Search Results (8)

The emerging energy and environmental concerns nowadays are highlighting the need to turn to clean fuels, such as hydrogen. In this regard, hydrogen sulfide (H₂S), an abundant chemical compound found in several natural sources and industrial streams, can be considered a potential carbon-free H₂ source through its decomposition. In the present work, the H₂S decomposition performance of Co₃O₄/CeO₂ mixed oxide catalysts toward hydrogen production is investigated under excess H₂O conditions (1 v/v% H₂S, 90 v/v% H₂O, Ar as diluent), simulating the concentrated H₂S-H₂O inflow by the Black Sea deep waters. The effect of key operational parameters such as feed composition, temperature (550–850 °C), and cobalt loading (0–100 wt.%) on the catalytic performance of Co₃O₄/CeO₂ catalysts was systematically explored. In order to gain insight into potential structure-performance relationships, various characterization studies involving BET, XRD, SEM/EDX, and sulfur elemental analysis were performed over the fresh and spent samples. The experimental results showed that the 30 wt.% Co/CeO₂ catalyst demonstrated the optimum catalytic performance over the entire temperature range with a H₂ production rate of ca. 2.1 μmol H₂∙g⁻¹·s⁻¹ at 850 °C and a stable behavior after 10 h on stream, ascribed mainly to the in-situ formation of highly active and stable cobalt sulfided phases. Full article

Metal–organic frameworks (MOFs) have been widely used as porous nanomaterials for different applications ranging from industrial to biomedicals. An unpredictable one-pot method is introduced to synthesize NH₂-MIL-53 assisted by high-gravity in a greener media for the first time. Then, porphyrins were deployed to adorn the surface of MOF to increase the sensitivity of the prepared nanocomposite to the genetic materials and in-situ cellular protein structures. The hydrogen bond formation between genetic domains and the porphyrin’ nitrogen as well as the surface hydroxyl groups is equally probable and could be considered a milestone in chemical physics and physical chemistry for biomedical applications. In this context, the role of incorporating different forms of porphyrins, their relationship with the final surface morphology, and their drug/gene loading efficiency were investigated to provide a predictable pattern in regard to the previous works. The conceptual phenomenon was optimized to increase the interactions between the biomolecules and the substrate by reaching the limit of detection to 10 pM for the Anti-cas9 protein, 20 pM for the single-stranded DNA (ssDNA), below 10 pM for the single guide RNA (sgRNA) and also around 10 nM for recombinant SARS-CoV-2 spike antigen. Also, the MTT assay showed acceptable relative cell viability of more than 85% in most cases, even by increasing the dose of the prepared nanostructures. Full article

Efflorescence is aesthetically undesirable to all cementitious materials products and mainly results from the carbonation of hydrates and salt precipitation. Alternative binders without portlandite formation theoretically have much lower efflorescence risk, but in practice, the efflorescence of ettringite-rich systems is still serious. This study reports the impacts of mineral additives on the efflorescence of ettringite-rich systems and the corresponding microstructural evolution. The effects of silica fume, limestone powder, and diatomite on efflorescence and the capillary pore structure of mortars were investigated from a multi-scale analysis. The composition and microstructure of efflorescent phases were revealed by optical microscope (O.M.), in-situ Raman spectroscopy, and Scanning Electron Microscopy (SEM). Results indicate that the addition of mineral additives can efficiently inhibit the efflorescence of reference, especially with silica fume. Similar to the ettringite-rich system, the efflorescence substances of all modifies are composed of ettringite and CaCO₃, indicating that the addition of mineral admixture does not lead to chemical reactions, lower capillary absorption coefficient of mineral additives modified specimen, the denser pore structure and the lower efflorescence degree. Full article

The enhancement of both thermal and mechanical properties of epoxy materials using nanomaterials becomes a target in coating of the steel to protect it from aggressive environmental conditions for a long time, with reducing the cost. In this respect, the adhesion properties of the epoxy with the steel surfaces, and its proper superhyrophobicity to repel the seawater humidity, can be optimized via addition of green nanoparticles (NPs). In-situ modification of silver (Ag) and calcium carbonate (CaCO₃) NPs with oleic acid (OA) was carried out during the formation of Ag−OA and CaCO₃−OA, respectively. The epoxide oleic acid (EOA) was also used as capping for Ca−O₃ NPs by in-situ method and epoxidation of Ag−OA NPs, too. The morphology, thermal stability, and the diameters of NPs, as well as their dispersion in organic solvent, were investigated. The effects of the prepared NPs on the exothermic curing of the epoxy resins in the presence of polyamines, flexibility or rigidity of epoxy coatings, wettability, and coatings durability in aggressive seawater environment were studied. The obtained results confirmed that the proper superhyrophobicity, coating adhesion, and thermal stability of the epoxy were improved after exposure to salt spray fog for 2000 h at 36 °C. Full article

The electrochemical reduction of carbon dioxide into carbon monoxide, hydrocarbons and formic acid has offered an interesting alternative for a sustainable energy scenario. In this context, Sn-based electrodes have attracted a great deal of attention because they present low price and toxicity, as well as high faradaic efficiency (FE) for formic acid (or formate) production at relatively low overpotentials. In this work, we investigate the role of tin oxide surfaces on Sn-based electrodes for carbon dioxide reduction into formate by means of experimental and theoretical methods. Cyclic voltammetry measurements of Sn-based electrodes, with different initial degree of oxidation, result in similar onset potentials for the CO₂ reduction to formate, ca. −0.8 to −0.9 V vs. reversible hydrogen electrode (RHE), with faradaic efficiencies of about 90–92% at −1.25 V (vs. RHE). These results indicate that under in-situ conditions, the electrode surfaces might converge to very similar structures, with partially reduced or metastable Sn oxides, which serve as active sites for the CO₂ reduction. The high faradaic efficiencies of the Sn electrodes brought by the etching/air exposition procedure is ascribed to the formation of a Sn oxide layer with optimized thickness, which is persistent under in situ conditions. Such oxide layer enables the CO₂ “activation”, also favoring the electron transfer during the CO₂ reduction reaction due to its better electric conductivity. In order to elucidate the reaction mechanism, we have performed density functional theory calculations on different slab models starting from the bulk SnO and Sn₆O₄(OH)₄ compounds with focus on the formation of -OH groups at the water-oxide interface. We have found that the insertion of CO₂ into the Sn-OH bond is thermodynamically favorable, leading to the stabilization of the tin-carbonate species, which is subsequently reduced to produce formic acid through a proton-coupled electron transfer process. The calculated potential for CO₂ reduction (E = −1.09 V vs. RHE) displays good agreement with the experimental findings and, therefore, support the CO₂ insertion onto Sn-oxide as a plausible mechanism for the CO₂ reduction in the potential domain where metastable oxides are still present on the Sn surface. These results not only rationalize a number of literature divergent reports but also provide a guideline for the design of efficient CO₂ reduction electrocatalysts. Full article

Formic acid (FA) is a promising reservoir for hydrogen storage and distribution. Its dehydrogenation releases CO₂ as a by-product, which limits its practical application. A proof of concept for a bio-catalytic system that simultaneously combines the dehydrogenation of formic acid for H₂, in-situ capture of CO₂ and its re-hydrogenation to reform formic acid is demonstrated. Enzymatic reactions catalyzed by carbonic anhydrase (CA) and formate dehydrogenase (FDH) under ambient condition are applied for in-situ CO₂ capture and re-hydrogenation, respectively, to develop a sustainable system. Continuous production of FA from stripped CO₂ was achieved at a rate of 40% using FDH combined with sustainable co-factor regeneration achieved by electrochemistry. In this study, the complete cycle of FA dehydrogenation, CO₂ capture, and re-hydrogenation of CO₂ to FA has been demonstrated in a single system. The proposed bio-catalytic system has the potential to reduce emissions of CO₂ during H₂ production from FA by effectively using it to recycle FA for continuous energy supply. Full article

Wood flours (WFs) are bulky lignocellulosic materials that can increase the bulk and stiffness of paper. To be used in printing paper for replacing chemical pulp, WFs were first fractionated by a 200-mesh screen to improve smoothness; second, they were coated with calcium carbonate by an in-situ CaCO₃ formation method (coated wood flours, CWFs) to improve brightness. The performance of CWFs for printing paper was compared to those of bleached wood flours (BWFs) and bleached chemical pulp. Equivalent brightness and much higher smoothness were obtained for the CWFs compared to the BWFs. Furthermore, BWFs caused a significant loss of yield and required wastewater treatment in the bleaching process, while the CWFs increased the yield greatly by attaching CaCO₃ to the wood flours, and caused no wastewater burden. An accelerated aging test showed that the CWFs caused lesser brightness and strength loss than the bleached chemical pulp and BWFs. CWFs still had room for improvement to replace chemical pulp, but showed slower aging in optical and close strength properties. Full article

A novel and simple transcription strategy has been designed for the template-synthesis of CePO₄·xH₂O nanofibers having an improved nanofibrous morphology using a pH-sensitive nanofibrous hydrogel (glycine-alanine lipodipeptide) as structure-directing scaffold. The phosphorylated hydrogel was employed as a template to direct the mineralization of high aspect ratio nanofibrous cerium phosphate, which in-situ formed by diffusion of aqueous CeCl₃ and subsequent drying (60 °C) and annealing treatments (250, 600 and 900 °C). Dried xerogels and annealed CePO₄ powders were characterized by conventional thermal and thermogravimetric analysis (DTA/TG), and Wide-Angle X-ray powder diffraction (WAXD) and X-ray powder diffraction (XRD) techniques. A molecular packing model for the formation of the fibrous xerogel template was proposed, in accordance with results from Fourier-Transformed Infrarred (FTIR) and WAXD measurements. The morphology, crystalline structure and composition of CePO₄ nanofibers were characterized by electron microscopy techniques (Field-Emission Scanning Electron Microscopy (FE-SEM), Transmission Electron Microscopy/High-Resolution Transmission Electron Microscopy (TEM/HRTEM), and Scanning Transmission Electron Microscopy working in High Angle Annular Dark-Field (STEM-HAADF)) with associated X-ray energy-dispersive detector (EDS) and Scanning Transmission Electron Microscopy-Electron Energy Loss (STEM-EELS) spectroscopies. Noteworthy, this templating approach successfully led to the formation of CePO₄·H₂O nanofibrous bundles of rather co-aligned and elongated nanofibers (10–20 nm thick and up to ca. 1 μm long). The formed nanofibers consisted of hexagonal (P6₂22) CePO₄ nanocrystals (at 60 and 250 °C), with a better-grown and more homogeneous fibrous morphology with respect to a reference CePO₄ prepared under similar (non-templated) conditions, and transformed into nanofibrous monoclinic monazite (P21/n) around 600 °C. The nanofibrous morphology was highly preserved after annealing at 900 °C under N₂, although collapsed under air conditions. The nanofibrous CePO₄ (as-prepared hexagonal and 900 °C-annealed monoclinic) exhibited an enhanced UV photo-luminescent emission with respect to non-fibrous homologues. Full article