Microcrystalline Cellulose-Supported Gold Nanoparticle Catalysts for Homocoupling of Phenylboronic Acids.

A solid-grinding strategy for the large-scale synthesis of solid microcrystalline cellulose (MCC)-supported gold nanoparticle (NP) catalysts without using solvents and a sophisticated purification technique is reported. In contrast to typical solution-based methods, the deposition of high loading of gold NPs with greater uniformity on native MCC polymers without chemical modifications was achieved rapidly by manual grinding. The Fourier transform infrared (FT-IR) study revealed that the abundant hydroxyl functional groups present on the MCC support could effectively hold tiny gold NPs through hydrogen bonding between the -OH groups of MCC and gold NPs, thereby making the MCC-supported gold NPs stable heterogeneous catalysts. Thus, the Au/MCC catalyst exhibits higher catalytic activity and selectivity toward homocoupling of phenylboronic acids into corresponding biphenyls in water under air. Compared to other solid-supported gold NP catalysts, the MCC-supported gold catalysts showed greater catalytic activity and selectivity in the homocoupling of phenylboronic acids. The kinetics study on the homocoupling reaction catalyzed by Au/MCC reveals that the catalysts possess much lower apparent activation energy than the reported gold catalysts. Thus, the present sustainable approach may inspire more studies on the design of renewable biopolymer matrix-supported gold NPs in a large scale for heterogeneous catalysis.

Reduced oxide sites and surface corrugation affecting the reactivity, thermal stability, and selectivity of supported Au-Pd bimetallic clusters on SiO2/Si(100).

The morphology and surface elemental composition of Au-Pd bimetallic nanoclusters are reported to be sensitive to and affected by reduced silicon defect sites and structural corrugation on SiO2/Si(100), generated by argon ion sputtering under ultrahigh vacuum (UHV) conditions. Metastable structures of the bimetallic clusters, where Au atoms are depleted from the top surface upon annealing, are stabilized by the interaction with the reduced silica sites, as indicated from CO temperature programmed desorption (TPD) titration measurements. Acetylene conversion to ethylene and benzene has been studied as a probe reaction, revealing the modification of selectivity and reactivity enhancement in addition to improved thermal stability on substrates rich in reduced-silica sites. These observations suggest that these unique sites play an important role in anchoring thermodynamically metastable conformations of supported Au-Pd bimetallic catalysts and dictate their high-temperature activity.

Synthesis of bimetallic gold-silver alloy nanoclusters by simple mortar grinding.

A macroscale quantity of bimetallic Au-Ag alloy nanoclusters was achieved through sequential reduction by simple mortar grinding. The chitosan biopolymer was used as both a stabilizing and reducing agent. These nanoclusters exhibit excellent catalytic activity toward the reduction of 4-nitrophenol.

Magnetically recoverable magnetite/gold catalyst stabilized by poly(N-vinyl-2-pyrrolidone) for aerobic oxidation of alcohols.

Fe(3)O(4):PVP/Au nanocomposite synthesized via a two-step procedure was tested as a quasi-homogenous alcohol oxidation catalyst. It was found that the nanocomposite was able to carry out aerobic oxidation of alcohols in water at room temperature. Studies show rapid magnetic recoverability and reusability characteristics.