Cu-doped GdFeO3 perovskites as electrocatalysts for the oxygen evolution reaction in alkaline media

Development of electrocatalysts for the oxygen evolution reaction (OER) plays a critical role in electrochemical water splitting systems. In this aim, iron based perovskite oxides with composition GdFe_1-x Cu_x O₃ (0 ≤ x ≤ 0.3) have been investigated. The effect of copper doping, calcination temperature on the OER performance in alkaline media was studied. The incorporation of Cu²⁺ (0 ≤ x ≤ 0.3) decreases the activity of calcined electrodes at 800 °C from 6.33 to 2.79 mA cm⁻², while that containing 0.2 mol of copper calcined at 600 °C, exhibits the higher activity (9.66 mA cm⁻²) at 0.66 V. The stability study during 8 h indicates that the undoped electrode calcined at 800 °C, exhibits relatively a better stability of the OER performance compared to that doped with 20% of copper calcined at 600 °C. The achieved results show promising potential for cost-effective hydrogen generation using earth-abundant materials and cheap fabrication processes.     

Photon absorption in a hybrid slurry photocatalytic reactor: Assessment of differential approximations

Radiative transfer inside a slurry photocatalytic reactor with hybrid illumination from both solar radiation and lamps is examined. The local volumetric rate of photon absorption is evaluated. For this purpose, the P1 and the modified differential approximations (MDAs) are used, and results compared to a solution by the Monte Carlo method. It is found that significant differences may arise between the predictions of the above approximations and the exact results provided by the Monte Carlo simulations. The P1 approximation is very inaccurate near to the radiation entrance for the partially collimated solar radiation, although it improves, as optical depth increases. As expected, the MDA improves the results near to the boundary. Surprisingly, it turns out to be much worse than the P1 approximation at medium and large optical depths. In the case of lamp irradiation, the behavior of the MDA is the opposite; it works better at small optical depths. © 2011 American Institute of Chemical Engineers AIChE J, 58: 3256–3265, 2012     

Fe7S8/FeS2/C as an efficient catalyst for electrocatalytic water splitting

Exploring effective bi-functional catalysts is of great significance to enhance the electrochemical activity for overall water splitting. To date, Fe₇S₈ has been rarely reported to realize electrochemical overall water splitting because of its intrinsic poor conductivity. In this paper, Fe₇S₈/FeS₂ heterostructured nanosheets with interface structures and defect sites are prepared via a facile hydrothermal method. Fe₇S₈/FeS₂/C electrocatalysts are constructed through the addition of carbon powder to weaken the electron transfer barrier. As expected, Fe₇S₈/FeS₂/C requires the overpotential of 262 mV and 198 mV to reach 10 mA/cm² toward oxygen evolution reaction and hydrogen evolution reaction, respectively. Moreover, Fe₇S₈/FeS₂/C attains a voltage of 1.67 V at 10 mA/cm² and maintains long-term stability for 24 h toward overall water splitting in a two-electrode system. The excellent activity can be related to interface structures and surface defect sites, which boost the charge transfer rate owing to the rich active sites.     

NiMo/Cu-nanosheets/Ni-foam composite as a high performance electrocatalyst for hydrogen evolution over a wide pH range

We designed and fabricated non-precious and highly efficient electrocatalysts of nickelmolybdenum/copper-nanosheets/nickel-foam composites (NiMo/Cu-NS/NF) by step electrodepositions, combining with chemical oxidation method. The catalysts were charaterized by means of SEM, XRD and XPS spectra. Their electrocatalytic activities were assessed by hydrogen evolution reactions (HER) over a wide pH range, where acidic, neutral and alkaline electrolytes were used, respectively. Benefiting from the unique midlayer Cu nanosheets (NS) architecture and optimum Mo–Ni composition at the surface layer which led to high electronic conductivity and large electrochemically active surface area (ECSA), the NiMo/Cu-NS/NF-2 catalyst displayed superior electrocatalytic activities with low overpotentials of η₁₀ = 43, 86 and 89 mV in 0.5 M H₂SO₄, 1.0 M PBS and 1.0 M KOH electrolyte, respectively. Especially in the acidic condition, it exhibited the best electrocatalytic activity with smaller Tafel slope of 54 mV dec^?1 and higher exchange current density of 1.93 mA cm^?2.     

Amorphous FeOOH decorated hierarchy capillary-liked CoAl LDH catalysts for efficient oxygen evolution reaction

Electrocatalytic water splitting is a promising route for the generation of clean hydrogen. However, the anodic oxygen evolution reaction (OER) suffers greatly from low reaction kinetics and thereby hampers the energy efficiency of alkaline water electrolysers. In recent years, tremendous efforts have been dedicated to the pursuit of highly efficient, low cost and stable electrocatalysts for oxygen evolution reaction. Herein, an amorphous FeOOH roughened capillary-liked CoAl layered double hydroxide (LDH) catalyst grown on nickel foam (denoted as FeOOH–CoAl LDH/NF) was reported for OER electrolysis. The developed FeOOH–CoAl LDH/NF electrode shows excellent OER activity with overpotentials of 228 mV and 250 mV to deliver a current density of 50 mA cm^?2 and 100 mA cm^?2 in 1.0 M KOH solution, respectively, ranking it one of the most promising OER catalysts based on transition-metal-based LDH. This is owed to the formed capillary-liked hierarchy structure with high-porosity as well as the strong electronic interaction between FeOOH and CoAl LDH. The developed morphological engineering approach to build hierarchal porous structures together with facile amorphous FeOOH modification may be extended to other layered double hydroxide catalyst for enhanced OER activities.     

NiFe2O4–Ni3S2 nanorod array/Ni foam composite catalyst indirectly controlled by Fe3+ immersion for an efficient oxygen evolution reaction

A NiFe alloy was designed on nickel foam (NF) as a precursor using cathodic electrodeposition. NiFe₂O₄–Ni₃S₂ nanorods (NRs) composite catalysts were prepared by Fe³⁺ impregnation and further hydrothermal sulfuration methods. NiFe₂O₄–Ni₃S₂ nanosheets (NSs) were also prepared by direct hydrothermal sulfuration of the NiFe alloy for comparison. Compared to the dense NS structure of the NiFe₂O₄–Ni₃S₂ NSs/NF, the NiFe₂O₄–Ni₃S₂ NRs/NF showed better oxygen evolution performance due to its unique weed-like NR array structure composed of additional oxygen evolution reaction (OER) active sites, with a strong electron interaction for Ni and Fe and the active sulfide synergistic effect with oxides. Therefore, Driving a current density of 10 mA cm^?2 only requires an overpotential of 189 mV and the catalyst could provide 100 mA cm^?2 continuously and be constant for more than 80 h in 1.0 M KOH. This experiment indicated that Fe³⁺ immersion had an indirect regulating effect on the morphological growth of the catalyst, which provided a novel concept for designing better OER catalysts.     

Facile synthesis of IrO2 nanoparticles decorated @ WO3 as mixed oxide composite for outperformed oxygen evolution reaction

Oxygen evolution reaction (OER) electrocatalysts play the critical role in efficiency and durability for different hydrogen production systems. We have successfully synthesized the earth abundant WO₃ coupled with IrO₂ as mixed oxide composite by a facile two-step chemical method. 50% reduction in noble metal contents (IW-50) followed by two times enhancement in activity, four-folds increase in bulk mass specific activity along with the stability of mixed oxide composite as compared to state –of –the art IrO₂ catalyst are affirmed. Superior performance of mixed oxide composites are perceived due to four times increase in electrochemical surface area, reduction of Tafel slope, four-fold increase of turn over frequency, electronic distortion in Ir-4f spectrum of IW-50 along with the bridging of lattice oxygen atoms between iridium and tungsten metals. We believe that it would open up the new avenues for effective utilization of noble metal with high valence tungsten metal in corrosive environment.     

临空经济区空间发展模式及趋势展望

随着机场由交通场所向区域节点的跨越转变,临空经济区也随之相应地发生着变化,其产业和空间形态已由孤立的城市边缘空间向融入区域一体化发展转变。因此,需要对临空经济区的产生机理、空间布局规律和特点、未来发展趋势进行总结及展望。研究从梳理国内外临空经济区的文献出发,对临空经济区的概念和空间发展模式进行探讨。从机场与临空经济区的关系出发,研究临空经济区与机场、中心城市、腹地之间在产业和空间上的互动关系—集聚效应与分散效应,勾勒出临空经济空间布局演变过程:独立机场区—机场产业化区—空港都市区,结合临空经济区出现的新变化和特点,探索和展望临空经济区的未来发展趋势—航空市镇群的发展。     

Curing kinetics of a novolac resin modified with oxidized multi‐walled carbon nanotubes

The influence of oxidized multi‐walled carbon nanotubes (o‐MWCNTs) on the curing kinetics of a novolac resin was studied by means of non‐isothermal differential scanning calorimetry. Regarding the kinetics issues, the high concentration of hydroxyl groups on the o‐MWCNTs slightly modified the curing reaction of the novolac resin, shifting the differential scanning calorimetry exothermic peak to higher temperatures. The effective activation energy of the curing reaction was calculated by the isoconversional Kissinger‐Akahira‐Sunose method and increased by the presence of o‐MWCNTs with respect to neat novolac. This change was attributed to the increase of the material viscosity. In addition, thermogravimetric analysis revealed that nanocomposites samples containing 0.4 and 1.0 wt% o‐MWCNTs presented increased char yield values, indicating an improvement of flame retardancy.     

Elastic stress field model and micro-crack evolution for isotropic brittle materials during single grit scratching

An analytical model for the elastic stress field in isotropic hard and brittle materials during scratching is presented. The model considers the entire elastic stress field and the effect of material densification that was ignored in past studies, and is developed under a cylindrical coordinate system to make the modeling process simpler. Based on the model's predictions, the location and sequence of crack nucleation are estimated and the associated mechanisms are discussed. A single grit scratching experiment with an increasing scratch depth up to 2 µm is conducted for two types of optical glasses representing isotropic brittle materials: fused silica and BK7 glasses. It is found that the model's predictions correlate well with experimental data. Median cracks are found to be formed first during scratching, and the corresponding depth of the scratch sets the basis for determining the critical depth for brittle to ductile machining. Lateral cracks are initiated in the plastic yielding region and deflect to the work surface to cause material removal, while Hertzian cracks interact with lateral cracks to help remove lateral-cracked material. Furthermore, it is found that, owing to its open network molecular structure, fused silica has a much worse ductile machinability than the BK7 glass.