Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.     

Two-dimensional numerical pore-scale investigation of oxygen evolution in proton exchange membrane electrolysis cells

Oxygen blocking the porous transport layer (PTL) increases the mass transport loss, and then limits the high current density condition of proton exchange membrane electrolysis cells (PEMEC). In this paper, a two-dimensional transient mathematical model of anode two-phase flow in PEMEC is established by the fluid volume method (VOF) method. The transport mechanism of oxygen in porous layer is analyzed in details. The effects of liquid water flow velocity, porosity, fiber diameter and contact angle on oxygen pressure and saturation are studied. The results show that the oxygen bubble transport in the porous layer is mainly affected by capillary pressure and follows the transport mechanism of ‘pressurization breakthrough depressurization’. The oxygen bubble goes through three stages of growth, migration and separation in the channel, and then be carried out of the electrolysis cell by liquid water. When oxygen breaks through the porous layer and enters the flow channel, there is a phenomenon that the branch flow is merged into the main stream, and the last limiting throat affects the maximum pressure and oxygen saturation during stable condition. In addition, increasing the liquid water velocity is helpful to bubble separation; changing the porosity and fiber diameter directly affects the width of pore throat and the correlative capillary pressure; increasing porosity, reducing fiber diameter and contact angle can promote oxygen breakthrough and reduce the stable saturation of oxygen.     

Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Microscopic high-speed video observation of oxygen bubble generation behavior and effects of anode electrode shape on OER performance in alkaline water electrolysis

An important difficulty associated with alkaline water electrolysis is the rise in anode overpotential attributable to bubble coverage of the electrode surface. For this study, a system with a high-speed video camera was developed, achieving in-situ observation of bubble generation on an electrode surface, monitoring an area of 1.02 mm² at 6000 frames per second. The relation between polarization curve (current density up to 3.0 A cm^?2) and oxygen bubble generation behavior on nickel electrodes having cylindrical wires and rectangular wires of different sizes (100–300 μm) was clarified. The generated bubbles slide upward, contacting the electrode surface and detaching at the top edge. Observations indicate that small electrodes have short bubble residence time and thin bubble covering layer on the electrode. As a result, the small electrode diameter contributes to smaller overpotential at high current density.     

Acidification of the electrolyte during the galvanic corrosion of AA7075: A numerical and experimental study

The electrochemical interactions between aluminum alloy 7075 and low-carbon steels under gelled electrolytes were studied. Such electrolytes provided the opportunity to investigate both thick and thin electrolyte systems. The electrolyte was chemically modified to visually track the acidic fronts during the anodic reaction and the subsequent hydrolysis process. Two mathematical models were validated for both thick and ultrathin electrolytes. The acidification of thick electrolytes was extended some millimeters beyond the aluminum alloy surface, whereas the acidic front was localized next to the metallic joint using ultrathin electrolytes. The combination of both numerical and experimental results allows proving (and explaining why) that the acidification process is more aggressive under dilute than under concentrated electrolytes.     

Evaluation of atmospheric galvanic aluminum corrosion in electrical transmission towers at different sites in the Valparaíso region,Chile. Wire-on-Bolt Test (CLIMAT)

This study evaluates environmental aggressiveness and atmospheric galvanic corrosivity categories in Chile (Classification of Industrial and Marine ATmospheres test) by installing bolts in electrical transmission towers in the Valparaiso region across four exposure sites: Playa Ancha, San Sebastián, Las Vegas, and San Felipe. Classifications of marine corrosion index (MCI), industrial corrosion index (ICI), and atmospheric corrosion index (ACI) used different galvanic couples: aluminum/steel for MCI, aluminum/copper for ICI, and aluminum/polyethylene for ACI. Corrosion indices varied by season (summer, autumn, winter, and spring), for which couples were exchanged every 3 months. Intraseason variation depended mainly on the meteorochemical variables of the zone, the Cl⁻/SO₂ ratio, and the presence of general and pitting corrosion in the aluminum. The results indicate that, regardless of environmental condition, the aluminum in Al/steel (MCI) and Al/copper (ICI) couples presented a higher corrosion rate than when not forming a galvanic couple (ACI). Moreover, under higher environmental chloride, these differences increase. The Playa Ancha station presented the highest ACI.     

Effects of environmental factors on corrosion behavior of aluminum

Aluminum, used as a material for heat exchangers in air conditioners, often has problems of leakage of refrigerant on the Al surface due to corrosion. The problems originate from pitting corrosion of the Al in an external environment. To understand corrosion problems, it is necessary to study the corrosion behavior of Al in various environments. In this study, the effects of environmental factors on the corrosion behavior of Al were studied by the surface analysis and electrochemical testing in 3.5 wt% NaCl solutions, with changes of dissolved oxygen, temperature, and concentration of Cl⁻ and S ions. Among the external environmental factors, the presence of oxygen and the increase of Cl⁻ ion concentration do not significantly affect the corrosion potential of Al, leading to an increase of only 1.1 and 6 times, respectively. There was a significant decrease in the corrosion resistance of Al, approximately 40 and 800 times, respectively, with the increase of concentration of S and temperature.     

Performance of BaZrO3/Y2O3 dual-phase refractory applied to TiAl alloy melting

Vacuum induction melting is a potential process for the preparation of TiAl alloys with good homogeneity and low cost. But the crucial problem is a selection of high stability refractory. In this study, a BaZrO₃/Y₂O₃ dual-phase refractory was prepared and its performance for melting TiAl alloys was studied and compared with that of a Y₂O₃ refractory. The results showed the dual-phase refractory consisted of BaZr_1-xY_xO_3-δ and Y₂O₃(ZrO₂), exhibited a thinner interaction layer (30 μm) than the Y₂O₃ refractory (90 μm) after melting the TiAl alloy. Although the TiAl alloys melted in the dual-phase and Y₂O₃ refractory exhibited similar oxygen contamination (<0.1 wt%), the alloy melted in the dual-phase refractory had smaller Y₂O₃ inclusion content and size than that in the Y₂O₃ refractory, indicating that the dual-phase refractory exhibited a better melting performance than the Y₂O₃ refractory. This study provides insights into the process of designing highly stable refractory for melting TiAl alloys.     

等温退火对8030铝合金导线组织性能的影响

研究了不同等温退火工艺对8030铝合金导线组织及性能的影响。结果表明:等温退火前后合金均由α-Al基体和Al₆Fe相组成。在同一等温温度下,随着等温时间的延长组织逐渐趋于均匀化;同一等温时间下,随着等温温度的升高,组织趋于均匀化的时间缩短。经过等温退火处理后铝合金导线的导电率均有所提高,在470 ℃均匀化退火24 h后再经240 ℃等温4 h,合金导电率达到最高值57.21%IACS,比未经热处理试样的导电率提高了2.4%IACS。经过等温退火处理后铝合金导线的硬度及抗拉强度均有所降低,塑性大幅度提高。在470 ℃均匀化退火24 h后再经260 ℃等温8 h,合金的伸长率最高可达23.64%。热处理前后合金均为塑性断裂。