The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH2) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.@en

Gold (1 wt.%) was loaded on several carbon materials, namely, polymer based carbon xerogel, activated carbon, microdiamonds, nanodiamonds, graphite and silicon carbide by double impregnation and sol immobilisation. The obtained catalysts were characterised by N₂ adsorption at -196 ºC, high-resolution transmission electron microscopy, high-angle annular dark-field imaging (Z-contrast), temperature programmed desorption, atomic absorption spectroscopy and X-ray photoelectron spectroscopy. The obtained materials were tested on the microwave-assisted solvent-free oxidation of 1-phenylethanol by tert-butyl hydroperoxide (TBHP) to produce acetophenone. The results showed that the catalytic activity was influenced by several factors, namely, the nature of the support, reaction time and temperature, amount of catalyst, presence of additives, among others. The best values for acetophenone yield (99.9%) were obtained with Au deposited on microdiamonds by the colloidal method. Catalyst recyclability was tested up to six consecutive cycles at the optimized conditions for each catalyst, and it was found that Au on microdiamonds, prepared by the colloidal method, also maintained higher activity after several reaction cycles as compared to the other carbon supports.

@en

Pristine nanodiamonds (NDs) obtained by detonation, or functionalized by different treatments, namely oxidation, hydrogenation and amination, were used to synthesize composites by insertion in TiO₂ matrixes. The different treatments of the NDs lead to materials containing diverse texture properties and surface chemistry functionalities, particularly concerning the insertion of nitrogen and oxygen groups. The photocatalytic activity of the prepared composites was evaluated for the oxidative degradation of two water soluble pharmaceuticals – diphenhydramine and amoxicillin – under near-UV/Vis irradiation. The most active photocatalyst in what concerns both pollutants degradation under near-UV/Vis irradiation was the composite containing pristine NDs (NDDT). The photocatalytic performances were dependent on the specific surface area and on the amount of functional groups incorporated over the NDs. The influence of ND in the composites activity is well correlated with the observed photoluminescence quenching of TiO₂, which corresponds to a delay in the recombination rate of charge carriers that benefices the photocatalytic reaction. Scavenging of photogenerated holes and radicals by employing sacrificial hole and radical agents revealed that the holes played the main role on both pollutants degradation under UV/Vis irradiation. Reutilization experiments proved that the ND composites have good stability and reusability.

@en

The C-scorpionate iron(II) complex [FeCl₂(Tpm)] [Tpm=κ³-HC(C₃H₃N₂)₃] (1) was immobilized on five different nanostructured carbon materials (nanodiamonds, graphene nanoplatelets, graphene oxide, reduced graphene oxide, and nanohorns) to produce active, selective, and recyclable catalysts for alkane and alcohol oxidations. The heterogenized systems (including the first ever reported complexes supported on carbon nanohorns) exhibited good activity concomitant with rather high selectivity to the formation of ketone alcohol (KA) oil (cyclohexanol and cyclohexanone mixture, yields up to 29%) from microwave-assisted oxidation of cyclohexane, and allowed their easy recovery and reuse, at least for five consecutive cycles maintaining 90.3% of the initial activity. Moreover, the functionalized nanodiamond supports (used for the first time as supports for iron complexes) were also able to effectively (yields up to 97%) catalyze the microwave-induced oxidation of 1- and 2-phenylethanol to acetophenone and 2-phenylacetaldehyde, respectively, and could be reused for seven consecutive cycles without losing catalytic activity.

@en

In this work, the use of nanodiamonds (NDs; 2-10 nm) in the seeding of diamond films grown by chemical vapor deposition (CVD) and in the synthesis of composite TiO₂-nanodiamond photocatalysts is discussed. First, enhanced growth of faceted, nanocrystalline diamond (NCD) films by hot filament CVD at moderate substrate temperature (650°C) and carbon-lean gas chemistry (1.0% CH₄ in H₂) is demonstrated. The enhancement of diamond nucleation and growth on Si substrates is achieved by using a sputter deposition of different metallic (Cr, Nb, Ti, V, and W) nanolayers and an ultrasonic seeding with NDs. We conclude that the kinetics of diamond nucleation in the NCD film growth is determined by the number density of NDs embedded on the nanorough metallic surfaces after ultrasonic pretreatment and by the specific surface chemistry (i.e., carbon diffusivity and carburization) during diamond growth. Second., the synthesis and application of composites based on microdiamonds and NDs for the photocatalytic degradation of diphenhydramine pharmaceutical water pollutant is demonstrated. Micro- A nd nanodiamond powders were combined with TiO₂, varying the carbon phase content and tested as composite photocatalysts under near UV-Vis irradiation. The thus prepared composites exhibited higher photocatalytic activity than the respective bare materials. Best photocatalytic performance was observed in the case of using composites with 15 wt.% of NDs oxidized in air at 703 K.

@en