Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Investigation of liquid water heterogeneities in large area proton exchange membrane fuel cells using a Darcy two-phase flow model in a multiphysics code

Proper management of the liquid water and heat produced in proton exchange membrane (PEM) fuel cells remains crucial to increase both its performance and durability. In this study, a two-phase flow and multicomponent model, called two-fluid model, is developed in the commercial COMSOL Multiphysics® software to investigate the liquid water heterogeneities in large area PEM fuel cells, considering the real flow fields in the bipolar plate. A macroscopic pseudo-3D multi-layers approach has been chosen and generalized Darcy's relation is used both in the membrane-electrode assembly (MEA) and in the channel. The model considers two-phase flow and gas convection and diffusion coupled with electrochemistry and water transport through the membrane. The numerical results are compared to one-fluid model results and liquid water measurements obtained by neutron imaging for several operating conditions. Finally, according to the good agreement between the two-fluid and experimentation results, the numerical water distribution is examined in each component of the cell, exhibiting very heterogeneous water thickness over the cell surface.     

Recent trends in the development of reactor systems for hydrogen production via methanol steam reforming

Hydrogen is currently receiving significant attention as an alternative energy resource, and among the various methods for producing hydrogen, methanol steam reforming (MSR) has attracted great attention because of its economy and practicality. Because the MSR reaction is inherently activated over catalytic materials, studies have focused on the development of noble metal-based catalysts and the improvement of existing catalysts with respect to performance and stability. However, less attention has been paid to the modification and development of innovative MSR reactors to improve their performance and efficiency. Therefore, in this review paper, we summarize the trends in the development of MSR reactor systems, including microreactors and membrane reactors, as well as the various structured catalyst materials appropriate for application in complex reactors. In addition, other engineering approaches to achieve highly efficient MSR reactors for the production of hydrogen are discussed.     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.     

Influence of CO2 inleakage on the slight-alkalization of generator internal cooling water

The slight-alkalization of generator internal cooling water (GICW) is widely used to inhibit the corrosion of hollow copper conductor and thereby ensure the safe operation of the generator. CO₂ inleakage is increasingly identified as a potential security risk for GICW system. In this paper, the influence of CO₂ inleakage on the slight-alkalization of GICW was theoretically discussed. Based on the equilibriums of the CO₂-NaOH-H₂O system, CO₂ inleakage saturation was derived to quantify the amount of the dissolved CO₂ in GICW. This parameter can be directly calculated with the measured conductivity and the [Na⁺] of GICW. The influence of CO₂ inleakage on the slight-alkalization conditioning of GICW and the measurement of its water quality parameters were then analyzed. The more severe the inleakage, the narrower the water quality operation ranges of GICW, resulting in the more difficult the slight-alkalization conditioning of GICW. The temperature calibrations of the conductivity and the pH value of GICW show non-linear correlations with the amount of CO₂ inleakage and the NaOH dosage. This study provides insights into the influence of CO₂ inleakage on the slight-alkalization of GICW, which can serve as the theoretical basis for the actual slight-alkalization when CO₂ inleakage occurs.     

Impact behavior and fractographic study of carbon nanotubes grafted carbon fiber-reinforced epoxy matrix multi-scale hybrid composites

Carbon nanotubes are the most promising reinforcement for high performance composites. Multiwall carbon nanotubes were directly grown onto the carbon fiber surface by catalytic thermal chemical vapor deposition technique. Multi-scale hybrid composites were fabricated using the carbon nanotubes grown fibers with epoxy matrix. Morphology of the grown carbon nanotubes was investigated using field emission scanning electron microscopy and transmission electron microscopy. The fabricated composites were subjected to impact tests which showed 48.7% and 42.2% higher energy absorption in Charpy and Izod impact tests respectively. Fractographic analysis of the impact tested specimens revealed the presence of carbon nanotubes both at the fiber surface and within the matrix which explained the reason for improved energy absorption capability of these composites. Carbon nanotubes presence at various cracks formed during loading provided a direct evidence of micro crack bridging. Thus the enhanced fracture strength of these composites is attributed to stronger fiber–matrix interfacial bonding and simultaneous matrix strengthening due to the grown carbon nanotubes.     

Al2O3/Yttria‐Stabilized Zirconia Hollow‐Fiber Membrane Incorporated with Iron Oxide for Pb(II) Removal

Removal by absorptive ceramic membranes can simultaneously absorb and separate metal ions from water. Alumina/yttria‐stabilized zirconia (Al₂O₃/YSZ) hollow‐fiber membranes, fabricated using phase inversion and sintering process, were deposited with iron oxide by an in‐situ hydrothermal process. The results showed that α‐Fe₂O₃ was produced and incorporated across the membranes. A reduction in flux was recorded with the deposition of α‐Fe₂O_3. However, it improved the adsorption capacity for heavy metal adsorption. The adsorption‐separation test demonstrated that the optimized membrane is able to completely remove Pb(II) ions after two hours.     

ZnIn2S4/In(OH)3 hollow microspheres fabricated by one-step l-cysteine-mediated hydrothermal growth for enhanced hydrogen production and MB degradation

An intervening barrier for photocatalytic water decomposition and pollutant degradation is the frustratingly quick recombination of e⁻ - h⁺ pairs. Delicate design of heterojunction photocatalysts by coupling the semiconductors at nanoscale with well-matched geometrical and electronic alignments is an effective strategy to ameliorate the charge separation. Here a facile and environment-friendly l-cysteine-assisted hydrothermal process under weakly alkaline conditions is demonstrated for the first time to fabricate ZnIn₂S₄/In(OH)₃ hollow microspheres with intimate contact, which are verified by XRD, SEM, (HR)TEM, XPS, N₂ adsorption-desorption, UV–Vis DRS and photoluminescence spectra. ZnIn₂S₄/In(OH)₃ heterostructure (L-cys/Zn²⁺ = 4, molar ratio) with a band-gap of 2.50 eV, demonstrates the best photocatalytic performance for water reduction and MB degradation under visible light, outperforming its counterparts (In(OH)₃ and ZnIn₂S₄). The excellent activity of ZnIn₂S₄/In(OH)₃ heterostructure arises from the intercrossed band-edge positions as well as the unique hollow structure with large surface area and wide pore-size distribution, which are beneficial for the efficient charge migration from bulk to surface as well as at the interface between ZnIn₂S₄ and In(OH)₃. This work provides an efficient and eco-friendly strategy for one-pot synthesis of heterostructured composites with intimate contact for photocatalytic application.     

Colloidal Synthesis of Hollow Cobalt Sulfide Nanocrystals

Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature‐dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell‐size statistics and transmission electron microscopy images of as‐grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.     

Encapsulation and Ostwald Ripening of Au and Au–Cl Complex Nanostructures in Silica Shells

We report a general template strategy for rational fabrication of a new class of nanostructured materials consisting of multicore shell particles. Our approach is demonstrated by encapsulating Au or Pt nanoparticles in silica shells. Other superstructures of these hollow shells, like dimers, trimers, and tetramers can also be formed by nanoparticle‐mediated self‐assembly. We have also used the as‐prepared multicore Au–silica hollow particles to perform the first studies of Ostwald ripening in confined microspace, in which chloride was found to be an efficient mediating ligand. After treatment with aqua regia, Au–Cl complex is formed inside the shell, and is found to be very active under in situ transmission electron microscopy observations while confined in a microcell. This aspect of the work is expected to motivate further in situ studies of confined crystal growth.