Visible-Light-Driven Photocatalytic H2 Production Using Composites of Co-Al Layered Double Hydroxides and Graphene Derivatives.

The direct conversion of solar energy into chemical energy represents an enormous challenge for current science. One of the commonly proposed photocatalytic systems is composed of a photosensitizer (PS) and a catalyst, together with a sacrificial electron donor (ED) when only the reduction of protons to H2 is addressed. Layered double hydroxides (LDH) have emerged as effective catalysts. Herein, two Co-Al LDH and their composites with graphene oxide (GO) or graphene quantum dots (GQD) have been prepared by coprecipitation and urea hydrolysis, which determined their structure and so their catalytic performance, giving H2 productions between 1409 and 8643 µmol g-1 using a ruthenium complex as PS and triethanolamine as ED at 450 nm. The influence of different factors, including the integration of both components, on their catalytic behavior, has been studied. The proper arrangement between the particles of both components seems to be the determining factor for achieving a synergistic interaction between LDH and GO or GQD. The novel Co-Al LDH composite with intercalated GQD achieved an outstanding catalytic efficiency (8643 µmol H2 g-1) and exhibited excellent reusability after 3 reaction cycles, thus representing an optimal integration between graphene materials and Co-Al LDH for visible light driven H2 photocatalytic production.

Modified surfatron device to improve microwave-plasma-assisted generation of RONS and methylene blue degradation in water.

Microwave-induced plasmas generated at atmospheric pressure are very attractive for a great variety of applications since they have a relatively high electron density and can generate large amounts of reactive species. Argon plasmas can be sustained inside dielectric tubes but are radially contracted and exhibit filamentation effects when the diameter of the tube is not narrow enough (over 1.5 mm). In this work, we describe a new approach for creating microwave (2.45 GHz) plasmas under atmospheric pressure conditions by using a surfatron device and power from 10 W. This modified design of the reactor enables the sustenance of non-filamented argon plasmas. These new plasmas have a higher gas temperature and electron density than the plasma generated in the original surfatron configuration. The new design also allows for the maintenance of plasmas with relatively high proportions of water, resulting in the generation of larger quantities of excited hydroxyl radicals (·OH*). Thus, this novel configuration extends the applicability of microwave-induced plasmas by enabling operation under new conditions. Finally, the degradation of methylene blue (MB) in aqueous solutions has been assessed under different initial dye concentrations and argon flow conditions. The new plasma produces a substantial increase in hydrogen peroxide and nitrate concentrations in water and leads to a noteworthy enhancement in MB degradation efficiency. The introduction of water into the plasma produces a minor additional improvement.

Iridium-Complexed Dipyridyl-Pyridazine Organosilica as a Catalyst for Water Oxidation.

The heterogenization of metal-complex catalysts to be applied in water oxidation reactions is a currently growing field of great scientific impact for the development of energy conversion devices simulating the natural photosynthesis process. The attachment of IrCp*Cl complexes to the dipyridyl-pyridazine N-chelating sites on the surface of SBA-15 promotes the formation of metal bipyridine-like complexes, which can act as catalytic sites in the oxidation of water to dioxygen, the key half-reaction of artificial photosynthetic systems. The efficiency of the heterogeneous catalyst, Ir@NdppzSBA, in cerium(IV)-driven water oxidation was thoroughly evaluated, achieving high catalytic activity even at a long reaction time. The reusability and stability were also examined after three reaction cycles, with a slight loss of activity. A comparison with an analogous homogeneous iridium catalyst revealed the enhanced durability and performance of the heterogeneous system based on the Ir@NdppzSBA catalyst due to the stability of the SBA-15 structure as well as the isolated metal active sites. Thereby, this new versatile synthesis route for the preparation of water oxidation catalysts opens a new avenue for the construction of alternative heterogeneous catalytic systems with high surface area, ease of functionalization, and facile separation to improve the efficiency in the water oxidation reaction.

Copper-complexed dipyridyl-pyridazine functionalized periodic mesoporous organosilica as a heterogeneous catalyst for styrene epoxidation.

A new heterogeneous catalyst has been synthesized by immobilization of a copper complex on dipyridyl-pyridazine functionalized periodic mesoporous organosilica (dppz-vPMO). This ordered support was first prepared by a co-condensation reaction between vinyltriethoxysilane and 1,2-bis(trimethoxysilyl)ethane and further post-functionalized through a hetero Diels-Alder reaction with 3,6-di-2-pyridyl-1,2,4,5-tetrazine. Techniques such as XRD, N2 isotherms, TEM, 13C NMR, XPS and DRIFT, among others, were employed to characterize the surface functionalized materials. These results have proven the ordered mesostructure of the materials as well as the presence of novel nitrogen-chelating heterocyclic compounds on the pore surface after the post-modification process. Additionally, the successful anchoring of a copper complex on the dipyridyl-pyridazine (dppz) ligands has been confirmed. The resulting material was evaluated as a heterogeneous catalyst in the epoxidation of styrene using tert-butylhydroperoxide (TBHP) as an oxidant. Under the optimized reaction conditions, Cu@dppz-vPMO showed a high styrene conversion (86.0%) and a remarkable selectivity to styrene oxide (41.9%). Indeed, this catalyst provided excellent catalytic results in terms of stability, reaction rate, conversion and selectivity compared to other bipyridine-like copper catalysts.

MIL-88A Metal-Organic Framework as a Stable Sulfur-host Cathode for Long-cycle Li-S Batteries.

Lithium-sulfur (Li-S) batteries have received enormous interest as a promising energy storage system to compete against limited, non-renewable, energy sources due to their high energy density, sustainability, and low cost. Among the main challenges of this technology, researchers are concentrating on reducing the well-known "shuttle effect" that generates the loss and corrosion of the active material during cycling. To tackle this issue, metal-organic frameworks (MOF) are considered excellent sulfur host materials to be part of the cathode in Li-S batteries, showing efficient confinement of undesirable polysulfides. In this study, MIL-88A, based on iron fumarate, was synthesised by a simple and fast ultrasonic-assisted probe method. Techniques such as X-ray diffraction (XRD), Raman spectroscopy, Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), and N2 adsorption/desorption isotherms were used to characterise structural, morphological, and textural properties. The synthesis process led to MIL-88A particles with a central prismatic portion and pyramidal terminal portions, which exhibited a dual micro-mesoporous MOF system. The composite MIL-88A@S was prepared, by a typical melt-diffusion method at 155°C, as a cathodic material for Li-S cells. MIL-88A@S electrodes were tested under several rates, exhibiting stable specific capacity values above 400 mAh g-1 at 0.1 C (1C = 1675 mA g-1). This polyhedral and porous MIL-88A was found to be an effective cathode material for long cycling in Li-S cells, retaining a reversible capacity above 300 mAh g-1 at 0.5 C for more than 1000 cycles, and exhibiting excellent coulombic efficiency.

Luminescent Graphene-Based Materials via Europium Complexation on Dipyridylpyridazine-Functionalized Graphene Sheets.

Graphene-based materials exhibit outstanding physical properties and so are potentially applicable in a great variety of fields. Unlike their corresponding oxides, graphite and graphene are not prone to functionalization. Diels-Alder reactions are among the scarce reactions that they can occur without disrupting their conjugated sp2 systems. Herein, the reaction between graphite and 3,6-di(2-pyridyl)-1,2,4,5-tetrazine under different conditions affords several graphene-based materials consisting of dipyridylpyridazine-functionalized few-layer graphene, multilayer graphene and graphite, the sheets of which act as ligands for the grafting of a europium complex. These three materials show strong red emission under 365 nm UV radiation. Their emitting particles can be visualized by confocal microscopy. The rich coordination chemistry of dipyridylpyridazine ligands has potential novel properties for similarly functionalized graphene-based materials grafted with other metal complexes.

A Comparative Study of Particle Size Distribution of Graphene Nanosheets Synthesized by an Ultrasound-Assisted Method.

Graphene-based materials are highly interesting in virtue of their excellent chemical, physical and mechanical properties that make them extremely useful as privileged materials in different industrial applications. Sonochemical methods allow the production of low-defect graphene materials, which are preferred for certain uses. Graphene nanosheets (GNS) have been prepared by exfoliation of a commercial micrographite (MG) using an ultrasound probe. Both materials were characterized by common techniques such as X-ray diffraction (XRD), Transmission Electronic Microscopy (TEM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). All of them revealed the formation of exfoliated graphene nanosheets with similar surface characteristics to the pristine graphite but with a decreased crystallite size and number of layers. An exhaustive study of the particle size distribution was carried out by different analytical techniques such as dynamic light scattering (DLS), nanoparticle tracking analysis (NTA) and asymmetric flow field flow fractionation (AF4). The results provided by these techniques have been compared. NTA and AF4 gave higher resolution than DLS. AF4 has shown to be a precise analytical technique for the separation of GNS of different sizes.

Fast ultrasound-assisted synthesis of highly crystalline MIL-88A particles and their application as ethylene adsorbents.

Highly crystalline MIL-88A particles have been successfully synthesized via fast ultrasound-assisted processes. The influence of the sonication generator and synthesis time on the structure, crystallinity, morphology and surface area of the materials were studied in detail. Under this modified ultrasonic method, X-ray diffraction patterns of MIL-88A particles showed highly crystalline structures in contrast to those reported in literature. Significant differences on surface areas and microporosity were appreciated under ultrasound conditions employed. Specific surface areas in the range between 179 and 359 m2 g-1 were obtained. That material synthesized under ultrasound batch conditions during 1 h had the highest surface area and microporous character. Different particle sizes and morphologies were obtained depending on the synthesis procedure. In general, probe sonicators led to smaller particle sizes. Moreover, a comparative study of the ethylene adsorption of the MIL-88A particles and several common MOFs in the ethylene adsorption was investigated. The results suggest that the modified ultrasound-assisted procedure for the synthesis of MIL-88A is effective to obtain highly crystalline particles, which are very efficient to adsorb ethylene molecules.

Coumarin Derivatives Solvent-Free Synthesis under Microwave Irradiation over Heterogeneous Solid Catalysts.

A suitable methodology of synthesis of coumarin derivatives by Pechmann reaction over heterogeneous solid acid catalysts in a free solvent media under microwave irradiation is described. Resorcinol, phenol and ethyl acetoacetate were selected as model reactants in the Pechmann condensation. The catalytic activity of several materials-Amberlyst-15, zeolite ß and sulfonic acid functionalized hybrid silica-in solvent-free microwave-assisted synthesis of the corresponding coumarin derivatives has been investigated in detail. 7-Hydroxy-4-methylcoumarin and 4-methylcoumarin were obtained in 97% and 43% yields, respectively, over Amberlyst-15. This was the most active catalyst in the Pechmann reaction under studied conditions.