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.     

成分配比对稀土钨电极材料组织及力学性能影响

通过固液掺杂、等静压压制、中频烧结的方法，制备了不同的氧化镧、氧化钇、氧化锆三元掺杂成分比例的钨电极材料烧结棒材，探究了不同成分配比对样品显微组织、第二相粒子分布以及宏观力学性能的影响。结果表明，氧化镧、氧化钇、氧化锆三元复合添加能够有效改善第二相粒子在钨基体中的分布形态，降低第二相在晶界的过度富集，提高钨电极材料的综合力学性能。并且当添加成分镧、钇、锆质量比为3:1:1时，材料具有最好的综合力学性能，致密度可达96.04%，显微硬度可达549.37HV0.3，抗压强度可达3785MPa，原因是此配比下第二相粒子最为细小均匀，弥散程度最高，对基体晶粒的细化作用最好，该配比下钨基体平均晶粒尺寸达到10.3μm。     

Development of high pressure membraneless alkaline electrolyzer

A technology for cyclic generation of hydrogen and oxygen using electrodes made of variable valency material that does not need the use of separating ion-exchange membranes is presented. The technological solution enables to fabricate electrolyzers for uninterrupted producing high-pressure hydrogen with reduced energy intensity of the production. The total work for compressing 1 m³ of hydrogen and 0.5 m³ of oxygen has been estimated. Results of investigation of influence of discrete supply of DC current to the electrolysis cell, in order to improve the processes of gas evolution and to simplify the power systems of the electrolysis plant, have been considered. There is also considered an electrolysis installation equipped with a thermosorption compressor in which LaNi₅ is used as a hydride-forming compound. The comparative characteristics of the developed electrolyzer and the currently used hydrogen generators are given.     

Development of an SFMM/CGO composite electrode with stable electrochemical performance at different oxygen partial pressures

This paper carefully evaluates the electrocatalytic activity of Sr₂FeMo_0.5Mn_0.5O₆ (SFMM) double perovskite as a candidate to substitute the state-of-the-art Ni/YSZ fuel electrode. The electrochemical performance of a 40% SFMM/CGO composite electrode was studied in CO/CO₂ and H₂ with different oxygen partial pressure. Two different cell configurations are prepared at a relatively low temperature of 800 °C to increase the electrochemically active surface area. The cell was supported with a 150 μm 10Sc1CeSZ electrolyte in the first configuration. The cell in the second configuration was made by applying a 400 nm thin 8YSZ layer on 150 μm CGO electrolyte to improve the electrolyte ionic conductivity. Improving catalytic activity with increasing oxygen partial pressure is a key characteristic of the developed electrode. The polarization resistance of about 0.34 and 0.56 Ω cm² at 750 °C in 3%H₂O + H₂ and 60% CO/CO₂ makes this electrode a promising candidate for SOCs application.     

Influence of Al3+ doping for V5+ on the structural,optical, thermal and electrical properties of V2-xAlxO5-δ (x=0–0.20) ceramics

This paper reports an investigation on the structure-properties correlation of trivalent metal oxide (Al₂O₃)-doped V₂O₅ ceramics synthesized by the melt-quench technique. XRD patterns confirmed a single orthorhombic V₂O₅ phase formation with increasing strain on the doping of Al₂O₃ in place of V₂O₅ in the samples estimated by Williamson-Hall analysis. FTIR and Raman investigations revealed a structural change as [VO₅] polyhedra converts into [VO₄] polyhedra on the doping of Al₂O₃ into V₂O₅. The optical band gap was found in a wide semiconductor range as confirmed by UV–visible spectroscopy analysis. The thermal and conductivity behavior of the prepared samples were studied using thermal gravimetric analysis (TGA) and impedance analyzer, respectively. All the prepared ceramics exhibit good DC conductivity (0.22–0.36 Sm^-1) at 400 ?C. These materials can be considered for intermediate temperature solid oxide fuel cell (IT-SOFC)/battery applications due to their good conductivity and good thermal stability.     

{X,Y}-Cyclacene Graphs with Next Nearest Neighbor Interactions

Eigensolutions of {X( = C,B,N),Y( = C,B,N)}-cyclacene graphs with next nearest neighbor (nnn) interactions have been obtained in analytical forms by adapting n-fold rotational symmetry followed by two-fold rotational symmetry (or a plane of symmetry). Expressions of eigensolution indicate the subspectral relationship among such cyclacenes with an even number of hexagonal rings e.g., eigenvalues of {X,Y}-di-cyclacene are found in the eigenspectra of all such even cyclacenes. Total π-electron energies and highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO) gaps are calculated using the analytical expressions obtained and are found to vary negligibly with the variation of nnn interactions in such cyclacenes. Total π-electron energy is found to increase due to increase in restriction intensity of nnn interactions, whereas the HOMO–LUMO gap of polyacenecs having the even number of hexagonal rings and with one electron at each site (atom) decreases with increase in the restriction intensity since such systems contain degenerate half-filled HOMO (bonding or nonbonding) that are much more vulnerable for perturbations imposed through nnn interactions.     

How Cells Communicate with Each Other in the Tumor Microenvironment: Suggestions to Design Novel Therapeutic Strategies in Cancer Disease

Connexin- and pannexin (Panx)-formed hemichannels (HCs) and gap junctions (GJs) operate an interaction with the extracellular matrix and GJ intercellular communication (GJIC), and on account of this they are involved in cancer onset and progression towards invasiveness and metastatization. When we deal with cancer, it is not correct to omit the immune system, as well as neglecting its role in resisting or succumbing to formation and progression of incipient neoplasia until the formation of micrometastasis, nevertheless what really occurs in the tumor microenvironment (TME), which are the main players and which are the tumor or body allies, is still unclear. The goal of this article is to discuss how the pivotal players act, which can enhance or contrast cancer progression during two important process: “Activating Invasion and Metastasis” and the “Avoiding Immune Destruction”, with a particular emphasis on the interplay among GJIC, Panx-HCs, and the purinergic system in the TME without disregarding the inflammasome and cytokines thereof derived. In particular, the complex and contrasting roles of Panx1/P2X7R signalosome in tumor facilitation and/or inhibition is discussed in regard to the early/late phases of the carcinogenesis. Finally, considering this complex interplay in the TME between cancer cells, stromal cells, immune cells, and focusing on their means of communication, we should be capable of revealing harmful messages that help the cancer growth and transform them in body allies, thus designing novel therapeutic strategies to fight cancer in a personalized manner.     

All-printed and highly stable organic resistive switching device based on graphene quantum dots and polyvinylpyrrolidone composite

We propose all printed and highly stable organic resistive switching device (ORSD) based on graphene quantum dots (G-QDs) and polyvinylpyrrolidone (PVP) composite for non-volatile memory applications. It is fabricated by sandwiching G-QDs/PVP composite between top and bottom silver (Ag) electrodes on a flexible substrate polyethylene terephthalate (PET) at ambient conditions through a cost effective and eco-friendly electro-hydrodynamic (EHD) technique. Thickness of the active layer is measured around 97 nm. The proposed ORSD is fabricated in a 3 × 3 crossbar array. It operates switching between high resistance state (HRS) and low resistance state (LRS) with OFF/ON ratio ∼14 for more than 500 endurance cycles, and retention time for more than 30 days. The switching voltage for set/reset of the devices is ±1.8 V and the bendability down to 8 mm diameter for 1000 cycles are tested. The elemental composition and surface morphology are characterized by XPS, FE-SEM, and microscope.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

Simulation studies on a rotating ring disk electrode: Effects of ionic migration with kinetic complication-disk results

In continuation to my previous work (Guha S. AIChE J. 2013;59(4):1390-1399), in this work, effects of ionic migration are evaluated for disk region of a rotating ring disk electrode system by numerically solving complex differential equations, developed for mass transfer along with kinetic complication in presence of ionic migration under limiting current condition. The system for simulation is 0.01 M Fe₂(SO₄)₃ solution with H₂SO₄ as supporting electrolyte. Simulation cases are presence and absence of ionic migration with kinetic complication (oxidation of Fe²⁺ to Fe³⁺ under O₂ pressure). Results show that concentration boundary layer thickness of reactant Fe³⁺ reduces appreciably and steady-state disk current reduces substantially in presence of migration. Simulated steady-state disk current in absence of migration case agrees well with published data. Results indicate higher Fe²⁺ concentration in presence of migration and thereby higher rate of oxidation of Fe²⁺ to Fe³⁺ at all rate constant values.