Formation and Properties of Hydrogenation Catalysts Based on Palladium Complexes with Primary Phosphines

Belykh, L. B.; Goremyka, T. V.; Гусарова, Н. К.; Сухов, Б. Г.; Шмидт, Ф. К.

doi:10.1007/s10975-005-0111-y

Cited by 4 publications

(3 citation statements)

References 4 publications

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“…The striking lack of CO accessibility to bridging edges in the organometallic-derived Pd sites might be explained by blockage of these sites by phosphide/phosphate species on the nanoparticle surfaces. This rationale comes from the fact that high temperature reduction of materials containing phosphorus (including phosphate) and Pd precursors are known to yield phosphided Pd species. − In the present case, it is also possible that the close proximity of the phosphorus species to the Pd in the organometallic precursor facilitates migration of the phosphorus onto the Pd nanoparticles to achieve site blockage, although it should be noted that spatial proximity alone does not guarantee this to occur. As further confirmation of this hypothesis, energy dispersive X-ray (EDX) mapping was performed on the ( tBu PCP)Pd-SiO 2 -red sample, which reveals higher P concentrations in locations proximate to the Pd nanoparticles (Figure S2).…”

Section: Discussionmentioning

confidence: 94%

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

et al. 2016

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Highly dispersed low-coordinate Pd sites on SiO 2 are fabricated by grafting the Pd II PCP-pincer complex ( tBu PCP)Pd−OH ( tBu PCP = 2,6-C 6 H 3 (CH 2 P t Bu 2 ) 2 ) on SiO 2 , followed by calcination with ozone (100 °C) and reduction with H 2 (300 °C). The chemisorption process and structure of this organometallic complex on SiO 2 is established by solutionphase 1 H and 31 P NMR and solid-state 31 P CPMAS NMR spectroscopy, XPS, DRIFTS, and AC-HAADF-STEM. The CO adsorption properties of the Pd centers reveal a surprisingly high fraction of adsorption sites where CO is bound in a linear fashion, indicative of low-coordinate Pd. Furthermore, enhanced selectivity of these catalyst centers in aerobic alcohol oxidation versus a control catalyst argues that these low-coordinate sites are the catalytically active sites.

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Section: Discussionmentioning

confidence: 94%

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

et al. 2016

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“…[19,20] It is widely known that the presence of isolated metal atoms, as found in homogeneous and single atoms catalysts, results in optimized catalyst performance, especially in terms of selectivity. [6,7,21] Palladium phosphides have been reported as catalysts for hydrogenation, [12,15,16,19,[22][23][24][25] hydrodesulfurizations [10,11,26] and CÀ C coupling reactions, [20] as well as for catalytic water splitting. [27] In all of these cases, the authors have reported the positive effect of phosphorus incorporation into palladium with respect to the catalytic performance.…”

Section: Introductionmentioning

confidence: 99%

A Supported Palladium Phosphide Catalyst for the Wacker‐Tsuji‐Oxidation of Styrene

2023

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The substitution of pure metal particles by metal phosphides in catalysis represents a promising opportunity to lower the required metal quantity in the context of a sustainable use of metal resources. Herein we show the synthesis of palladium phosphide, Pd 3 P, supported on silica, which is tested as catalyst for the Wacker-Tsuji-oxidation of styrene to acetophenone. The synthesized catalyst is characterized by PXRD, SEM-EDX, FTIR, ICP-AES and XPS measurements. Four different reaction systems are investigated in this study including different co-catalysts and reaction media. Conversions of styrene up to 95 % with a selectivity of 73 % towards acetophenone are observed using Pd 3 P/SiO 2 as catalyst, CuCl 2 as co-catalyst and O 2 as oxidant. An enhanced selectivity up to 100 % towards acetophenone is obtained in other reaction systems. The use of Pd 3 P/SiO 2 leads to an optimized selectivity and conversion in the oxidation reaction in comparison with the purely Pd-based system Pd/ SiO 2 . These results give an insight on how the incorporation of phosphorus has a great effect on the performance of heterogeneous catalysts.

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“…The use of phosphorus in catalysis has greatly been extended from the conventional application as phosphine ligands in homogeneous catalysis [1][2][3] and has now also found significant attention in the field of heterogeneous catalysis. [4][5][6] Hereby, transition metal phosphides have been investigated in detail in various catalytic reactions, [7] such as hydroformylation, [8][9][10] hydrogenation, [11][12][13][14][15][16][17][18][19] photocatalytic Suzuki coupling [20] and desulfurization reactions. [21][22][23] The high catalytic activity of transition metal phosphides can be traced back to the dilution of the transition metal using phosphorus, which leads to the formation of highly uniform and defined "frustrated" single metal sites.…”

Section: Introductionmentioning

confidence: 99%

Support Engineering for the Stabilisation of Heterogeneous Pd₃P‐Based Catalysts for Heck Coupling Reactions

Neyyathala,

Flecken,

Rang

et al. 2023

Chemistry A European J

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Herein we report the use of a supported Pd3P catalyst for Heck coupling reactions. For the stabilisation of Pd3P and Pd, as reference system, the silica support material was modified via phosphorus doping (0.5 and 1 wt.% P). Through this so‐called support engineering approach, the catalytic activity of Pd3P was clearly enhanced. Whereas an iodobenzene conversion of 79% was witnessed for Pd3P@SiO2 in the coupling of styrene and iodobenzene in 1h, 90% conversion could be achieved using Pd3P@1P‐SiO2. This improved catalytic activity probably stems from an electronic modulation of the support surface via the introduction of phosphorus. Simultaneously, the recyclability was boosted and the Pd3P@1P‐SiO2 catalyst has shown to maintain its catalytic activity over several recovery tests. Hereby, metal leaching could almost be suppressed completely to 3% by the use of a P‐modified silica support.

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Formation and Properties of Hydrogenation Catalysts Based on Palladium Complexes with Primary Phosphines

Cited by 4 publications

References 4 publications

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

A Supported Palladium Phosphide Catalyst for the Wacker‐Tsuji‐Oxidation of Styrene

Support Engineering for the Stabilisation of Heterogeneous Pd₃P‐Based Catalysts for Heck Coupling Reactions

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Formation and Properties of Hydrogenation Catalysts Based on Palladium Complexes with Primary Phosphines

Cited by 4 publications

References 4 publications

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO2 via Surface Organometallic Chemistry

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO2 via Surface Organometallic Chemistry

A Supported Palladium Phosphide Catalyst for the Wacker‐Tsuji‐Oxidation of Styrene

Support Engineering for the Stabilisation of Heterogeneous Pd3P‐Based Catalysts for Heck Coupling Reactions

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Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

Direct Synthesis of Low-Coordinate Pd Catalysts Supported on SiO₂ via Surface Organometallic Chemistry

Support Engineering for the Stabilisation of Heterogeneous Pd₃P‐Based Catalysts for Heck Coupling Reactions