Search

In the present investigation, Cu2O-based composites were successfully prepared through a multistep method where cubic Cu2O nanoparticles (CU Cu2O) have been grown on Reduced Graphene Oxide (RGO) nanosheets. The structural and morphological properties of the materials have been studied through a comprehensive characterization, confirming the coexistence of crystalline Cu2O and RGO. Microscopical imaging revealed the intimate contact between the two materials, affecting the size and the distribution of Cu2O nanoparticles on the support. The features of the improved morphology strongly affected the electrochemical behavior of the composites, increasing the activity and the faradaic efficiencies towards the electrochemical CO2 reduction reaction process. CU Cu2O/RGO 2:1 composite displayed selective CO formation over H2, with higher currents compared to pristine Cu2O (−0.34 mA/cm2 for Cu2O and −0.64 mA/cm2 for CU Cu2O/RGO 2:1 at the voltage of −0.8 vs. RHE and in a CO2 atmosphere) and a faradaic efficiency of 50% at −0.9 V vs. RHE. This composition exhibited significantly higher CO production compared to the pristine materials, indicating a favorable *CO intermediate pathway even at lower voltages. The systematic investigation on the effects of nanostructuration on composition, morphology and catalytic behavior is a valuable solution for the formation of effective interphases for the promotion of catalytic properties providing crucial insights for future catalysts design and applications. [ABSTRACT FROM AUTHOR]

The shape-controlled synthesis of cuprous oxide (Cu2O) photocatalysts with both low or high index crystal planes has received increasing attention due to their unique facet-dependent properties. Since they are cheap and earth abundant, these well-defined Cu2O nanostructures are extensively used for different photocatalytic reactions, also because of their strong visible light absorption capability. However, further development will still be needed to enhance the efficiency and photostability of Cu2O to expand its industrial application. We start this review by summarizing the synthetic advancement in the facet engineering of Cu2O and other associated hybrid Cu2O-based heterostructures with a special emphasis put on their growth mechanism. We then discuss different facet-dependent properties, which are relevant to photocatalysis. In the subsequent section, we present a critical discussion on the photocatalytic performance of faceted Cu2O nanostructures during organic synthesis, hydrogen production, and carbon dioxide photoreduction. The relation between photocatalytic efficiency and product selectivity with exposed crystal facets or with different compositions of hybrid nanostructures is also discussed. Finally, important strategies are proposed to overcome the photostability issue, while outlining the course of future development to further boost the technological readiness of well-defined Cu2O-based photocatalysts. [ABSTRACT FROM AUTHOR]

We report the highly facet-dependent catalytic activity of Cu2O nanocubes, octahedra, and rhombic dodecahedra for the multicomponent direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3. The catalytic activities of clean surfactant-removed Cu2O nanocrystals with the same total surface area were compared. Rhombic dodecahedral Cu2O nanocrystals bounded by {110} facets were much more catalytically active than Cu2O octahedra exposing {111} facets, whereas Cu2O nanocubes displayed the slowest catalytic activity. The superior catalytic activity of Cu2O rhombic dodecahedra is attributed to the fully exposed surface Cu atoms on the {110} facet. A large series of 1,4-disubstituted 1,2,3-triazoles have been synthesized in excellent yields with high regioselectivity under green conditions by using these rhombic dodecahedral Cu2O catalysts, including the synthesis of rufinamide, an antiepileptic drug, demonstrating the potential of these nanocrystals as promising heterogeneous catalysts for other important coupling reactions. [ABSTRACT FROM AUTHOR]

The synthetic value of this method is demonstrated by preparation of rufinamide (XIII). [ABSTRACT FROM AUTHOR]

Cu 2 O cubes, octahedra, and rhombic dodecahedra can be pseudomorphically converted into Cu crystals of corresponding shapes through reduction by ammonia borane in ethanol at 50 °C or below within 3 min, demonstrating the feasibility of making challenging polyhedral metal particles from metal oxide crystals. Hydrogen gas is also produced from ammonia borane in the process. The obtained Cu crystals have a slightly nanoporous interior. Addition of diphenylacetylene in the formation of Cu rhombic dodecahedra leads to complete stereoselective production of sterically hindered ( Z )-stilbene. Semihydrogenation of other alkynes also gives pure ( Z )-alkenes. Cu cubes and octahedra also showed considerable ( Z )-stilbene selectivity along with minor formation of ( E )-stilbene and bibenzyl as compared to CuCl 2 and commercial Cu 2 O particles. Mechanistic studies reveal that the low binding affinity of alkenes on the rhombic dodecahedra surfaces leads to high product selectivity. These Cu crystals act as a green and low-cost catalyst for the synthesis of high-purity ( Z )-alkenes.

Au-Pd core-shell nanocrystals with tetrahexahedral (THH), cubic, and octahedral shapes and comparable sizes were synthesized. Similar-sized Au and Pd cubes and octahedra were also prepared. These nanocrystals were used for the hydrogen-evolution reaction (HER) from ammonia borane. Light irradiation can enhance the reaction rate for all the catalysts. In particular, Au-Pd THH exposing {730} facets showed the highest turnover frequency for hydrogen evolution under light with 3-fold rate enhancement benefiting from lattice strain, modified surface electronic state, and a broader range of light absorption. Finite-difference time-domain (FDTD) simulations show a stronger electric field enhancement on Au-Pd core-shell THH than those on other Pd-containing nanocrystals. Light-assisted nitro reduction by ammonia borane on Au-Pd THH was also demonstrated. Au-Pd tetrahexahedra supported on activated carbon can act as a superior recyclable plasmonic photocatalyst for hydrogen evolution., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Gold nanocubes, octahedra, and rhombic dodecahedra were examined for facet-dependent catalytic activity in the formation of triazoles. Rhombic dodecahedra gave 100% regioselective 1,4-triazoles. The product yield was increased by decreasing the particle size. However, a mixture of 1,4- and 1,5-triazoles was obtained in lower yields when cubes and octahedra of similar sizes were used. The lowest Au-atom density on the {110} surface and largest unsaturated coordination number of surface Au atoms may explain their best catalytic efficiency and product regioselectivity. Various spectroscopic techniques were employed to verify the formation of the Au-acetylide intermediate and establish the reaction mechanism, in which phenylacetylene binds to the Au {110} surface through the terminal-binding mode to result in the exclusive formation of 1,4-triazoles. The smallest rhombic dodecahedra can give diverse 1,4-disubstituted triazoles in good yields by coupling a wide variety of alkynes and organic halides., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this study, rhombic dodecahedral gold nanocrystals were used as cores for the generation of Au-Ag core-shell nanocrystals with cubic, truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures. Gold nanocrystals were added to an aqueous mixture of cetyltrimethylammonium chloride (CTAC) surfactant, AgNO3, ascorbic acid, and NaOH to form the core-shell nanocrystals. The nanocrystals are highly uniform in size and shape, and can readily self-assemble into ordered packing structures on substrates. Results from observation of solution color changes and variation in the reaction temperature suggest octahedra are produced at a higher growth rate, while slower growth favors cube formation. The major localized surface plasmon resonance (LSPR) band positions for these nanocrystals are red-shifted compared to those for pristine silver particles with similar dimensions due to the LSPR effect from the gold cores. By increasing the concentrations of reagents, Au-Ag core-shell cubes and octahedra with tunable sizes were obtained. Au-Ag cubes with body diagonals of 130, 144, and 161 nm and octahedra with body diagonals of 113, 126, and 143 nm have been prepared, allowing the investigation of size effect on their optical properties. Au-Ag octahedra with thinner Ag shells (12-16.5 nm) exhibit a blue-shifted major LSPR band relative to the LSPR band at 538 nm for the gold cores. For Au-Ag octahedra and cubes with thicker shells (22.5-37 nm), the major LSPR band is progressively red-shifted from that of the gold cores with increasing shell thickness and particle size. The Au-Ag octahedra show higher catalytic activity than cubes toward reduction of 2-amino-5-nitrophenol by NaBH4 at 30 °C, but both particle shapes display significantly enhanced catalytic efficiency at 40 °C.

We report the highly facet-dependent catalytic activity of Cu2O nanocubes, octahedra, and rhombic dodecahedra for the multicomponent direct synthesis of 1,2,3-triazoles from the reaction of alkynes, organic halides, and NaN3. The catalytic activities of clean surfactant-removed Cu2O nanocrystals with the same total surface area were compared. Rhombic dodecahedral Cu2O nanocrystals bounded by {110} facets were much more catalytically active than Cu2O octahedra exposing {111} facets, whereas Cu2O nanocubes displayed the slowest catalytic activity. The superior catalytic activity of Cu2O rhombic dodecahedra is attributed to the fully exposed surface Cu atoms on the {110} facet. A large series of 1,4-disubstituted 1,2,3-triazoles have been synthesized in excellent yields with high regioselectivity under green conditions by using these rhombic dodecahedral Cu2O catalysts, including the synthesis of rufinamide, an antiepileptic drug, demonstrating the potential of these nanocrystals as promising heterogeneous catalysts for other important coupling reactions., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)