanoscale via the galvanic replacement reaction (GRR) is described. A PdZn/SiO2 catalyst, which exhibited high activity for the hydrogenation of phenylacetylene, was prepared. The GRR between the metallic Zn of the SiO2-supported PdZn intermetallic nanoparticles and the third metal precursor (e.g., Pb, Bi, Sn, Au, Ag, and Ga) was carried out, affording well-modified surface Pd sites. Among a series of catalysts modified by the third metals, the Pb-replaced catalyst exhibited an excellent yield of styrene, with the minimum overhydrogenation rate for alkane. The Pb-replaced catalysts were characterized by X-ray diffraction, scanning transmission electron microscopy–energy-dispersive X-ray spectroscopy, CO Fourier transform infrared, and X-ray absorption fine structure measurements. The combination of these characterization methods revealed that (1) surface Zn atoms are successfully replaced by Pb during the GRR and (2) the prepared catalysts exhibit a bulk PdZn intermetallic structure, with their surface modified by Pb. The as-prepared catalysts were used for the selective hydrogenation of phenylacetylene to styrene. A control experiment using a Pd–Zn–Pb trimetallic solid-solution alloy led to a low catalytic activity, highlighting the validity and specificity of the Pb-modified PdZn surface structure.

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“…It was also found that PdIn catalysts demonstrate high selectivity in the liquid-phase hydrogenation of internal alkynes comparable with that of the commercial Lindlar catalyst. Remarkably, excellent activity/selectivity characteristics were attained at a significantly lower Pd content [ 14 ]. These results are in the good agreement with the data reported by Feng et al [ 15 ].…”

Section: Introductionmentioning

confidence: 99%

Highly-Ordered PdIn Intermetallic Nanostructures Obtained from Heterobimetallic Acetate Complex: Formation and Catalytic Properties in Diphenylacetylene Hydrogenation

et al. 2018

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Formation of PdIn intermetallic nanoparticles supported on α-Al2O3 was investigated by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and hydrogen temperature-programmed desorption (H2-TPD) methods. The metals were loaded as heterobimetallic Pd(μ-O2CMe)4In(O2CMe) complex to ensure intimate contact between Pd and In. Reduction in H2 at 200 °C resulted in Pd-rich PdIn alloy as evidenced by XRD and the disappearance of Pd hydride. A minor amount of Pd1In1 intermetallic phase appeared after reduction at 200 °C and its formation was accomplished at 400 °C. Neither monometallic Pd or in nor other intermetallic structures were found after reduction at 400–600 °C. Catalytic performance of Pd1In1/α-Al2O3 was studied in the selective liquid-phase diphenylacetylene (DPA) hydrogenation. It was found that the reaction rate of undesired alkene hydrogenation is strongly reduced on Pd1In1 nanoparticles enabling effective kinetic control of the hydrogenation, and the catalyst demonstrated excellent selectivity to alkene.

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Supported catalysts based on Pd–In nanoparticles for the liquid- phase hydrogenation of terminal and internal alkynes: 2. catalytic properties

Cited by 17 publications

References 22 publications

Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes

Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes

Surface Modification of PdZn Nanoparticles via Galvanic Replacement for the Selective Hydrogenation of Terminal Alkynes

Highly-Ordered PdIn Intermetallic Nanostructures Obtained from Heterobimetallic Acetate Complex: Formation and Catalytic Properties in Diphenylacetylene Hydrogenation

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