Efficient and recyclable carbon-supported Pd nanocatalysts for the Suzuki–Miyaura reaction in aqueous-based media: Microwave vs conventional heating

doi:10.1016/j.apcata.2013.08.036

Applied Catalysis A: General

Volume 468, 5 November 2013, Pages 59-67

https://doi.org/10.1016/j.apcata.2013.08.036 Get rights and content

Highlights

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New PdNPs on carbon materials nanocatalysts were prepared and fully characterized.
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The nanocatalysts were found to be highly active in the Suzuki coupling reaction.
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The hybrid systems were re-used up to 10 times without any loss of activity in PEG.
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Reaction media was found to influence strongly the re-use of the nanocatalysts.

Abstract

Three new hybrid nanocatalysts based on carbon-supported Pd nanoparticles (NPs) were prepared by decomposition of an organometallic palladium precursor under H₂ atmosphere in the presence of carbon materials with different surface and textural properties. The so-obtained Pd NPs displayed mean sizes in the range of 2–2.5 nm. The hybrid nanocatalysts were evaluated in the aqueous Suzuki–Miyaura cross-coupling reaction under both conventional and microwave heating. Excellent activities were obtained at short reaction times (5–10 min) reaching TOF values up to 3000 h⁻¹ under microwave radiation. Recycling studies showed that the nanocatalysts could be re-used up to 10 (conventional heating) and to 5 (microwave irradiation) reaction cycles without any loss of activity. The reaction media was found to have a strong influence on the recyclability of the nanocatalysts, which could be improved in the presence of polyethylene glycol.

Graphical abstract

Introduction

The preparation [1], characterization [2], [3], surface reactivity [4], [5], and application of transition metal nanoparticles (MNPs) have attracted much attention in recent years. As MNPs display much larger surface area than the bulk metals, they have been used as catalysts in a wide range of chemical reactions showing high activities and selectivity as well as long lifetimes [6], [7], [8]. However, the widespread use of MNPs as catalysts is still hampered by some drawbacks related to manipulation and recovery difficulties as well as agglomeration tendency under reaction conditions. MNPs stabilization to prevent their agglomeration has been reported. This stabilization is generally conducted by two main methods: (1) by using different stabilizing agents, namely ligands, surfactants, ionic liquids, thus resulting in homogenized heterogeneous catalysts [9], [10], [11] or (2) the MNPs immobilization on various solid supports including mesoporous silica [12], inorganic oxides [13], molecular sieves [14], polymers [15], capsules [16], or carbon materials [17], [18]. From an industrial viewpoint, the deposition method is preferred since the obtained catalysts are easier to handle, recover and re-use in the selected process.

Within transition metals, palladium is one of the more versatile for catalytic applications. It is an excellent catalyst for a significant number of reactions in homogeneous and heterogeneous conditions including cross-coupling, alkoxycarbonylation, oxidation and reduction reactions [19], [20], [21].

The use of carbon materials as solid supports for the immobilization of Pd NPs offer very interesting advantages such as good mechanical and chemical properties and an adequate pore size distribution. Furthermore, these materials have a rich surface chemistry which allows modifications by straight-forward procedures to enhance MNPs immobilization and stabilization as well as a high stability combined with the desired water-tolerant properties for aqueous catalytic processes. In the light of these premises, the combination of MNPs (e.g. Pd) and carbon materials with aqueous phase conditions can provide a promising alternative for the development of environmentally friendly catalytic processes.

Herein, novel hybrid catalytic systems composed of Pd NPs immobilized on different carbon materials were prepared by direct reduction of a palladium organometallic precursor previously impregnated on the solid support. The catalytic activity as well as the recyclability of these systems were investigated in the Suzuki–Miyaura cross-coupling reaction between phenylboronic acid and various arylhalides under conventional and microwave heating, using water or a polyethylene glycol (PEG) in water mixture as solvents. The influence of the textural and chemical surface properties of the carbon materials on the catalytic activity of the supported Pd NPs is also discussed.

Section snippets

Chemical reagents and solvents

All operations were carried out using standard Schlenk techniques, Fischer-Porter bottles or in a glove-box under Ar atmosphere unless otherwise stated. Tris(dibenzylideneacetone)dipalladium (0) complex [Pd₂(dba)₃] from Strem Chemicals, polyethylene glycol (PEG) solution in water (50 wt.%), para-bromobenzaldehyde, bromobenzene, para-bromoanisole, para-chlorobenzaldehyde, NaOH, K₂CO₃, KOAc and n-decane from Sigma–Aldrich and H₂ from air liquid were used without any further purification. Toluene

Surface properties of the carbon materials

Prior to discuss the results of the activity of the hybrid Pd nanocatalysts designed, the surface properties of MB, MB-LTA and MB-2000-LTA carbon materials used as supports are considered. The textural parameters (surface area and pore volume) and surface chemical analysis (total oxygen and carbon, and oxygen distribution in functional groups) have been summarized in Table 1. For comparison, data of heat-treated MB-2000 are also included. The starting MB material shows relatively high micro

Conclusions

Decomposition of the impregnated organometallic complex [Pd₂(dba)₃] on three carbon supports displaying different surface properties led to small and well-dispersed carbon-supported Pd NPs with mean sizes in the range 2.0–2.5 nm. The mesoporous character of the carbon material support as well as the presence of abundant oxygen groups on its surface seems to improve the immobilization of Pd NPs as regards population and size. These hybrid phosphine-free Pd nanocatalysts were evaluated in the

Acknowledgements

Financial support from CNRS and CSIC is gratefully acknowledged. E. J. García-Suárez thanks CSIC and PCTI of Asturias (Spain) for JAE Doc and Clarín postdoctoral grants, respectively, to develop the work. The authors also thank I. Fourquaux (UPS-CMEAB) for ultramicrotomy, L. Datas and V. Collière (UPS-TEMSCAN) for HR-TEM facilities. R.L. gratefully acknowledges support from the Spanish MICINN via the concession of a RyC contract (ref. RYC-2009-04199) and funding under projects P10-FQM-6711

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Efficient and recyclable carbon-supported Pd nanocatalysts for the Suzuki–Miyaura reaction in aqueous-based media: Microwave vs conventional heating

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemical reagents and solvents

Surface properties of the carbon materials

Conclusions

Acknowledgements

Micropor. Mesopor. Mater.

J. Organomet. Chem.

Tetrahedron Lett.

J. Catal.

J. Catal.

Tetrahedron Lett.

ChemCatChem

J. Mater. Chem.

Dalton Trans.

Angew. Chem. Int. Ed.

Catal. Lett.

Chem. Rev.

Chem. Soc. Rev.

ChemSusChem