Performance degradation studies on PBI/H3PO4 high temperature PEMFC and one-dimensional numerical analysis

Five hundred hours continuous aging test at constant discharge current (640 mA cm⁻²) was performed on PBI/H₃PO₄ high temperature PEMFC unit cell, electrochemical techniques-linear sweep voltammetry (LSV) and AC impedance measurement were used to investigate the changes of electrochemical surface area (ESA) and high frequency resistance (internal resistance) with time. Initial experimental results showed that during 500 h continuous aging test the main reason for cell performance degradation is the decrease of ESA caused by sintering. In addition, a one-dimensional mathematical model was constructed, the concentration distributions of cathode reactant gases (O₂ and gaseous H₂O) were calculated and polarization curves recorded during aging test were simulated based on the model, the simulated polarization curves compare well with the experimental results.     

Oxidation of activated carbon by dry and wet methods: Surface chemistry and textural modifications

The effects of dry and wet oxidation treatments of activated carbon (AC) on the surface chemistry and porous structure are studied. Using cherry stones (CS), AC was first prepared by carbonization at 900 °C for 2 h in N₂ and activation at 850 °C for 2 h in CO₂. Then, the resulting AC was oxidized in O₂(air) or O₃ atmosphere and with HNO₃ and H₂O₂ solutions. The acidic-basic surface sites were analyzed by FT-IR spectroscopy, Boehm method, and pH of the point of zero charge (pH_pzc) and the porous structure by N₂ adsorption and mercury porosimetry. It has been found that the oxidizing agent, under specific reaction conditions, rather than whether it was a gas or a solute in aqueous solution, is the main factor that controls the changes produced in the surface chemistry and porous structure of AC. O₃ and HNO₃ are the most effective oxidants to form acidic oxygen surface groups. However, the content of basic groups decreases for the four oxidants, the effect being much stronger for HNO₃. A microporosity reduction is also observed, which is more important for O₂(air) and especially for HNO₃ than for O₃ and H₂O₂. The percentage of microporosity loss is as high as 43.3 for HNO₃. Mesoporosity significantly develops, whereas macroporosity usually remains practically unchanged. Dry oxidation of AC at 100 °C in O₃ has proved to be the most promising method to increase the content of acidic oxygen surface groups in the material without greatly decreasing the content of basic sites and microporosity and with a significant mesoporosity development.     

Electrocatalytic degradation of 4-chlorophenol on F-doped PbO2 anodes

PbO₂ and F-doped PbO₂ (F-PbO₂) anodes have been prepared by a standard thermal decomposition-electrodeposition technique. The electrochemical stability of these anodes has been investigated by the accelerated life tests in sulphuric acid solution. The results show that the service life of the F-PbO₂ anodes is almost three times longer than that of the PbO₂ anodes. Furthermore, in the degradation of 4-chlorophenol (4-CP), the F-PbO₂ anodes give a higher degradation rate than that observed for the PbO₂ anodes. The influence of F⁻ anion doping on the stability and activity of PbO₂ anodes has been discussed. With the F-PbO₂ anodes, the degradation of 4-CP is investigated according to the results of high-performance liquid chromatograph (HPLC), ionic chromatograph (IC) and cyclic voltammetry (CV). In addition, the electron spin resonance (ESR) technique using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as the spin-trap reagent has been applied to detect free radical intermediates generated during in situ the electrocatalytic degradation of aqueous 4-CP on the F-PbO₂ anodes. ESR measurements give the direct evidence that the active species (OH) are responsible for the decomposition of 4-CP over F-PbO₂ under anodic bias potential, strongly suggesting that the electrocatalytic degradation of most organic compounds on F-PbO₂ anodes proceed via surface intermediates of water oxidation, not via direct oxidation at electrode surface. The formation mechanism of surface intermediates is also discussed.     

Electrodeposition of mesoscopic Pt-Ru on reticulated vitreous carbon from reverse emulsions and microemulsions: Application to methanol electro-oxidation

High surface area Pt-Ru (between 120 and 400 cm² mg⁻¹) meso-sized particles and mesoporous coatings were electrodeposited on reticulated vitreous carbon (RVC) three-dimensional electrodes using reverse emulsions and microemulsions. The organic phase of the colloidal media was composed of cyclohexane, Triton X-100 non-ionic surfactant and tetrabutylammonium perchlorate (for ionic conductivity) while the aqueous phase contained H₂PtCl₆ and RuCl₃ (or (NH₄)₂RuCl₆). For microemulsification to occur isopropanol was also added as co-surfactant. The catalytic activity for the electro-oxidation of methanol was assessed by cyclic voltammetry and chronopotentiometry in conjunction with surface area measurement by Cu underpotential deposition. The composition and morphology of the Pt-Ru deposit was analyzed by inductively coupled plasma atomic emission spectroscopy and scanning electron microscopy, respectively. The effects on the catalytic activity of the deposition current density, temperature, RVC pretreatment and plating bath composition are presented. It was found that the electrodeposition of Pt-Ru in reverse microemulsion yielded the highest specific surface area (400 cm² mg⁻¹) and catalytic activity toward CH₃OH electro-oxidation as shown, for example, by a 50-200 mV more negative anode potential determined by chronopotentiometry compared to a catalyst obtained by pure aqueous and emulsion electroplating.     

Properties of nano-crystalline LiMn2O4 thin films deposited by pulsed laser deposition

Properties of LiMn₂O₄ thin films deposited on polished stainless steel substrates at 400 °C and 200 mTorr of oxygen by pulsed laser deposition have been characterized by electrochemical measurements and physical analyses. The film was mainly composed of nano-crystals less than 100 nm. A maximum specific capacity of 141.9 mAh/g cycled between 3.0 and 4.5 V with a current density of 20 μAh/cm² has been achieved. The film exhibited an excellent cycling stability up to 500 cycles. The low charge-transfer resistance at high potentials as revealed by AC impedance resulted in high charge/discharge potential and more capacity. The effect of overdischarge was limited and Jahn-Teller effect was overcome to a significant extent in this nano-crystalline film. Ex situ XRD, Raman and XPS provided supporting evidence in the changes in structure, reactivity and cycling stability of nano-crystalline LiMn₂O₄ film cathodes under different charge/discharge states and cycling tests. SEM images also revealed the stability of the surface topography after a long-term cycling test.     

Characterisation of thermal barrier coatings and ultra high temperature composites deposited in a low pressure plasma reactor

A low pressure plasma process working at 600-800 Pa was used to deposit from aqueous solution ZrO₂-4 mol% Y₂O₃ (Yttria partially stabilized Zirconia-YpSZ) layers and stacks of Ta₂O₅/YpSZ layers for use as thermal barrier coatings (TBC). The observation of the cross section revealed a high porosity. The thermal diffusivity of the layers (1 × 10⁻⁷ m² s⁻¹) was measured by a laser flash technique and compared with values obtained on air plasma sprayed material (3 × 10⁻⁷ m² s⁻¹). The plasma reactor were also used to deposit ZrB₂-ZrO₂-SiC layers used as Ultra High Temperature Composite (UHTC) from aqueous solutions of zirconyl and Boron nitrates containing suspensions of SiC. Layers up to 100 μm thick were obtained on SiC substrates. XRD was used to study the crystallinity of the layer. The presence of ZrB₂ and SiC phases was confirmed after the deposition. XRD analysis showed that heat treatment at 1073 K under oxidizing conditions led to the loss of ZrB₂ and the appearance of ZrO₂ phases. To understand the behaviour of the layers to interaction with atomic oxygen (combustion for TBC and spacecraft re-entry phase for UHTC), we have measured the atomic oxygen recombination coefficient to determine the number of adsorption sites on the surface of the coatings. This was accomplished by using a low pressure plasma reactor coupled with optical spectroscopic measurements as a diagnostic technique.     

Controllable synthesis of CaTi2O4(OH)2 nanoflakes by a facile template-free process and its properties

Serrated leaf-like CaTi₂O₄(OH)₂ nanoflake crystals were synthesized via a template-free and surfactant-free hydrothermal process. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The growth process for CaTi₂O₄(OH)₂ nanoflakes was dominated by a crystallization–dissolution–recrystallization growth mechanism. BET analysis showed that CaTi₂O₄(OH)₂ nanoflakes had mesoporous structure with an average pore size of 8.7 nm, and a large surface area of 88.4 m² g⁻¹. Cyclic voltammetry and galvanostatic charge–discharge tests revealed that the electrode synthesized from CaTi₂O₄(OH)₂ nanoflakes reached specific capacitances of 162 F g⁻¹ at the discharge current of 2 mA cm⁻², and also exhibited excellent electrochemical stability.     

Synthesis and electrochemical performance of Li2FeSiO4/carbon/carbon nano-tubes for lithium ion battery

Li₂FeSiO₄/carbon/carbon nano-tubes (Li₂FeSiO₄/C/CNTs) and Li₂FeSiO₄/carbon (Li₂FeSiO₄/C) composites were synthesized by a traditional solid-state reaction method and characterized comparatively by X-ray diffraction, scanning electron microscopy, BET surface area measurement, galvanostatic charge-discharge and AC impedance spectroscopy, respectively. The results revealed that the Li₂FeSiO₄/C/CNT composite exhibited much better rate performance in comparison with the Li₂FeSiO₄/C composite. At 0.2 C, 5 C and 10 C, the former composite electrode delivered a discharge capacity of 142 mAh g⁻¹, 95 mAh g⁻¹, 80 mAh g⁻¹, respectively, and after 100 cycles at 1 C, the discharge capacity remained 95.1% of its initial value.     

Electrodeposited PbO2 thin film as positive electrode in PbO2/AC hybrid capacitor

Lead dioxide (PbO₂) thin films were prepared on Ti/SnO₂ substrates by means of electrodeposition method. Galvanostatic technique was applied in PbO₂ film formation process, and the effect of deposition current on morphology and crystalline form of the PbO₂ thin films was studied by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The energy storage capacity of the prepared PbO₂ electrode was investigated by means of cyclic voltammetry (CV) and charge/discharge cycles, and a rough surface structure PbO₂ film was selected as positive electrode in the construction of PbO₂/AC hybrid capacitor in a 1.28 g cm⁻³ H₂SO₄ solution. The electrochemical performance was determined by charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results showed that the PbO₂/AC hybrid capacitor exhibited high capacitance, good cycling stability and long cycle life. In the voltage range of 1.8-0.8 V during discharge process, considering the weight of all components of the hybrid capacitor, including the two electrodes, current collectors, H₂SO₄ electrolyte and separator, the specific energy and power of the device were 11.7 Wh kg⁻¹ and 22 W kg⁻¹ at 0.75 mA cm⁻², and 7.8 Wh kg⁻¹ and 258 W kg⁻¹ at 10 mA cm⁻² discharge currents, respectively. The capacity retains 83% of its initial value after 3000 deep cycles at the 4 C rate of charge/discharge.     

UVA-LED assisted persulfate/nZVI and hydrogen peroxide/nZVI for degrading 4-chlorophenol in aqueous solutions

Photocatalytic degradation of 4-chlrophenol (4-CP) using UVA-LED assisted persulfate and hydrogen peroxide activated by the nZVI (Nano Zero Valent Iron) in a batch photocatalytic reactor was investigated. The reaction involved a lab-scale photoreactor irradiated with UVA-LED light emitted at 390 nm. The efficiency of the reaction was evaluted in terms of 4-CP degradation and mineralization degree at different pH of solution, initial concentrations of nZVI, persulfate, hydrogen peroxide and 4-CP. In UVA-LED/H₂O₂/nZVI process, complete degradation of 4-CP (>99%) and 75% mineralization was achieved at pH of 3, hydrogen peroxide concentration of 0.75 mM, nZVI dosage of 1mM and initial 4-CP concentration of 25mg/L at the reaction time of 30 min. The optimum conditions obtained for the best 4-CP degradation rate were at an initial concentration of 25mg/l, persulfate concentration of 1.5mM, nZVI dosage of 1mM, pH of 3 and reaction time of 120min for UVA-LED/persulfate/nZVI process. It was also observed that the 4-CP degradation rate is dependent on initial 4-CP concentrations for both processes. The pseudo-first-order kinetic constant at 25mg/L initial concentration of 4-CP was found to be 1.4×10^?1 and 3.8×10^?2 in UVA-LED/H₂O₂/nZVI and UVA-LED/persulfate/nZVI processes, respectively. Briefly, the UVA-LED/H₂O₂/nZVI process enhanced the degradation rate of 4-CP by 3.67-times in comparison to UVA-LED/persulfate/nZVI process at 30min contact time, which serves as a new and feasible approach for the degradation of 4-CP as well as other organic contaminants containing wastewater.     

Sol–gel deposition of multiply doped thermographic phosphor coatings Al2O3:(Cr,M) (M = Dy,Tm) for wide range surface temperature measurement application

A promising method of measuring surface temperatures in harsh environments is the use of thermographic phosphor coatings. There, the surface temperature is evaluated from the phosphorescence decay lifetime following a pulsed laser or flash lamp light excitation. Depending on the used dopant, single doped M³⁺:α-Al₂O₃ (M = Cr, Dy, Tm) emit at 694 nm (Cr³⁺), 488 nm (Dy³⁺), 584 nm (Dy³⁺), and 459 nm (Tm³⁺), respectively. However, the accessible temperature range with a single dopant is limited: for the Cr³⁺-transition from 293 K up to 900 K, and for the Dy³⁺ and Tm³⁺-transitions both from 1073 K up to 1473 K. In the present study a new approach is followed to extend these limitations by co-doping two dopants using the sol–gel method and dip coating of α-Al₂O₃ thin films. For that application (Dy³⁺ + Cr³⁺) co-doped thin α-Al₂O₃ films and (Tm³⁺ + Cr³⁺) co-doped α-Al₂O₃ films with thicknesses of 4–6 μm were prepared, and the temperature-dependent luminescence properties (emission spectra and lifetimes) were analysed after pulsed laser excitation in the UV (355 nm). The phosphorescence lifetime as a function of temperature were measured between 293 K and 1473 K. A considerably extended range for surface temperature evaluation was established following this new approach by combining different dopants on the molecular level.     

TiO2 nanotube arrays annealed in CO exhibiting high performance for lithium ion intercalation

Anatase titania nanotube arrays were fabricated by means of anodization of Ti foil and annealed at 400 °C in respective CO and N₂ gases for 3 h. Electrochemical impendence spectroscopy study showed that CO annealed arrays possessed a noticeably lower charge-transfer resistance as compared with arrays annealed in N₂ gas under otherwise the same conditions. TiO₂ nanotube arrays annealed in CO possessed much improved lithium ion intercalation capacity and rate capability than N₂ annealed samples. At a high charge/discharge current density of 320 mA g⁻¹, the initial discharge capacity in CO annealed arrays was found to be as high as 223 mAh g⁻¹, 30% higher than N₂ annealed arrays, ∼164 mAh g⁻¹. After 50 charge/discharge cycles, the discharge capacity in CO annealed arrays remained at ∼179 mAh g⁻¹. The improved intercalation capacity and rate capability could be attributed to the presence of surface defects like Ti-C species and Ti³⁺ groups with oxygen vacancies, which not only improved the charge-transfer conductivity of the arrays but also possibly promoted phase transition.     

Direct synthesis of H2O2 acid solutions on carbon cathode prepared from activated carbon and vapor-growing-carbon-fiber by a H2/O2 fuel cell

Direct synthesis of H₂O₂ acid solutions was studied using a gas-diffusion cathode prepared from activated carbon (AC), vapor-growing-carbon-fiber (VGCF) and poly-tetra-fluoro-ethylene (PTFE) powders, with a new H₂/O₂ fuel cell reactor. O₂ reduction to H₂O₂ was remarkably enhanced at the three-phase boundary (O₂(g)-electrode(s)-acid(l)) at the [AC + VGCF] cathode. Fast diffusion processes of O₂ to the active surface and of H₂O₂ to the bulk acid solutions were essential for H₂O₂ accumulation. Synergy of AC and VGCF was observed for the H₂O₂ formation. RRDE and cyclic voltammetry studies indicated that the surface of AC functioned as the active phase for O₂ reduction to HO₂, and VGCF functioned as an electron conductor and a promoter to convert HO₂ to H₂O₂. A maximum H₂O₂ concentration of 353 mM (1.2 wt%) was accomplished under short-circuit conditions (current density 12.7 mA cm⁻², current efficiency 40.1%, geometric area of cathode 1.3 cm², reaction time 6 h).     

Synthesis, microstructure, and photocatalysis of In2O3 hollow particles

Indium oxide (In₂O₃) microspheres with hollow interiors have been prepared by a facile implantation route which enables indium ions released from indium-chloride precursors to implant into nonporous polymeric templates in C₂Cl₄ solvent. The templates are then removed upon calcination at 500 °C in air atmosphere, forming hollow In₂O₃ particles. Specific surface area (0.5-260 m² g⁻¹) and differential pore volume (7 × 10⁻⁹ to 3.8 × 10⁻⁴ m³ g⁻¹ Å⁻¹) of the hollow particles can be tailored by adjusting the precursor concentration. For the hollow In₂O₃ particles with high surface area (260 m² g⁻¹), an enhanced photocatalytic efficiency (up to ∼one-fold increase) against methylene blue (MB) dye is obtained under UV exposure for the aqueous In₂O₃ colloids with a dilute solids concentration of 0.02 wt.%.     

Improvement of the structural and chemical properties of a commercial activated carbon for its application in electrochemical capacitors

The present paper shows that the performance of an inexpensive activated carbon used in electrochemical capacitors can be significantly enhanced by a simple treatment with KOH at 850 °C. The changes in the specific surface area, as well as in the surface chemistry, lead to high capacitance values, which provide a noticeable energy density.The KOH-treatment of a commercial activated carbon leads to highly pure carbons with effective surface areas in the range of 1300-1500 m² g⁻¹ and gravimetric capacitances as high as three times that of the raw carbon.For re-activated carbons, one obtains at low current density (50 mA g⁻¹) values of 200 F g⁻¹ in aqueous electrolytes (1M H₂SO₄ and 6M KOH) and around 150 F g⁻¹ in 1M (C₂H₅)₄NBF₄ in acetonitrile. Furthermore, the resulting carbons present an enhanced and stable performance for high charge/discharge load in organic and aqueous media.This work confirms the possibilities offered by immersion calorimetry on its own for the prediction of the specific capacitance of carbons in (C₂H₅)₄NBF₄/acetonitrile. On the other hand, it also shows the limitations of this technique to assess, with a good accuracy, the suitability of a carbon to be used as capacitor electrodes operating in aqueous electrolytes (H₂SO₄ and KOH).     

Methanol dehydration to dimethyl ether over highly porous xerogel alumina catalyst: Flow rate effect

Template-free sol-gel synthesis in the absence of an acid catalyst resulted in mesoporous nanocrystalline γ-alumina, meso-γ-Al₂O₃, possessing high surface areas, 400-460 m²/g, and high porosity, 1.4-1.9 cm³/g. The prepared alumina was characterized by powder XRD, SEM, and N₂ adsorption for BET surface area and porosity measurements. FTIR spectroscopy was employed to study the catalytic activity of meso-γ-Al₂O₃ and commercial γ-alumina, com-γ-Al₂O₃, in the dehydration reaction of methanol to dimethyl ether, DME. The prepared meso-γ-Al₂O₃ showed higher catalytic activity than the commercial catalyst with a conversion around 86% and DME selectivity around 99%. The products' selectivity showed a significant dependence on the flow rate of the feed gas stream. As the flow rate increased, the selectivity to DME increased on the account of the minor products, CO₂ and CH₄. However, as the flow rate decreased, more CO₂ formed and the DME selectivity decreased.     

Rapid microwave-assisted synthesis of graphene nanosheet/Co3O4 composite for supercapacitors

Graphene nanosheet (GNS)/Co₃O₄ composite has been rapidly synthesized by microwave-assisted method. Field emission scanning electron microscopy and transmission electron microscopy observation reveals the homogeneous distribution of Co₃O₄ nanoparticles (3-5 nm in size) on graphene sheets. Electrochemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. A maximum specific capacitance of 243.2 F g⁻¹ has been obtained at a scan rate of 10 mV s⁻¹ in 6 M KOH aqueous solution for GNS/Co₃O₄ composite. Furthermore, the composite exhibits excellent long cycle life along with ∼95.6% specific capacitance retained after 2000 cycle tests.     

Reduction behaviors and catalytic properties for methanol steam reforming of Cu-based spinel compounds CuX2O4 (X=Fe,Mn, Al,La)

In this study, various Cu-based spinel compounds, i.e., CuFe₂O₄, CuMn₂O₄, CuAl₂O₄ and CuLa₂O₄, were fabricated by a solid-state reaction method. Reduction behaviors and morphological changes of these materials have been characterized by H₂ temperature-programmed reduction (H₂-TPR), X-ray diffraction (XRD), Scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Moreover, the catalytic properties for steam reforming of methanol (SRM) of these Cu-based spinel compounds were investigated. H₂-TPR results indicated that the reducibility of Cu-based spinel compounds was strongly dependent on the B-site component while the CuFe₂O₄ catalyst revealed the lowest reduction temperature (190 °C), followed respectively by CuAl₂O₄ (267 °C), CuMn₂O₄ (270 °C), and CuLa₂O₄ (326 °C). The reduced CuAl₂O₄ catalyst demonstrated the best performance in terms of catalytic activity. Based on the SEM and XRD results, pulverization of the CuAl₂O₄ particles due to gas evolution and a high concentration of nanosized Cu particles (≈50.9 nm) precipitated on the surfaces of the Al₂O₃ support were observed after reduction at 360 °C in H₂. The BET surface area of the CuAl₂O₄ catalyst escalated from 5.5 to 13.2 m²/g. Reduction of Cu-based spinel ferrites appear to be a potential synthesis route for preparing a catalyst with high catalytic activity and thermal stability. The catalytic performance of these copper-oxide composites was superior to those of conventional copper catalysts.     

Alkali carbonate-coated graphite electrode for lithium-ion batteries

Charge and discharge behavior of a graphite electrode for rechargeable lithium-ion batteries was successfully improved by pretreatment of graphite powders with A₂CO₃ (A = Li, Na, and K) aqueous solutions. In the process of the pretreatment, graphite powders were simply dispersed in the aqueous solutions, and then filtered and dried to modify the surface of graphite powder with solid alkali carbonate. With the optimum concentration of each carbonate, 1 wt.% Li₂CO₃, 5 wt.% Na₂CO₃, and 1 wt.% K₂CO₃, the irreversible reaction at the initial cycle was suppressed by the pretreatment which was capable of modifying the solid electrolyte interphase formed on the graphite electrode surface. Furthermore, the rate capability was improved by the surface modification, that is, the reversible discharge capacities at 175 mA g⁻¹ increased with adequate capacity retention in a 1 mol dm⁻³ LiClO₄ ethylene carbonate:diethyl carbonate electrolyte solution because of the kinetics enhancement of lithium-ion transfer at the interface.     

Adsorption of 4-chlorophenol by inexpensive sewage sludge-based adsorbents

Sewage sludge was used as precursor to develop a potential inexpensive adsorbent by both simple drying and pyrolysis. The resulting materials were evaluated as adsorbents for the removal of 4-chlorophenol (4-CP) from aqueous solution. The dried biosolids showed a BET surface area lower than 3 m²/g, which yield a maximum adsorption capacity of 0.73 mmol 4-CP/g at pH 5.0 and 15 °C. The carbonization of biosolids under relatively mild conditions allowed obtaining materials with BET surface area up to 45 m²/g, which led to a significant increase of the maximum adsorption capacity (1.36 mmol 4-CP/g). The high ash content of the starting material (23%, d.b.) limits the development of porosity on a total dry-weight basis. Adsorption data were well fitted to the Redlich–Peterson isotherm equation whereas the most commonly used Langmuir and Freundlich equations were less satisfactory probably because of the occurrence of summative adsorption phenomenon. A thermodynamic study of the adsorption showed the spontaneous and exothermic nature of the process. Thus, simple drying and carbonization provide two ways of valorization of sewage sludge through its conversion into inexpensive low-rank adsorbents potentially useful for the removal of some hazardous water pollutants, like chlorophenols and related compounds.