Understanding Gas-Induced Structural Deformation of ZIF-8.

ZIF-8 is a zeolitic imidazolate framework with very good thermal and chemical stability that opens up many applications that are not feasible by other metal-organic frameowrks (MOFs) and zeolites. Several works report the adsorption properties of ZIF-8 for strategic gases. However, despite the vast experimental corpus of data reported, there seems yet to be a dearth in the understanding of the gas adsorption properties. In this work we provide insights at a molecular level on the mechanisms governing the ZIF-8 structural deformation during molecular adsorption. We demonstrate that the ZIF-8 structural deformation during the adsorption of different molecules at cryogenic temperature goes beyond the gas-induced rotation of the imidazolate linkers. We combine experimental and simulation studies to demonstrate that this deformation is governed by the polarizability and molecular size and shape of the gases, and that the stepped adsorption behavior is defined by the packing arrangement of the guest inside the host.

Solid-phase synthesis of graphitic carbon nanostructures from iron and cobalt gluconates and their utilization as electrocatalyst supports.

We present a novel and facile synthesis methodology for obtaining graphitic carbon structures from Fe(II) and Co(II) gluconates. The formation of graphitic carbon can be carried out in only one step by means of heat treatment of these organic salts at a temperature of 900 degrees C or 1000 degrees C under inert atmosphere. This process consists of the following steps: (a) pyrolysis of the organic gluconate and its transformation to amorphous carbon, (b) conversion of Fe(2+) and Co(2+) ions to Fe(2)O(3) and CoO and their subsequent reduction to metallic nanoparticles by the carbon and (c) conversion of a fraction of formed amorphous carbon to graphitic structures by Fe and Co nanoparticles that act as catalysts in the graphitization process. The removal of the amorphous carbon and metallic nanoparticles by means of oxidative treatment (KMnO(4) in an acid solution) allows graphitic carbon nanostructures (GCNs) to be selectively recovered. The GCNs thus obtained (i.e. nanocapsules and nanopipes) have a high crystallinity as evidenced by TEM/SAED, XRD and Raman analysis. In addition, we used these GCNs as supports for platinum nanoparticles, which were well dispersed (mean Pt size approximately 2.5-3.2 nm). Most electrocatalysts prepared in this way have a high electrocatalytical surface area, up to 90 m(2) g(-1) Pt, and exhibit high catalytic activities toward methanol electrooxidation.