Study of the Synthesis of Multi-Cationic Sm-Co-O, Sm-Ni-O, Al-Co-O, Al-Ni-O, and Al-Co-Ni-O Aerogels and Their Catalytic Activity in the Dry Reforming of Methane.

Dense multi-cationic Sm-Co-O, Sm-Ni-O, Al-Co-O, Al-Ni-O, and Al-Ni-Co-O oxide aerogels were prepared by epoxide-driven sol-gel synthesis. Catalysts for dry reformation of methane, Sm2O3/Co, Sm2O3/Ni, Al2O3/Co, Al2O3/Ni, Al2O3/Co, and Ni were prepared by reduction of aerogels with hydrogen and their catalytic activities and C-deposition during dry reformation of methane were tested. Catalytic tests showed high methane conversion (93-98%) and C-deposition (0.01-4.35 mg C/gcat.h). The highest content of C-deposits after catalytic tests was determined for Al2O3/Co and Al2O3/Ni catalysts, which was related to the formation of Al alloys with Co and Ni. A uniform distribution of Co0 and Ni0 nanoparticles (in the form of a CoNi alloy) was found only for the Al2O3/Co and Ni catalysts, which showed the highest activity as well as low C deposition.

The first solid-state route to luminescent Au(I)-glutathionate and its pH-controlled transformation into ultrasmall oligomeric Au10-12(SG)10-12 nanoclusters for application in cancer radiotheraphy.

There is still a need for synthetic approaches that are much faster, easier to scale up, more robust and efficient for generating gold(I)-thiolates that can be easily converted into gold-thiolate nanoclusters. Mechanochemical methods can offer significantly reduced reaction times, increased yields and straightforward recovery of the product, compared to the solution-based reactions. For the first time, a new simple, rapid and efficient mechanochemical redox method in a ball-mill was developed to produce the highly luminescent, pH-responsive Au(I)-glutathionate, [Au(SG)]n. The efficient productivity of the mechanochemical redox reaction afforded orange luminescent [Au(SG)]n in isolable amounts (mg scale), usually not achieved by more conventional methods in solution. Then, ultrasmall oligomeric Au10-12(SG)10-12 nanoclusters were prepared by pH-triggered dissociation of [Au(SG)]n. The pH-stimulated dissociation of the Au(I)-glutathionate complex provides a time-efficient synthesis of oligomeric Au10-12(SG)10-12 nanoclusters, it avoids high-temperature heating or the addition of harmful reducing agent (e.g., carbon monoxide). Therefore, we present herein a new and eco-friendly methodology to access oligomeric glutathione-based gold nanoclusters, already finding applications in biomedical field as efficient radiosensitizers in cancer radiotherapy.