This communication describes the synthesis of Pt-M (M = Au, Ni, Pd) icosahedral nanocrystals based on the gas reducing agent in liquid solution method. Both CO gas and organic surface capping agents play critical roles in stabilizing the icosahedral shape with {111} surfaces. Among the Pt-M alloy icosahedral nanocrystals generated, Pt(3)Ni had an impressive ORR specific activity of 1.83 mA/cm(2)(Pt) and 0.62 A/mg(Pt). Our results further show that the area-specific activity of icosahedral Pt(3)Ni catalysts was about 50% higher than that of the octahedral Pt(3)Ni catalysts (1.26 mA/cm(2)(Pt)), even though both shapes are bound by {111} facets. Density functional theory calculations and molecular dynamics simulations indicate that this improvement may arise from strain-induced electronic effects.
Enhanced kinetics for hydrogen exchange in LiBH 4 incorporated within nanoporous carbon scaffolds are described. Dehydrogenation rates up to 50 times faster than those in the bulk material are measured at 300 °C in a nanostructured hydride formed by filling a porous carbon aerogel host with LiBH 4 . Furthermore, the activation energy for hydrogen desorption, measured using the approach developed by Ozawa, is reduced from 146 kJ/mol for bulk LiBH 4 to 103 kJ/mol for nanostructured LiBH 4 , and the faster kinetics result in desorption temperatures that are reduced by up to 75 °C. In addition, nanostructured hydrides exhibit increased cycling capacity over multiple sorption cycles. This work demonstrates that confinement within a porous scaffold host is a promising approach for enhancing hydrogen uptake and release in reversible light-metal complex hydrides.
The shape of metal alloy nanocrystals plays an important role in catalytic performances. Many methods developed so far in controlling the morphologies of nanocrystals are however limited by the synthesis that is often material and shape specific. Here we show using a gas reducing agent in liquid solution (GRAILS) method, different Pt alloy (Pt-M, M = Co, Fe, Ni, Pd) nanocrystals with cubic and octahedral morphologies can be prepared under the same kind of reducing reaction condition. A broad range of compositions can also be obtained for these Pt alloy nanocrystals. Thus, this GRAILS method is a general approach to the preparation of uniform shape and composition-controlled Pt alloy nanocrystals. The area-specific oxygen reduction reaction (ORR) activities of Pt(3)Ni catalysts at 0.9 V are 0.85 mA/cm(2)(Pt) for the nanocubes, and 1.26 mA/cm(2)(Pt) for the nanooctahedra. The ORR mass activity of the octahedral Pt(3)Ni catalyst reaches 0.44 A/mg(Pt).
Sodalite zeolitic imidazolate frameworks containing Co (ZIF-67) and Zn (ZIF-8) were synthesized at room temperature under aqueous conditions in 10 min. A trialkylamine deprotonated the 2-methylimidazole ligand and nucleated the frameworks. Furthermore, the ligand acted as a structure directing agent in place of an organic solvent.
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