New gold standard: weakly capped infant Au nanoclusters with record high catalytic activity for 4-nitrophenol reduction and hydrogen generation from an ammonia borane-sodium borohydride mixture.

Increasing the surface area-to-volume ratio of materials through size reduction is a desired approach to access maximum possible surface sites in applications such as catalysis. However, increase in the surface energy with the decrease in dimension warrants strong ligands to stabilize nanosystems, which mask the accessibility of the active surface sites. Owing to this, the realization of the true potential of a catalyst's surface remains challenging. Here, we employed a rationally designed strategy to synthesize infant Au nanoclusters-that alleviates the requirement of any separate ligand removal step-to unleash their actual potential to register a record high maximum turn-over frequency (TOFmax) of 72 900 h-1 and 65 500 h-1 in the benchmark catalytic reduction of 4-nitrophenol and catalytic H2 generation from an ammonia borane-sodium borohydride mixture, respectively. Such a phenomenal catalytic activity has been realized via the synthesis and stabilization of Au nanoclusters using solid citric acid and a super-concentrated aqueous AuCl3 solution, a pathway entirely different from the conventional modifications of the Turkevich and Brust methods. The crux of the synthetic strategy lies in precise control of the water content and thereby ensuring that the final Au nanoclusters remain in the solid state. During the synthesis, citric acid not only acts as a reducing agent to yield 'infant' Au nanoclusters but also provides a barrier matrix to arrest their growth. In solution, its weak capping ability and rapid dissolution allows the reactants to easily access the active sites of Au nanoclusters, thus leading to faster catalysis. Our study reveals that the true potential of metal nanoclusters as catalysts is actually far higher than what has been reported in the literature.

Large Scale Solid-state Synthesis of Catalytically Active Fe3O4@M (M = Au, Ag and Au-Ag alloy) Core-shell Nanostructures.

Solvent-less synthesis of nanostructures is highly significant due to its economical, eco-friendly and industrially viable nature. Here we report a solid state synthetic approach for the fabrication of Fe3O4@M (where M = Au, Ag and Au-Ag alloy) core-shell nanostructures in nearly quantitative yields that involves a simple physical grinding of a metal precursor over Fe3O4 core, followed by calcination. The process involves smooth coating of low melting hybrid organic-inorganic precursor over the Fe3O4 core, which in turn facilitates a continuous shell layer post thermolysis. The obtained core-shell nanostructures are characterized using, XRD, XPS, ED-XRF, FE-SEM and HR-TEM for their phase, chemical state, elemental composition, surface morphology, and shell thickness, respectively. Homogeneous and continuous coating of the metal shell layer over a large area of the sample is ascertained by SAXS and STEM analyses. The synthesized catalysts have been studied for their applicability towards a model catalytic hydrogen generation from NH3BH3 and NaBH4 as hydrogen sources. The catalytic efficacy of the Fe3O4@Ag and Ag rich alloy shell materials are found to be superior to the corresponding Au counterparts. The saturation magnetization studies reveal the potential of the core-shell nanostructured catalysts to be magnetically recoverable and recyclable.