Two-step growth mechanism of supported Co3O4-based sea-urchin like hierarchical nanostructures

The formation mechanism of Co3O4-based sea-urchin like nanostructures from Co-O-B layers is unveiled. In this process, promoted by oxidizing annealing, B plays a major role, inducing first a chemical reduction of Co and the formation of a metallic particle core. The growth of nano-needles from the particle surface occurs through outdiffusion and oxidation of Co from the metallic reservoir

Towards the Development of a Z-Scheme FeOx/g-C3N4 Thin Film and Perspectives for Ciprofloxacin Visible Light-Driven Photocatalytic Degradation

Thermally synthesized graphitic carbon nitride (g-C3N4) over pulsed laser deposition (PLD) produced urchin-like iron oxide (FeOx) thin films were fabricated via in situ and ex situ processes. Materials characterisation revealed the formation of the graphitic allotrope of C3N4 and a bandgap Eg for the combined FeOx/g-C3N4 of 1.87 and 1.95 eV for each of the different fabrication strategies. The in situ method permitted to develop a novel petal-like morphology, whereas for the ex situ method, a morphological mixture between FeOx bulk and g-C3N4 was observed. Given the improved optical and morphological properties of the in situ film, it was employed as a proof of concept for the direct photocatalysis and photo-Fenton removal of ciprofloxacin antibiotic (CIP) under visible light irradiation. Improved photocatalytic activity (rate constant k = 8.28 × 10−4 min−1) was observed, with further enhancement under photo-Fenton conditions (k = 2.6 × 10−3 min−1), in comparison with FeOx + H2O2 (k = 1.6 × 10−3 min−1) and H2O2 only (k = 1.3 × 10−4 min−1). These effects demonstrate the in situ methodology as a viable route to obtain working heterojunctions for solar photocatalysis in thin-film materials, rather than the more common powder materials

Catching the Reversible Formation and Reactivity of Surface Defective Sites in Metal-Organic Frameworks: An Operando Ambient Pressure-NEXAFS Investigation

In this work, we apply for the first time ambient pressure operando soft X-ray absorption spectroscopy (XAS) to investigate the location, structural properties, and reactivity of the defective sites present in the prototypical metal-organic framework HKUST-1. We obtained direct evidence that Cu+ defective sites form upon temperature treatment of the powdered form of HKUST-1 at 160 degrees C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu+/Cu2+ dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu2+/Cu2+ paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO2 may be reversibly adsorbed and desorbed from the surface defective Cu+/Cu2+ sites. These findings show that ambient pressure soft-XAS, combined with state-ofthe-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu+/Cu2+ complexes and their reversible restoration upon exposure to gaseous CO2

Development of Cobalt based Nanocatalysts for Energy and Environment

There is a rising concern about energy and environment for future. Transition from current fossil fuels to green fuels and building of cleaner environment to lead sustainable life is at enormous task. Hydrogen gas is recognized as a clean fuel and may be a sustainable solution. Hydrogen can be directly used as clean fuel in fuel cells with no harmful by-products. Chemical hydrides with high hydrogen storage capacity in terms of gravimetric and volumetric efficiencies are the most promising candidates to supply pure hydrogen at room temperature. Among them, Ammonia Borane (NH3BH3, AB) and Sodium borohydride (NaBH4, SBH) have drawn a lot of interest as they are stable, non-flammable, and nontoxic. Large amount of pure hydrogen gas is released during the hydrolysis of these hydrides in presence of certain catalysts and the by-products are non-toxic, environmentally safe and can be recycled. Co based catalysts are considered as good candidates for catalyzed hydrolysis owing to their good catalytic activity, low cost and effortless synthesis. In favor of environmental concern, especially the air pollution (conversion of CO to CO2) and water pollutions (organic pollutants) are vital problems and there is a serious need to mitigate these problems. Cobalt (Co) based materials are with high catalytic activity for hydrolysis, organic pollutants degradation and CO oxidation. So, a single Co based catalysts as powders and as immobilized coatings prepared by chemical reduction method and pulsed laser deposition (PLD) were studied for hydrogen production by hydrolysis of AB and SBH and thin film coatings Co3O4 were studied for CO oxidation and organic pollutants degradation. On the basis of characterization results, the role of catalyst to enhance catalytic activity is discussed in hydrolysis, CO oxidation and pollutants degradation reactions. The stability and re-usability of these catalysts have also been investigated

Effect of zeolites on thermal decomposition of ammonia borane

Chemical hydrides due to their light weight and high storage capacity are considered to be promising hydrogen storage materials for both mobile and stationary applications. Ammonia Borane (AB) is a novel material with very high hydrogen content (19.6 wt %) per mass. The decomposition of AB takes place in three steps at desorption temperatures of about 100 �C, 140 �C and above 1000 �C respectively releasing 1 mol of hydrogen in each step. The major obstacle towards the use of AB as a hydrogen store is its irreversibility and slow kinetics. With the additives the decomposition temperature could be reduced and the kinetics can be improved. Effect of addition of Zeolites on decomposition of Ammonia Borane at different temperatures is reported in this paper. It was observed that the kinetics behaviour is greatly affected by addition of Zeolites with considerable reduction in the induction or warm-up period

Effect of zeolites on thermal decomposition of ammonia borane

Chemical hydrides due to their light weight and high storage capacity are considered to be promising hydrogen storage materials for both mobile and stationary applications. Ammonia Borane (AB) is a novel material with very high hydrogen content (19.6 wt %) per mass. The decomposition of AB takes place in three steps at desorption temperatures of about 100 _C, 140 _C and above 1000 _C respectively releasing 1 mol of hydrogen in each step. The major obstacle towards the use of AB as a hydrogen store is its irreversibility and slow kinetics. With the additives the decomposition temperature could be reduced and the kinetics can be improved. Effect of addition of Zeolites on decomposition of Ammonia Borane at different temperatures is reported in this paper. It was observed that the kinetics behaviour is greatly affected by addition of Zeolites with considerable reduction in the induction or warm-up period

Understanding solid-gas reaction mechanisms by operando soft X-ray absorption spectroscopy at ambient pressure

Ambient-pressure operando soft X-ray absorption spectroscopy (soft-XAS) was applied to study the reactivity of hydroxylated SnO2 nanoparticles toward reducing gases. H2 was first used as a test case, showing that the gas phase and surface states can be simultaneously probed: Soft-XAS at the O K-edge gains sensitivity toward the gas phase, while at the Sn M4,5-edges, tin surface states are explicitly probed. Results obtained by flowing hydrocarbons (CH4 and CH3CHCH2) unequivocally show that these gases react with surface hydroxyl groups to produce water without producing carbon oxides and release electrons that localize on Sn to eventually form SnO. The partially reduced SnO2 – x layer at the surface of SnO2 is readily reoxidized to SnO2 by treating the sample with O2 at mild temperatures (>200 °C), revealing the nature of “electron sponge” of tin oxide. The experiments, combined with DFT calculations, allowed devising of a mechanism for dissociative hydrocarbon adsorption on SnO2, involving direct reduction of Sn sites at the surface via cleavage of C–H bonds and the formation of methoxy- and/or methyl-tin species at the surface