Elucidating the role of potassium addition on the surface chemistry and catalytic properties of cobalt catalysts for ammonia synthesis.

The ammonia synthesis process produces millions of tons of ammonia annually needed for the production of fertilisers, making it the second most produced chemical worldwide. Although this process has been optimised extensively, it still consumes large amounts of energy (around 2% of global energy consumption), making it essential to improve its efficiency. To accelerate this improvement, research on catalysts is necessary. Here, we studied the role of potassium in ammonia synthesis on cobalt catalysts and found that it was detrimental to the catalytic activity. It was shown that, regardless of the amount of introduced K, the activity of the K-modified catalysts was much lower than that of the undoped catalyst. K was found to be in the form of oxide; however, it was unstable and reducible to metallic K, which easily volatilised from the catalyst surface under activation conditions. In addition, potassium doping resulted in the sintering of the catalyst, the decrease in the surface basicity, and contributed to the loss of the active sites, mainly due to the coverage of Co surface by residual K species.

Functionalization of bamboo fibers with lawsone dye (Lawsonia inermis) to produce bioinspired hybrid color composite with antibacterial activity.

There is great interest in using eco-friendly functional colorants with antibacterial activity to produce colorful textile and plastic products. In this study, we designed, produced, and analyzed a novel multifunctional hybrid color composite colorant with antimicrobial properties, prepared from plant-based products. The new functional color composite was prepared by stabilizing lawsone dye onto amino-silanized cellulose from bamboo fibers. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy were performed to examine the possible interactions between the lawsone dye and silanized bamboo fibers. The color performance, morphology, chemical stability, and thermal stability of the prepared color composite were evaluated using scanning electron microscopy (SEM), UV-Vis spectrophotometry, and thermogravimetric analysis (TGA). The results were compared to those for pure lawsone dye. Modification of amino-silanized bamboo fibers with lawsone dye led to the formation of a light brown colorant that is more resistant to organic solvents (e.g. acetone, ethanol) and elevated temperatures than raw natural dye. Importantly, the designed bamboo fiber/lawsone system (BF-APTES-L) benefits from the synergistic combination of lawsone and bamboo fibers, showing strong antibacterial activity compared to the control sample of bamboo-as evidenced by noticeably inhibited growth of E. coli, S. aureus, and B. subtilis.

Microwave-Reactor-Based Preparation of Red Iron Oxide Pigment from Waste Iron Sulfate.

This article presents a two-step method of iron red synthesis based on waste long-term deposited iron(II) sulfate. The first step is the purification of waste iron sulfate, and then the pigment is synthesized by precipitation using a microwave reactor. The newly developed method of purification allows for quick and thorough purification of iron salt. The use of a microwave reactor in the synthesis of iron red makes it possible to reduce the temperature of the goethite-hematite phase transition from 500 °C to 170 °C and skip the calcination process. A temperature reduction in the synthesis decreases the formation of agglomerates of synthesized materials compared to commercial ones. The results of the research showed a change in the physicochemical properties of the obtained pigments depending on the conditions of synthesis. Waste iron(II) sulfate is a promising raw material for the synthesis of iron red pigments. Laboratory pigments are found to be differ from commercial pigments. The difference in properties speaks in favor of synthesized materials.

Co nanoparticles supported on mixed magnesium-lanthanum oxides: effect of calcium and barium addition on ammonia synthesis catalyst performance.

The synthesis of ammonia in the Haber-Bosch process produces millions of tons of ammonia annually needed for producing fertilisers required to feed the growing population. Although this process has been optimised extensively, it still accounts for about 2% of global energy consumption. It is, therefore, desirable to develop an efficient ammonia synthesis catalyst. Over the last decades, many attempts have been made to improve the ammonia synthesis catalyst efficiency under mild conditions. Here, we studied the effect of adding Ca and Ba to the cobalt ammonia synthesis catalyst. The combination of the different experimental results allows concluding that Ca served as an inactive additive, whereas Ba served as an electronic promoter. The Ca addition did not change the textural, structural, and chemisorptive properties of the Ca-doped Co catalyst. On the other hand, the Ba addition had a major effect on the nature of active Co sites. It contributed to the formation of new active sites for hydrogen and nitrogen adsorption and dissociation. Barium addition also contributed to the generation of new basic sites, particularly the strong ones. These unique characteristics were ascribed to the formation of Co(core)-BaO(shell) structures. It is likely that the donation of electrons from BaO to N2 via Co markedly promoted ammonia synthesis. This catalyst exhibited ammonia synthesis activity 4 times higher than that of the undoped Co catalyst and 2 times higher than that of the industrial Fe catalysts under identical conditions.

On the effect of metal loading on the performance of Co catalysts supported on mixed MgO-La2O3 oxides for ammonia synthesis.

Synthesis of ammonia from nitrogen and hydrogen is one of the largest manmade chemical processes, with annual production reaching 170 million tons. The Haber-Bosch process is the main industrial method for producing ammonia, which proceeds at high temperatures (400-600 °C) and pressures (20-40 MPa) using an iron-based catalyst. It is thus highly desirable to develop new catalysts with sufficient activity and stability under mild conditions. In this work, we report cobalt catalysts supported on magnesium-lanthanum mixed oxide with different Co loading amounts synthesised via a simple wet impregnation method. We have found a clear relationship between the ammonia synthesis rate and the Co loading amount. Specifically, the NH3 synthesis rate increased on increasing cobalt loading and reached a maximum at 40 wt% Co deposition. A further increase in Co loading did not change the activity significantly. Interestingly, the surface-specific activity (TOF) remained almost unchanged regardless of the Co loading amount in the catalysts. It revealed that the resultant ammonia synthesis rate over the studied catalysts did not depend on the size and structure of Co nanoparticles but strongly on the Co loading amount. Finally, it is believed that the use of this type of catalyst will be a starting point toward energy-efficient ammonia production.

Influence of Magnesium Oxide on the Structure and Catalytic Activity of the Wustite Catalyst for Ammonia Synthesis.

The influence of a magnesium oxide admixture on the activation process and catalytic activity of the iron catalyst with a wustite structure was investigated during the ammonia synthesis reaction. The incorporation of magnesium oxide into wustite grains is considered to be a structure-forming and activating promoter. It stabilizes the α-Fe structure and increases the activity of the catalysts in the ammonia synthesis reaction. Moreover, magnesium oxide forms a solid solution with the wustite, which slows down the reduction of a catalyst precursor. Similar to calcium and potassium compounds, magnesium oxide is present on the α-Fe surface of the active form of the catalyst. The optimum MgO concentration in the catalyst structure was determined to be 1.2% wt.

Synthesis of Selected Mixed Oxide Materials with Tailored Photocatalytic Activity in the Degradation of Tetracycline.

The elimination of antibiotics occurring in the natural environment has become a great challenge in recent years. Among other techniques, the photocatalytic degradation of this type of pollutant seems to be a promising approach. Thus, the search for new photoactive materials is currently of great importance. The present study concerns the sol-gel synthesis of mono, binary and ternary TiO2-based materials, which are used as active photocatalysts. The main goal was to evaluate how the addition of selected components-zirconium dioxide (ZrO2) and/or zinc oxide (ZnO)-during the synthesis of TiO2-based materials and the temperature of thermal treatment affect the materials' physicochemical and photocatalytic properties. The fabricated mixed oxide materials underwent detailed physicochemical analysis, utilizing scanning-electron microscopy (SEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), energy-dispersive X-ray spectroscopy (EDS), low-temperature N2 sorption (BET model), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The synthesized mixed oxide materials were used as photocatalysts in the heterogeneous photodegradation of tetracycline (TC). The physicochemical properties of the fabricated photocatalysts, including morphology, crystalline and textural structure, as well as the pH of the reaction system in the photocatalytic tests, were taken into account in determining their photo-oxidation activity. LC-MS/MS analysis was used to identify the possible degradation products of the selected antibiotic.

Nitriding and Denitriding of Nanocrystalline Iron System with Bimodal Crystallite Size Distribution.

An artificially prepared nanocrystalline iron sample with bimodal crystallite size distribution was nitrided and denitrided in the NH3/H2 atmosphere at 350 °C and 400 °C. The sample was a 1:1 mass ratio mixture of two iron samples with mean crystallite sizes of 48 nm and 21 nm. Phase transformations between α-Fe, γ'-Fe4N and ε-Fe3-2N were observed by the in situ X-ray powder diffraction method. At selected steps of nitriding or denitriding, phase transformations paused at 50% of mass conversion and resumed after prominent variation of the nitriding atmosphere. This effect was attributed to the separation of phase transformations occurring between sets of iron crystallites of 48 nm and 21 nm, respectively. This was due to the Gibbs-Thomson effect, which establishes the dependence of phase transformation conditions on crystallite sizes.

Lignin-based dual component additives as effective electrode material for energy management systems.

A functional PbO-lignin electrode hydrid material composite was designed and manufactured. Moreover, its connection efficiency was confirmed using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). We noted that the superficial layers of PbO combined with layers of the biopolymer and that oxygen atoms present in both materials had influence on the chemical environment of the neighboring compound. Hence, it can be said that the addition of PbO significantly contributes to the improvement of thermal stability of the final inorganic-organic system. In the framework of the study, the dispersive, morphological and structural characteristics were determined using scanning electron microscopy (SEM) and laser diffraction method. Electrochemical studies indicated that the PbO-lignin material exhibits better electrochemical properties compared to PbO without the addition of kraft lignin (increased capacitance, lower charge transfer resistance), as the specific capacitance after 5000 charge/discharge cycles was still at 95% of the initial value. Such promising operating parameters show that this material can be successfully used as an electrode material for energy management systems.

Crystallization of TiO2-MoS2 Hybrid Material under Hydrothermal Treatment and Its Electrochemical Performance.

Hydrothermal crystallization was used to synthesize an advanced hybrid system containing titania and molybdenum disulfide (with a TiO2:MoS2 molar ratio of 1:1). The way in which the conditions of hydrothermal treatment (180 and 200 °C) and thermal treatment (500 °C) affect the physicochemical properties of the products was determined. A physicochemical analysis of the fabricated materials included the determination of the microstructure and morphology (scanning and transmission electron microscopy-SEM and TEM), crystalline structure (X-ray diffraction method-XRD), chemical surface composition (energy dispersive X-ray spectroscopy-EDS) and parameters of the porous structure (low-temperature N2 sorption), as well as the chemical surface concentration (X-ray photoelectron spectroscop-XPS). It is well known that lithium-ion batteries (LIBs) represent a renewable energy source and a type of energy storage device. The increased demand for energy means that new materials with higher energy and power densities continue to be the subject of investigation. The objective of this research was to obtain a new electrode (anode) component characterized by high work efficiency and good electrochemical properties. The synthesized TiO2-MoS2 material exhibited much better electrochemical stability than pure MoS2 (commercial), but with a specific capacity ca. 630 mAh/g at a current density of 100 mA/g.

Surface Studies of UV Irradiated Polypropylene Films Modified with Mineral Fillers Designed as Piezoelectric Materials.

Isotactic-polypropylene (i-PP) films with inorganic minerals such as Sillikolloid, perlite, or glass beads were prepared. The obtained polymeric films were subjected to an orientation process. Moreover, this paper includes results how the artificial accelerated weathering influences surface properties of the unoriented and oriented i-PP films with the mineral fillers. Changes in the ultraviolet (UV) treated polymeric films were studied with attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and by measuring contact angles. The results revealed that photooxidation of i-PP was more effective in the presence of the fillers and depended on the type of the filler but not on its amount. Moreover, the oriented samples experienced more effective photooxidation compared with the unoriented ones. In all studied samples the same photoproducts were detected, suggesting the same route of polymer photooxidation with and without the filler. These polymeric films were produced for potential applications in the devices in which piezoelectric effect can be used.

Different Approaches to Oxygen Functionalization of Multi-Walled Carbon Nanotubes and Their Effect on Mechanical and Thermal Properties of Polyamide 12 Based Composites.

In this work the preparation of polyamide 12 (PA12) based composites reinforced with pristine and surface-modified carbon nanotubes is reported. A qualitative and quantitative evaluation of multi-walled carbon nanotube functionalization with oxygen containing reactive groups achieved by different procedures of chemical treatment is presented. Simple strong oxidative acid treatment as well as chlorination with subsequent chloroacetic acid treatment were applied. Carbon nanotubes (CNTs) were also subjected to chlorine and ammonia in gaseous atmosphere with small differences in after-ammonia treatment. Commercial COOH-functionalized carbon nanotubes were compared with nanotubes that were laboratory modified. The effect of CNT functionalization was evaluated basing on the improvement of mechanical and thermal properties of polyamide 12 composites prepared by in situ polymerization. It was found that high concentration of oxygen-containing functional groups on nanotube surface is not sufficient to improve the composite performance if the structure of carbon nanotubes is defective. Indeed, the best effects were achieved for composites containing nanotubes modified under mild conditions, seemingly due to a compromise between morphology and surface chemical structure.

Nanocomposite Titania-Carbon Spheres as CO2 and CH4 Sorbents.

Photocatalysis can offer solutions for the transformation of greenhouse gases, such as methane and carbon dioxide. In the paper, a candidate for such a photocatalyst is presented, based on a composite of titania with carbon spheres. The material was obtained using microwave assisted solvothermal synthesis, enabling good dispersion of titania. The studies of carbon dioxide and methane adsorption were performed under ambient pressure and temperatures of 40, 60, and 80 °C. The effect of temperature increase was less favorable for carbon dioxide than for methane. Satisfying values of carbon dioxide and methane uptake were obtained-3.94 mmol CO2/g and 2.77 mmol CH4/g at 40 °C.

XPS and FTIR Studies of Polytetrafluoroethylene Thin Films Obtained by Physical Methods.

Two methods-attenuated total reflection Fourier infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)-have been used to analyze the chemical structure of polytetrafluorethylene (PTFE) thin coatings deposited by pulsed laser (PLD) and pulsed electron beam (PED) ablations. The volume of the analyzed materials is significantly different in these techniques which can be of great importance in the characterization of highly heterogeneous thin films. Optical microscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) have been additionally used to examine the coating surface morphology. The studies have shown that in the case of thin polymer coatings deposited by physical methods, the application for chemical structure evaluation of complementary techniques, with different surface sensitivity, together with the use of surface topography imaging, provide unique insight into the film morphology. The results can provide information contributing to an in-depth understanding of the deposition mechanism of polymer coatings.

Chemical Structure of EVA Films Obtained by Pulsed Electron Beam and Pulse Laser Ablation.

Poly(ethylene-co-vinyl acetate) (EVA) films were deposited for the first time using physical methods. The chemical structure of the films obtained using two techniques, pulsed electron beam deposition (PED) and pulsed laser deposition (PLD), was studied by attenuated total reflection Fourier infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Whilst significant molecular degradation of the EVA films was observed for the PLD method, the original macromolecular structure was only partially degraded when the PED technique was used, emphasizing the superiority of the PED method over PLD for structurally complex polymers such as EVA. Optical and scanning electron microscopic observations revealed compact and smooth EVA films deposited by pulsed electron beam ablation as opposed to heterogeneous films with many different sized particulates obtained by PLD.

Robust biodegradation of naproxen and diclofenac by laccase immobilized using electrospun nanofibers with enhanced stability and reusability.

Enzymatic biodegradation of pharmaceuticals, using enzymes such as laccase, is a green solution for the removal of toxic pollutants that has attracted growing interest over recent years. Moreover, the application of immobilized biocatalysts is relevant for industrial applications, due to the improved stability and reusability of the immobilized enzymes. Thus, in the present study, laccase was immobilized by adsorption and encapsulation using poly(l-lactic acid)-co-poly(ε-caprolactone) (PLCL) electrospun nanofibers as a tailor-made support. The produced biocatalytic systems were applied in the biodegradation of two commonly used anti-inflammatories, naproxen and diclofenac, which are present in wastewaters at environmentally relevant concentrations. The results showed that under optimal process conditions (temperature 25 °C, pH 5 and 3 for naproxen and diclofenac respectively), even from a solution at a concentration of 1 mg L-1, over 90% of both pharmaceuticals was removed by encapsulated laccase in batch mode. Both immobilized enzymes also exhibited high reusability: after five reaction cycles approximately 60% and 40% of naproxen and diclofenac were removed by encapsulated and adsorbed laccase respectively. In addition, a thorough analysis was made of the products of biodegradation of the two studied pollutants. Furthermore, toxicity study of the mixture after biodegradation of the pharmaceuticals showed that the solutions obtained after the process were approximately 65% less toxic than the initial naproxen and diclofenac solutions.

Influence of Preparation Procedure on Physicochemical and Antibacterial Properties of Titanate Nanotubes Modified with Silver.

Silver nanoparticles (NPs) are effective antibacterial agents; however, aggregation of NPs and uncontrolled release of Ag+ affect their efficiency and may pose a risk to the environment. To overcome these disadvantages, immobilization of Ag onto titanate nanotubes (TNTs) was investigated. This paper describes the physicochemical and antibacterial properties of silver incorporated titanate nanotubes (Ag/TNTs) prepared using five procedures and containing different Ag amounts (0.11-30.85 wt.%). The methods were (i) sol-gel followed by a hydrothermal process; (ii) photodeposition under ambient conditions; (iii) photodeposition under an inert atmosphere; (iv) NaBH4 reduction; and (v) electroless deposition after activation of TNTs with Sn2+. Depending on the synthesis procedure, the presence of metallic Ag NPs, AgO or AgCl was observed. The electroless method led to an additional deposition of SnO2 NPs. The antibacterial properties of Ag/TNTs were analyzed as a function of Ag content and released against Escherichia coli and Staphylococcus epidermidis. The best bactericidal properties exhibited Ag/TNTs prepared through the photodeposition process due to the higher interaction of exposed Ag NPs with bacteria. An increase of Ag loading resulted in improvement of antibacterial activity of Ag/TNTs although no direct correlation between silver content or release and inhibition of bacterial growth was found.

Carminic Acid Stabilized with Aluminum-Magnesium Hydroxycarbonate as New Colorant Reducing Flammability of Polymer Composites.

In this study, hybrid pigments based on carminic acid (CA) were synthesized and applied in polymer materials. Modification of aluminum-magnesium hydroxycarbonate (LH) with CA transformed the soluble chromophore into an organic-inorganic hybrid colorant. Secondary ion mass spectroscopy (TOF-SIMS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and UV-Vis spectroscopy were used to study the structure, composition, and morphology of the insoluble LH/CA colorant. Successful modification of the LH was confirmed by the presence of interactions between the LH matrix and molecules of CA. XPS analysis corroborated the presence of CA complexes with Mg2+ ions in the LH host. The batochromic shift in UV-Vis spectra of the organic-inorganic hybrid colorant was attributed to metal-dye interactions in the organic-inorganic hybrid colorants. Strong metal-dye interactions may also be responsible for the improved solvent resistance and chromostability of the modified LH. In comparison to uncolored ethylene-norbornene copolymer (EN), a modified EN sample containing LH/CA pigment showed lower heat release rate (HRR) and reduced total heat release (THR), providing the material with enhanced flame retardancy.

Ammonolysis of Cobalt Molybdenum Oxides - In Situ XRD Study.

The reduction of cobalt molybdenum oxide under an ammonia atmosphere resulting in the formation of ternary interstitial nitride Co3Mo3N was studied. Intermediate phases were identified by an in situ powder X-ray diffraction using a reaction chamber. It was supplemented by a thermogravimetric analysis of the process. The presence of intermediate phases, CoMoO4, Co2Mo3O8, Mo2N, metallic cobalt, and Co2Mo3N, was observed. A synthesis route of Co3Mo3N by an ammonolysis method was proposed.

A Comparison of Hydrogen Storage in Pt, Pd and Pt/Pd Alloys Loaded Disordered Mesoporous Hollow Carbon Spheres.

Comprehensive study to evaluate the ability of hydrogen uptake by disordered mesoporous hollow carbon spheres doped witch metal such as Pt, Pd or Pt/Pd was conducted. They were synthesized facilely using sonication and then calcination process under vacuum at the temperature of 550 °C. The effect on hydrogen sorption at neat-ambient conditions (40 °C, up to 45 bar) was thoroughly analyzed. The results clearly revealed that metal functionalization has a significant impact on the hydrogen storage capacity as the mechanism of gas uptake depends on two factors: metal type and certain size of particles. Thus, functionalized spheres adsorb hydrogen by physisorption forming metal hydrides or metal hydrides combined with hydrogen spillover effect. As a result, a sample with narrower distribution of nanoparticles and smaller specific size exhibited enhanced hydrogen uptake.