Catalytic investigation of Pd particles supported on MCM-41 for the selective hydrogenations of terminal and internal alkynes

Attila Papp, Árpád Molnár, A. Mastalir

Research output: Contribution to journalArticle

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Abstract

Pd-MCM-41 samples with different Pd contents were synthetized by using PdCl2, tetraethyl orthosilicate (TEOS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB). The template-free materials were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), N2 sorption, H2 chemisorption and TEM measurements. The representative samples Pd-MCM(1.39) and Pd-MCM(5.85) had Pd contents 1.39 and 5.85%, respectively. Although the formation of the Pd particles was found to decrease the crystalline character of the host material, the structure of the MCM-41 framework was retained for both samples. The evidence that the Pd crystallite sizes exceeded 5 nm suggested that the Pd particles were mainly situated on the surface of MCM-41, although some of the Pd content of Pd-MCM(5.85) may also be embedded in the mesopores. Accordingly, the Pd-MCMs can essentially be regarded as MCM-41-supported Pd materials. Both samples proved to be active and selective catalysts for the liquid-phase semihydrogenations of phenylacetylene, 3-butyn-1-ol, 4-octyne and 1-phenyl-1-butyne. The initial activity of Pd-MCM(1.39) surpassed that of Pd-MCM(5.85) for each reaction, indicating that the catalytic activity was dependent on the Pd crystallite size. In contrast, the selectivity of alkene formation was irrespective of the particle diameter for most reactants. For the semihydrogenation of 4-octyne, Pd-MCM(1.39) proved to be an extremely efficient catalyst. The pronounced (Z)-alkene stereoselectivities obtained for the hydrogenations of internal alkynes over both Pd-MCMs may be attributed to the participation of high-coordination terrace atoms as active sites. The catalytic activities of the Pd-MCMs were considerably higher than those of silica-supported Pd catalysts.

Original languageEnglish
Pages (from-to)256-266
Number of pages11
JournalApplied Catalysis A: General
Volume289
Issue number2
DOIs
Publication statusPublished - Aug 10 2005

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Alkynes
Multicarrier modulation
Hydrogenation
Alkenes
Crystallite size
Catalyst activity
Atomic emission spectroscopy
MCM-41
Stereoselectivity
Olefins
Catalysts
Cationic surfactants
Inductively coupled plasma
Chemisorption
Catalyst supports
Silicon Dioxide
Sorption
Crystalline materials
Transmission electron microscopy
X ray diffraction

Keywords

  • (Z)-alkene
  • Alkyne hydrogenation
  • MCM-41
  • N sorption
  • Palladium
  • Silica-supported palladium catalyst
  • Stereoselectivity
  • Transmission electron microscopy
  • X-ray diffraction

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Cite this

Catalytic investigation of Pd particles supported on MCM-41 for the selective hydrogenations of terminal and internal alkynes. / Papp, Attila; Molnár, Árpád; Mastalir, A.

In: Applied Catalysis A: General, Vol. 289, No. 2, 10.08.2005, p. 256-266.

Research output: Contribution to journalArticle

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abstract = "Pd-MCM-41 samples with different Pd contents were synthetized by using PdCl2, tetraethyl orthosilicate (TEOS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB). The template-free materials were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), N2 sorption, H2 chemisorption and TEM measurements. The representative samples Pd-MCM(1.39) and Pd-MCM(5.85) had Pd contents 1.39 and 5.85{\%}, respectively. Although the formation of the Pd particles was found to decrease the crystalline character of the host material, the structure of the MCM-41 framework was retained for both samples. The evidence that the Pd crystallite sizes exceeded 5 nm suggested that the Pd particles were mainly situated on the surface of MCM-41, although some of the Pd content of Pd-MCM(5.85) may also be embedded in the mesopores. Accordingly, the Pd-MCMs can essentially be regarded as MCM-41-supported Pd materials. Both samples proved to be active and selective catalysts for the liquid-phase semihydrogenations of phenylacetylene, 3-butyn-1-ol, 4-octyne and 1-phenyl-1-butyne. The initial activity of Pd-MCM(1.39) surpassed that of Pd-MCM(5.85) for each reaction, indicating that the catalytic activity was dependent on the Pd crystallite size. In contrast, the selectivity of alkene formation was irrespective of the particle diameter for most reactants. For the semihydrogenation of 4-octyne, Pd-MCM(1.39) proved to be an extremely efficient catalyst. The pronounced (Z)-alkene stereoselectivities obtained for the hydrogenations of internal alkynes over both Pd-MCMs may be attributed to the participation of high-coordination terrace atoms as active sites. The catalytic activities of the Pd-MCMs were considerably higher than those of silica-supported Pd catalysts.",
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AU - Papp, Attila

AU - Molnár, Árpád

AU - Mastalir, A.

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N2 - Pd-MCM-41 samples with different Pd contents were synthetized by using PdCl2, tetraethyl orthosilicate (TEOS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB). The template-free materials were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), N2 sorption, H2 chemisorption and TEM measurements. The representative samples Pd-MCM(1.39) and Pd-MCM(5.85) had Pd contents 1.39 and 5.85%, respectively. Although the formation of the Pd particles was found to decrease the crystalline character of the host material, the structure of the MCM-41 framework was retained for both samples. The evidence that the Pd crystallite sizes exceeded 5 nm suggested that the Pd particles were mainly situated on the surface of MCM-41, although some of the Pd content of Pd-MCM(5.85) may also be embedded in the mesopores. Accordingly, the Pd-MCMs can essentially be regarded as MCM-41-supported Pd materials. Both samples proved to be active and selective catalysts for the liquid-phase semihydrogenations of phenylacetylene, 3-butyn-1-ol, 4-octyne and 1-phenyl-1-butyne. The initial activity of Pd-MCM(1.39) surpassed that of Pd-MCM(5.85) for each reaction, indicating that the catalytic activity was dependent on the Pd crystallite size. In contrast, the selectivity of alkene formation was irrespective of the particle diameter for most reactants. For the semihydrogenation of 4-octyne, Pd-MCM(1.39) proved to be an extremely efficient catalyst. The pronounced (Z)-alkene stereoselectivities obtained for the hydrogenations of internal alkynes over both Pd-MCMs may be attributed to the participation of high-coordination terrace atoms as active sites. The catalytic activities of the Pd-MCMs were considerably higher than those of silica-supported Pd catalysts.

AB - Pd-MCM-41 samples with different Pd contents were synthetized by using PdCl2, tetraethyl orthosilicate (TEOS) and the cationic surfactant cetyltrimethylammonium bromide (CTAB). The template-free materials were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), N2 sorption, H2 chemisorption and TEM measurements. The representative samples Pd-MCM(1.39) and Pd-MCM(5.85) had Pd contents 1.39 and 5.85%, respectively. Although the formation of the Pd particles was found to decrease the crystalline character of the host material, the structure of the MCM-41 framework was retained for both samples. The evidence that the Pd crystallite sizes exceeded 5 nm suggested that the Pd particles were mainly situated on the surface of MCM-41, although some of the Pd content of Pd-MCM(5.85) may also be embedded in the mesopores. Accordingly, the Pd-MCMs can essentially be regarded as MCM-41-supported Pd materials. Both samples proved to be active and selective catalysts for the liquid-phase semihydrogenations of phenylacetylene, 3-butyn-1-ol, 4-octyne and 1-phenyl-1-butyne. The initial activity of Pd-MCM(1.39) surpassed that of Pd-MCM(5.85) for each reaction, indicating that the catalytic activity was dependent on the Pd crystallite size. In contrast, the selectivity of alkene formation was irrespective of the particle diameter for most reactants. For the semihydrogenation of 4-octyne, Pd-MCM(1.39) proved to be an extremely efficient catalyst. The pronounced (Z)-alkene stereoselectivities obtained for the hydrogenations of internal alkynes over both Pd-MCMs may be attributed to the participation of high-coordination terrace atoms as active sites. The catalytic activities of the Pd-MCMs were considerably higher than those of silica-supported Pd catalysts.

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KW - N sorption

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KW - Silica-supported palladium catalyst

KW - Stereoselectivity

KW - Transmission electron microscopy

KW - X-ray diffraction

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