Oxidized multiwall carbon nanotubes (CNT) were covalently modified with appropriate hydroxylending imidazolium salts using their carboxylic acid groups. Characterization of the imidazoliummodified samples through typical solid characterization techniques, such as TGA or XPS, allows for the determination of 16 wt.% in CNT-1 and 31 wt.% in CNT-2 as the amount of the imidazolic fragments in the carbon nanotubes. The imidazolium-functionalized materials were used to prepare nanohybrid materials containing iridium N-heterocyclic carbene (NHC) type organometallic complexes with efficiencies as high as 95 %. The nanotube-supported iridium-NHC materials were active in the heterogeneous iridium-catalyzed hydrogen-transfer reduction of cyclohexanone to cyclohexanol with 2-propanol/KOH as hydrogen source. The iridium hybrid materials are more efficient than related homogeneous catalysts based on acetoxy-functionalized Ir-NHC complexes with initial TOFs up to 5550 h -1 . A good recyclability of the catalysts, without any loss of activity, and stability on air was observed.

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One of the most attractive applications of carbon nanomaterials is as catalysts, due to their extreme surface-to-volume ratio. The substitution of C with heteroatoms (typically B and N as p- and n-dopants) has been explored to enhance their catalytic activity. Here we show that encapsulation within weakly doping macrocycles can be used to modify the catalytic properties of the nanotubes towards the reduction of nitroarenes, either enhancing it (n-doping) or slowing it down (p-doping). This artificial regulation strategy presents a unique combination of features found in the natural regulation of enzymes: binding of the effectors (the macrocycles) is noncovalent, yet stable thanks to the mechanical link, and their effect is remote, but not allosteric, since it does not affect the structure of the active site. By careful design of the macrocycles’ structure, we expect that this strategy will contribute to overcome the major hurdles in SWNT-based catalysts: activity, aggregation, and specificity.

In the quest for designing efficient and stable photocatalytic materials for CO2 reduction, hybridizing a selective noble-metal-free molecular catalyst and carbon-based light-absorbing materials has recently emerged as a fruitful approach. In this work, we report about Co quaterpyridine complexes covalently linked to graphene surfaces functionalized by carboxylic acid groups. The nanostructured materials were characterized by X-ray photoemission spectroscopy, X-ray absorption spectroscopy, IR and Raman spectroscopies, high-resolution transmission electron microscopy and proved to be highly active in the visible-light-driven CO2 catalytic conversion in acetonitrile solutions. Exceptional stabilities (over 200 h of irradiation) were obtained without compromising the selective conversion of CO2 to products (>97%). Most importantly, complete selectivity control could be obtained upon adjusting the experimental conditions: production of CO as the only product was achieved when using a weak acid (phenol or trifluoroethanol) as a co-substrate, while formate was exclusively obtained in solutions of mixed acetonitrile and triethanolamine.