Nanocrystalline and Amorphous Calcium Carbonate from Waste Seashells by Ball Milling Mechanochemistry Processes.

Nanocrystalline calcium carbonate (CaCO3) and amorphous CaCO3 (ACC) are materials of increasing technological interest. Nowadays, they are mainly synthetically produced by wet reactions using CaCO3 reagents in the presence of stabilizers. However, it has recently been discovered that ACC can be produced by ball milling calcite. Calcite and/or aragonite are the mineral phases of mollusk shells, which are formed from ACC precursors. Here, we investigated the possibility to convert, on a potentially industrial scale, the biogenic CaCO3 (bCC) from waste mollusk seashells into nanocrystalline CaCO3 and ACC. Waste seashells from the aquaculture species, namely oysters (Crassostrea gigas, low-Mg calcite), scallops (Pecten jacobaeus, medium-Mg calcite), and clams (Chamelea gallina, aragonite) were used. The ball milling process was carried out by using different dispersing solvents and potential ACC stabilizers. Structural, morphological, and spectroscopic characterization techniques were used. The results showed that the mechanochemical process produced a reduction of the crystalline domain sizes and formation of ACC domains, which coexisted in microsized aggregates. Interestingly, bCC behaved differently from the geogenic CaCO3 (gCC), and upon long milling times (24 h), the ACC reconverted into crystalline phases. The aging in diverse environments of mechanochemically treated bCC produced a mixture of calcite and aragonite in a species-specific mass ratio, while the ACC from gCC converted only into calcite. In conclusion, this research showed that bCC can produce nanocrystalline CaCO3 and ACC composites or mixtures having species-specific features. These materials can enlarge the already wide fields of applications of CaCO3, which span from medical to material science.

Unraveling the optoelectronic properties of CoSbx intrinsic selective solar absorber towards high-temperature surfaces.

The combination of the ability to absorb most of the solar radiation and simultaneously suppress infrared re-radiation allows selective solar absorbers (SSAs) to maximize solar energy to heat conversion, which is critical to several advanced applications. The intrinsic spectral selective materials are rare in nature and only a few demonstrated complete solar absorption. Typically, intrinsic materials exhibit high performances when integrated into complex multilayered solar absorber systems due to their limited spectral selectivity and solar absorption. In this study, we propose CoSbx (2 < x < 3) as a new exceptionally efficient SSA. Here we demonstrate that the low bandgap nature of CoSbx endows broadband solar absorption (0.96) over the solar spectral range and simultaneous low emissivity (0.18) in the mid-infrared region, resulting in a remarkable intrinsic spectral solar selectivity of 5.3. Under 1 sun illumination, the heat concentrates on the surface of the CoSbx thin film, and an impressive temperature of 101.7 °C is reached, demonstrating the highest value among reported intrinsic SSAs. Furthermore, the CoSbx was tested for solar water evaporation achieving an evaporation rate of 1.4 kg m-2 h-1. This study could expand the use of narrow bandgap semiconductors as efficient intrinsic SSAs with high surface temperatures in solar applications.

An advanced PdNPs@MoS2 nanocomposite for efficient oxygen evolution reaction in alkaline media.

In response to the increasing availability of hydrogen energy and renewable energy sources, molybdenum disulfide (MoS2)-based electrocatalysts are becoming increasingly important for efficient electrochemical water splitting. This study involves the incorporation of palladium nanoparticles (PdNPs) into hydrothermally grown MoS2via a UV light assisted process to afford PdNPs@MoS2 as an alternative electrocatalyst for efficient energy storage and conversion. Various analytical techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDS), were used to investigate the morphology, crystal quality, and chemical composition of the samples. Although PdNPs did not alter the MoS2 morphology, oxygen evolution reaction (OER) activity was driven at considerable overpotential. When electrochemical water splitting was performed in 1.0 M KOH aqueous solution with PdNPs@MoS2 (sample-2), an overpotential of 253 mV was observed. Furthermore, OER performance was highly favorable through rapid reaction kinetics and a low Tafel slope of 59 mV dec-1, as well as high durability and stability. In accordance with the electrochemical results, sample-2 showed also a lower charge transfer resistance, which again provided evidence of OER activity. The enhanced OER activity was attributed to a number of factors, including structural, surface chemical compositions, and synergistic effects between MoS2 and PdNPs.

RuO2 Nanostructure as an Efficient and Versatile Catalyst for H2 Photosynthesis.

Photocatalytic H2 generation holds promise in the green production of alternative fuels and valuable chemicals. Seeking alternative, cost-effective, stable, and possibly reusable catalysts represents a timeless challenge for scientists working in the field. Herein, commercial RuO2 nanostructures were found to be a robust, versatile, and competitive catalyst in H2 photoproduction in several conditions. We employed it in a classic three-component system and compared its activities with those of the widely used platinum nanoparticle catalyst. We observed a hydrogen evolution rate of 0.137 mol h-1 g-1 and an apparent quantum efficiency (AQE) of 6.8% in water using EDTA as an electron donor. Moreover, the favorable employment of l-cysteine as the electron source opens possibilities precluded to other noble metal catalyst. The versatility of the system has also been demonstrated in organic media with impressive H2 production in acetonitrile. The robustness has been proved by the recovery of the catalyst by centrifugation and reusage alternatively in different media.

A high-sensitivity long-lifetime phosphorescent RIE additive to probe free volume-related phenomena in polymers.

The photophysical behaviour of phosphorescent rigidification-induced emission (RIE) dyes is highly affected by their micro- and nanoenvironment. The lifetime measure of RIE dyes dispersed in polymers represents an effective approach to gain valuable information on polymer free volume and thus develop materials potentially able to self-monitor physical ageing and mechanical stresses.

Persulfurated Benzene-Cored Asterisks with π-Extended ThioNaphthyl Arms: Synthesis, Structural, Photophysical and Covalent Dynamic Properties.

The synthesis of regioisomeric asterisks (5) and (6) incorporating a benzene core with six 1-naphthylthio or six 2-naphthylthio arms are reported in search for new materials with optoelectronic properties. The consequences on the extension of a π system surrounding a persulfurated benzene core provide a new avenue to study the structural, photophysical, and chemical properties of such family of all-organic phosphors. It also diverts the persulfuration mechanism after two radical cyclizations for making a [5]dithiohelicene by-product (7) and favors dynamic sulfur component exchange reactions surrounding the core. These exchanges convert asterisks (5) and (6), non-phosphorescent at 20 °C to the highly phosphorescent (4) (ϕ ∼100 %, solid state at 20 °C). For asterisks (5) and (6), the absence of the typical phosphorescence of the per(phenylthio)benzene core in the solid state at 20 °C and the presence of a weak naphthalene-based phosphorescence at 77 K is attributed to an energy transfer from the triplet state of the persulfurated benzene core to the outer naphthalene moieties, resulting in an antenna system.

Facile deposition of palladium oxide (PdO) nanoparticles on CoNi2S4microstructures towards enhanced oxygen evolution reaction.

Strong demand for renewable energy resources and clean environments have inspired scientists and researchers across the globe to carry out research activities on energy provision, conversion, and storage devices. In this context, development of outperform, stable, and durable electrocatalysts has been identified as one of the major objectives for oxygen evolution reaction (OER). Herein, we offer facile approach for the deposition of few palladium oxide (PdO) nanoparticles on the cobalt-nickel bi-metallic sulphide (CoNi2S4) microstructures represented as PdO@ CoNi2S4using ultraviolet light (UV) reduction method. The morphology, crystalline structure, and chemical composition of the as-prepared PdO@ CoNi2S4composite were probed through scanning electron microscopy, powder x-ray diffraction, high resolution transmission electron microscopy, energy dispersive spectroscopy and x-ray photoelectron spectroscopy techniques. The combined physical characterization results revealed that ultraviolet light (UV) light promoted the facile deposition of PdO nanoparticles of 10 nm size onto the CoNi2S4and the fabricated PdO@ CoNi2S4composite has a remarkable activity towards OER in alkaline media. Significantly, it exhibited a low onset potential of 1.41 V versus reversible hydrogen electrode (RHE) and a low overpotential of 230 mV at 10 mA cm-2. Additionally, the fabricated PdO@ CoNi2S4composite has a marked stability of 45 h. Electrochemical impedance spectroscopy has shown that the PdO@CoNi2S4composite has a low charge transfer resistance of 86.3 Ohms, which favours the OER kinetics. The PdO@ CoNi2S4composite provided the multiple number of active sites, which favoured the enhanced OER activity. Taken together, this new class of material could be utilized in energy conversion and storage as well as sensing applications.

Light-harvesting antennae based on copper indium sulfide (CIS) quantum dots.

Copper indium sulfide quantum dots (CIS QDs) and their core-shell analogues (CIS@ZnS QDs) were functionalized with pyrene chromophores via a dihydrolipoamide bifunctional binding moiety: UV excitation of the pyrene chromophores resulted in sensitized emission of the CIS core because of an efficient energy transfer process; the core-shell hybrid system exhibits a 50% increased brightness when excited at 345 nm.

Luminescent silicon nanocrystals appended with photoswitchable azobenzene units.

Confinement of multiple azobenzene chromophores covalently linked at the surface of luminescent silicon nanocrystals preserves the photoswitching behavior and modulates the nanocrystal polarity. Concomitantly, the thermal Z→E isomerization is strongly accelerated and the nanocrystal luminescence is reduced by an energy transfer process resulting in photosensitized E→Z isomerization.

Au-Decorated Ce-Ti Mixed Oxides for Efficient CO Preferential Photooxidation.

We investigated the photocatalytic behavior of gold nanoparticles supported on CeO2-TiO2 nanostructured matrixes in the CO preferential oxidation in H2-rich stream (photo-CO-PROX), by modifying the electronic band structure of ceria through addition of titania and making it more suitable for interacting with free electrons excited in gold nanoparticles through surface plasmon resonance. CeO2 samples with different TiO2 concentrations (0-20 wt %) were prepared through a slow coprecipitation method in alkaline conditions. The synthetic route is surfactant-free and environmentally friendly. Au nanoparticles (<1.0 wt % loading) were deposited on the surface of the CeO2-TiO2 oxides by deposition-precipitation. A benchmarking sample was also considered, prepared by standard fast coprecipitation, to assess how a peculiar morphology can affect the photocatalytic behavior. The samples appeared organized in a hierarchical needle-like structure, with different morphologies depending on the Ti content and preparation method, with homogeneously distributed Au nanoparticles decorating the Ce-Ti mixed oxides. The morphology influences the preferential photooxidation of CO to CO2 in excess of H2 under simulated solar light irradiation at room temperature and atmospheric pressure. The Au/CeO2-TiO2 systems exhibit much higher activity compared to a benchmark sample with a non-organized structure. The most efficient sample exhibited CO conversions of 52.9 and 80.2%, and CO2 selectivities equal to 95.3 and 59.4%, in the dark and under simulated sunlight, respectively. A clear morphology-functionality correlation was found in our systematic analysis, with CO conversion maximized for a TiO2 content equal to 15 wt %. The outcomes of this study are significant advancements toward the development of an effective strategy for exploitation of hydrogen as a viable clean fuel in stationary, automotive, and portable power generators.