Enhanced electrocatalytic oxygen reduction reaction from organic-inorganic heterostructure

Herein, molybdenum disulfide nanoflakes decorated copper phthalocyanine microrods (CuPc-MoS₂) are synthesized via two step simple hydrothermal method. The as synthesized hybrid along with pure molybdenum disulfide (MoS₂) nanoflower and pure copper phthalocyanine (CuPc) microrods are well characterized by various techniques that confirm phase, morphology, elemental compositions etc. Next, electrocatalytic oxygen reduction reaction towards fuel cell is investigated in alkaline medium and obtained results proclaim that our CuPc-MoS₂ heterostructure outperforms the other two constituent materials. Efficient oxygen reduction is achieved following four electron pathway by CuPc-MoS₂ whereas partial reduction is done through two electron process by CuPc and MoS₂ separately. Long-time durability test reveals almost 97.6% retention after 8000s that eventually dictate us that CuPc-MoS₂ heterostructure can be the efficient cathode electrocatalyst for future generation fuel cell.     

Structure engineering of amorphous P–CoS hollow electrocatalysts for promoted oxygen evolution reaction

Oxygen evolution reaction (OER) is a key process involved in many energy-related conversion systems. An ideal OER electrocatalyst should possess rich active sites and optimal binding strength with oxygen-containing intermediates. Although numerous endeavors have been devoted to the modification and optimization of transition-metal-based OER electrocatalysts, they are still operated with sluggish kinetics. Herein, an ion-exchange approach is proposed to realize the structure engineering of amorphous P–CoS hollow nanomaterials by utilizing the ZIF-67 nanocubes as the precursors. The precise structure control of the amorphous hollow nanostructure contributes to the large exposure of surface active sites. Moreover, the introduction of phosphorus greatly modifies the electronic structure of CoS₂, which is thus favorable for optimizing the binding energies of oxygenated species. Furthermore, the incorporation of phosphorus may also induce the formation of surface defects to regulate the local electronic structure and surface environment. As a result of this, such P–CoS hollow nanocatalysts display remarkable electrocatalytic activity and durability towards OER, which require an overpotential of 283 mV to afford a current density of 10 mA cm^?2, outperforming commercial RuO₂ catalyst.     

Investigation of fabrication of gas diffusion substrate for proton exchange membrane fuel cells

The gas diffusion substrate (GDS) is essential in the proton exchange membrane fuel cells. Its fabrication techniques affect the performance significantly and are worthy of investigation. In this study, a manufacturing process of the GDS is proposed to understand the formation process of GDS and promote its structure and performance more pertinently. Different states during the preparation process, raw carbon paper, pre-curing, curing, carbonation, and graphitization, are characterized and measured. Experimental and numerical methods are employed to determine the relationships between microstructure, transport, and mechanical performance variation with the fabricating processes. The results show that its porosity, average pore size, and effective diffusivity decrease first and increase after curing. These parameters after graphitization are lower than that of the carbon paper (CP). The electrical resistivity increases dramatically while pre-curing and decreases gradually after curing, carbonation, and graphitization, and it is much reduced after graphitization. Moreover, mechanical measurement results show that both the picks of tensile strength and flexural modulus occur after curing. Its tensile strength shows little change after graphitization compared to the initial paper's. In contrast, the flexural modulus is improved significantly.     

Technical,economic, and environmental analyses of the modernization of a chamber furnace operating on natural gas or hydrogen

The paper presents a technical, economic and environmental analyses of a chamber furnace used to heat the charge before forging. The energy efficiency of the furnace before the modernization was 18%, after the modernization it was 31% (partial modernization due to large financial outlays). Other variants were also analysed: complete modernization, the variant of furnace modernization with 30% hydrogen content in the gas and the variant with 100% hydrogen as fuel. The analyses showed that with the current gas price (0.025 EUR/kWh) and the price of emission allowances (nearly 60 EUR/MgCO₂) and 100 cycles/year, the difference in Net Present Value (NPV) before base variant and partial modernization is around 900,000 EUR and before base variant and full modernization is 1,200,000 EUR. The introduction of the gas and 30% of hydrogen co-combustion option versus the base scenario option for 150 cycles per year results in a NPV difference of at least 2 million EUR. The option of 100% hydrogen as a fuel is the most advantageous from the point of view of reducing CO₂ emissions - it is largely influenced by the rising prices of CO₂ emission allowances.     

Enhanced gaseous hydrogen solubility in ferritic and martensitic steels at low temperatures

Metals that are exposed to high pressure hydrogen gas may undergo detrimental failure by embrittlement. Understanding the mechanisms and driving forces of hydrogen absorption on the surface of metals is crucial for avoiding hydrogen embrittlement. In this study, the effect of stress-enhanced gaseous hydrogen uptake in bulk metals is investigated in detail. For that purpose, a generalized form of Sievert's law is derived from thermodynamic potentials considering the effect of microstructural trapping sites and multiaxial stresses. This new equation is parametrized and verified using experimental data for carbon steels, which were charged under gaseous hydrogen atmosphere at pressures up to 1000 bar. The role of microstructural trapping sites on the parameter identification is critically discussed. Finally, the parametrized equation is applied to calculate the stress-enhanced hydrogen solubility of thin-walled pipelines and thick-walled pressure vessels during service.     

Synergistic effect of high-intensity ultrasound and β-cyclodextrin treatments on browning control in apple juice

This work evaluated the synergistic effects of combined high-intensity ultrasound (HIU) with β-cyclodextrin (β-CD) treatments on inhibiting browning of apple juice and explored the mechanism through simulation system. The combined treatment of 300 W HIU with 0.006 g mL⁻¹ β-CD had a synergistic impact on maintaining juice colour, resulting in a 39.06% reduction in browning degree, only a 36.64% decrease in total phenolic content, and a 17.82% reduction in PPO activity. The inhibition of enzymatic browning in simulated system revealed that HIU suppressed the enzyme (Polyphenol oxidase, PPO) and β-CD inhibited enzyme (PPO) and embedded substrate (polyphenol). The results of spectroscopic analysis showed that the particle-size distribution of PPO narrowed, the content of α-helix in the secondary structure increased, the fluorescence intensity increased, and the maximum wavelength was red-shifted after HIU and β-CD treatment. Changes in structure could further result in PPO activity loss. Hence, the combined treatment could synthetically alleviate the browning of apple juice.     

Cation and polyhedron substitution strategies: Effects on local crystal structure and on Bi3+ and Eu3+ co-doped inverse garnet phosphors’ luminescence property

Following the rapid growth of lightning technology, the development of red-emitting phosphors is effective for improving color temperature and color rendering index for w-LEDs devices. Herein, a single phased garnet phosphor with cation and polyhedron substitution modification was firstly prepared. For Mg₃Gd₂Ge₃O₁₂: Bi³⁺, Eu³⁺, the intensity has been remarkably improved by about 16% compared to the one without Bi³⁺ sensitization. The energy transfer mechanism is identified in this work. Based on cation and polyhedron substitution strategies, novel phosphors with different compositions were obtained and further modified the PL properties. With Lu³⁺ substitution, the bond lengths between Bi³⁺ ion and anion ligands are decreased and the site symmetry has been strengthened, which leads to a 21 nm blue shift when Lu³⁺ totally replaced Gd³⁺ ions. In addition, Lu³⁺ and [SiO₄] substitution strategies both effectively increased symmetric rigid structure, which leads to a significant improvement in thermal stability, indicating the samples own great potential in optical applications This work provides a new insight to synthesis red-emitting phosphors for warm white-LEDs.     

Impact of spinel forming systems (Fe-/Mg-/Mn-Al-O) as functional coating materials for carbon-bonded alumina filters on steel melt filtration

Since solid, non-metallic inclusions influence considerably the quality of casted steel products, carbon-bonded alumina foam filters are used in secondary metallurgical treatments to remove these particles from steel melts. In order to attain a significant improvement of the filtration process, five different carbonaceous spinel compounds from the Fe-/Mg-/Mn-Al-O systems are applied on carbon-bonded alumina filters in this study and investigated with regard of their filtration efficiency. However, these spinel compounds decompose partially during sintering at 1400?°C under reducing atmosphere, wherefore the resulting coatings contain not only spinel compounds, but also oxidic and metallic components. The subsequent interaction with molten steel leads to the development of multicrystal structures on the filter surface, which stem from interfacial reactions between coating materials, molten steel, and inclusions. As a result of this procedure, a reduction of almost 60% alumina inclusions is measured with the aid of an automatic SEM, whereby spinel compounds from the Fe-Mn-Al-O system achieve highest filtration efficiencies.     

Design and synthesis of side-chain optimized poly(2,6-dimethyl-1,4-phenylene oxide)-g-poly(styrene sulfonic acid) as proton exchange membrane for fuel cell applications: Balancing the water-resistance and the sulfonation degree

Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g^?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm^?1 at 40 °C and 45.5 mS cm^?1 at 95 °C, respectively.     

Time and space dependence of large-scale synthesis of colloidal particle with special morphology and tuneable polymer film architecture

This paper describes a facile method to control the morphology of polymer colloids and the architecture of polymer film via miniemulsion polymerization. By taking advantage of cyclization between the symmetrical diacrylate cross-linker hexamethylene diacrylate (HDDA) and the pendent vinyl in colloidal particles, the morphology of polymer colloids and the architecture of the after-formed polymer film were able to be well controlled by tuning the loading of cross-linker HDDA and crosslinking time. Four kinds of polymer colloid morphologies and four kinds of film architecture (honeycomb, close-packed, loose-packed, and enhanced-honeycomb) were characterized by TEM. The film formation mechanisms behind them were proposed based on the special and interesting results including Z-average size of the colloidal particles, Mc (molecular weight between crosslinking points) and mechanical properties of polymer film. Our results highly suggested that the morphology of polymer colloids and the polymer film architecture together determine the adhesive properties of the colloidal polymer film. The best of 180°-peel resistance, T-peel resistance and shear resistance of the polymer films were 138.12 N/25 mm, 40.98 N/25 mm and 25.72 N/cm² at 2.0 phm, 2.0 phm and 0.4 phm with the same crosslinking time of 90 min, respectively. The proposed method is promising to be scaled up for industrial production due to its well adaptability.