The demand for nanocomposites of graphene and carbonaceous materials decorated with metallic nanoparticles is increasing on account of their applications in science and technology. Traditionally, the production of graphene-metal assemblies is achieved by the non-environmentally friendly reduction of metallic salts in carbonaceous suspensions. However, precursor residues during nanoparticle growth may reduce their surface activity and promote cross-chemical undesired effects. In this work we present a laser-based alternative to synthesize ligand-free gold nanoparticles that are anchored onto the graphene surface in a single reaction step. Laser radiation is used to generate highly pure nanoparticles from a gold disk surrounded by a graphene oxide suspension. The produced gold nanoparticles are directly immobilized onto the graphene surface. Moreover, the presence of graphene oxide influences the size of the nanoparticles and its interaction with the laser, causes only a slight reduction of the material. This work constitutes a green alternative synthesis of graphene-metal assemblies and a practical methodology that may inspire future developments.
The catalytic dehydrogenative coupling of silanes and alcohols represents a convenient process to produce hydrogen on demand. The catalyst, an iridium complex of the formula [IrCp*(Cl) 2 (NHC)] containing an NHC ligand functionalized with a pyrene tag, catalyzes efficiently the reaction at room temperature producing H 2 quantitatively within a few minutes. As a result, the dehydrogenative coupling of 1,4-disilabutane and methanol enables an effective hydrogen storage capacity of 4.3 wt% that is as high as the hydrogen contained in the dehydrogenation of formic acid, positioning the silane/alcohol pair as a potential liquid organic hydrogen carrier for energy storage. In addition, the heterogenization of the iridium complex on graphene presents a recyclable catalyst that retains its activity for at least ten additional runs. The homogeneous distribution of catalytic active sites on the basal plane of graphene prevents diffusion problems and the reaction kinetics are maintained after immobilization.
The compound [Ru(p-cym)(Cl) (NHC)] is an effective catalyst for the room-temperature coupling of silanes and alcohols with the concomitant formation of molecular hydrogen. High catalyst activity is observed for a variety of substrates affording quantitative yields in minutes at room temperature and with a catalyst loading as low as 0.1 mol %. The coupling reaction is thermodynamically and, in the presence of a Ru complex, kinetically favourable and allows rapid molecular hydrogen generation on-demand at room temperature, under air, and without any additive. The pair silane/alcohol is a potential liquid organic hydrogen carrier (LOHC) for energy storage over long periods in a safe and secure way. Silanes and alcohols are non-toxic compounds and do not require special handling precautions such as high pressure or an inert atmosphere. These properties enhance the practical applications of the pair silane/alcohol as a good LOHC in the automotive industry. The variety and availability of silanes and alcohols permits a pair combination that fulfils the requirements for developing an efficient LOHC.
The catalytic performance of gold complexes is evaluated at the molecular level and when supported onto reduced graphene oxide (rGO). Gold complexes of general formula [(NHC)AuX] catalyse the synthesis of indoles via intramolecular hydroamination reaction of alkynes. The catalytic properties of the molecular gold complexes are highly improved when supported onto graphene. Faster reaction rates and higher catalyst stability are observed for the immobilized gold complexes. The use of graphene as support of molecular complexes has a positive benefit in the catalytic gold properties in terms of activity and stability
Green efficient synthesis of carboxylic acids catalyzed by molecular ruthenium complexes supported on graphene using water as solvent and with the formation of molecular hydrogen as a by-product.
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