Stability and Reversible Oxidation of Sub-Nanometric Cu5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling.

Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude "breathing" motions. A chemical phase diagram for Cu oxidation states of the Cu5 -oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu.

Synthesis of photocatalytic cysteine-capped Cu≈10 clusters using Cu5 clusters as catalysts.

We report an easily scalable synthesis method for the preparation of cysteine-capped Cu≈10 clusters through the reduction of Cu(II) ions with NaBH4, using Cu5 clusters as catalysts. The presence of such catalytic clusters allows controlling the formation of the larger Cu≈10 clusters and prevents the production of copper oxides or Cu(I)-cysteine complexes, which are formed when Cu5 is absent or at lower concentrations, respectively. These results indicate that small catalytic clusters could be involved, as precursor species before the reduction step, in the different methods developed for the synthesis of clusters. The visible light-absorbing Cu≈10 clusters, obtained by the cluster-catalysed method, display high photocatalytic activities for the decomposition of methyl orange with visible light.

Efficient full solar spectrum-driven photocatalytic hydrogen production on low bandgap TiO2/conjugated polymer nanostructures.

The development of photocatalysts that can utilize the entire solar spectrum is crucial to achieving efficient solar energy conversion. The utility of the benchmark photocatalyst, TiO2, is limited only to the UV region due to its large bandgap. Extending the light harvesting properties across the entire spectrum is paramount to enhancing solar photocatalytic performance. In this work, we developed low bandgap TiO2/conjugated polymer nanostructures which exhibit full spectrum activity for efficient H2 production. The highly mesoporous structure of the nanostructures together with the photosensitizing properties of the conjugated polymer enabled efficient solar light activity. The mesoporous TiO2 nanostructures calcined at 550 °C exhibited a defect-free anatase crystalline phase with traces of brookite and high surface area, resulting in the best performance in hydrogen production (5.34 mmol g-1 h-1) under sunlight simulation. This value is higher not only in comparison to other TiO2-based catalysts but also to other semiconductor materials reported in the literature. Thus, this work provides an effective strategy for the construction of full spectrum active nanostructured catalysts for enhanced solar photocatalytic hydrogen production.

Silver Atomic Quantum Clusters of Three Atoms for Cancer Therapy: Targeting Chromatin Compaction to Increase the Therapeutic Index of Chemotherapy.

Nanomaterials with very low atomicity deserve consideration as potential pharmacological agents owing to their very small size and to their properties that can be precisely tuned with minor modifications to their size. Here, it is shown that silver clusters of three atoms (Ag3 -AQCs)-developed by an ad hoc method-augment chromatin accessibility. This effect only occurs during DNA replication. Coadministration of Ag3 -AQCs increases the cytotoxic effect of DNA-acting drugs on human lung carcinoma cells. In mice with orthotopic lung tumors, the coadministration of Ag3 -AQCs increases the amount of cisplatin (CDDP) bound to the tumor DNA by fivefold without modifying CDDP levels in normal tissues. As a result, CDDP coadministered with Ag3 -AQCs more strongly reduces the tumor burden. Evidence of the significance of targeting chromatin compaction to increase the therapeutic index of chemotherapy is now provided.

Large stability and high catalytic activities of sub-nm metal (0) clusters: implications into the nucleation and growth theory.

Clusters are stable catalytic species, which are produced during the synthesis of nanoparticles (NPs). Their existence contradicts the thermodynamic principles used to explain the formation of NPs by the classical nucleation and growth theories (NGTs). Using chemical and electrochemical methods we will show that depending on the experimental conditions one can produce either Ag clusters or Ag NPs. Moreover, using already prepared Ag clusters one can observe the disappearance of the usual induction period observed for the kinetics of NP formation, indicating that clusters catalyze the formation of NPs. Taking these data together with some previous examples of cluster-catalyzed anisotropic growth, we derived a qualitative approach to include the catalytic activities of clusters into the formation of NPs, which is incorporated into the NGT. Some qualitative conclusions about the main experimental parameters, which affect the formation of clusters versus NPs, as well as the catalytic mechanism versus the non-catalytic one, are also described.