In this chapter, we presented an overview of the major results obtained in the synthesis of metal nanoparticles from organometallic complexes and their investigation in catalysis for various reactions. Despite the poor handling of metal–organic precursors which are highly sensitive towards oxygen and moisture, the organometallic approach is still a versatile method in the preparation of both soluble and supported MNPs. It allows us to tune the nature of the MNPs for the precise control of size, shape, composition and surface state according to the aim of the catalytic reaction.
Table 4.9 Hydrogenation of furfural catalysed by carbon-supported PdNPs/carbon under microwave conditions.a,78
Pd(TOP)/MB-1500 30 75 20 72
Pd(TPP)/MB-H2O2 30 69 10 85
Pd(TPP)/MB-1500 30 65 o10 80
Pd/MB-H2O2 45 70 30 70
Pd/MB-1500 45 45 35 65
aReaction conditions: 2 mmol furfural, 1.5 mL formic acid, 1.5 mL water, 0.1 g catalyst, 100 1C, microwave power¼ 100–150 W, P ¼ 150–200 psi (developed in the systems).
23/06/2014 08:14:50. Published on 12 June 2014 on http://pubs.rsc.org | doi:10.1039/9781782621034-00047
In solution, the control of the characteristics of the MNPs is governed by a ligand that is stabilizing by nature and by controlling the key parameters of the syntheses such as the rate of nucleation and the rate of growth. With the experience gained from homogeneous catalysis, the ligands already known to orient catalytic properties, such as phosphine and carbene derivatives, can also be used for very small nanocatalysts. Moreover, ligands can be specific-ally chosen for their advantageous properties such as solubility or enantios-electivity. For instance, water soluble NPs are prepared using amphiphilic ligands. Enantioselective catalysis could also be achieved by using oxazoline or diphosphite ligands, but keeping in mind the low chiral induction. Con-cerning the immobilization of MNPs onto supports, the most promising results evidenced the important role of the functionalization of the support to increase the anchorage of the particles and consequently their catalytic per-formance by increasing the selectivity and the recovery of the catalyst.
The preparation of nanocatalysts displaying desirable catalytic perform-ance is one of the challenges which remain to be met in nanocatalysis.
Although numerous efforts with various capping agents have been made over the past few years by researchers all over the world, future progress will probably necessitate the design of molecules more appropriate for the metal surface to induce higher catalytic properties in terms of selectivity. The recycling and the recovery of the nanocatalysts are still to be improved at this point.
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