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Supercritical fluid has been adopted as an extraction media to remove various kinds of substances from distinct types of solid matrices since three decades ago. Compared to conventional extraction mode, supercritical fluid extraction technology is preferred because of the flexibility in adjusting its dissolving power and inherent elimination of organic solvent which means reducing time and money needed for subsequent purification. Utilization of this method as an environmental remedial technology, however, has become a trend only after its accomplishment in analytical chemistry was acknowledged. This review tries to summarize in a comprehensive manner the multitude aspects involved in hazardous compounds removal from miscellaneous class of environmental matrices. The industrial adsorbent regeneration using supercritical fluid technology is also discussed. Although, this technology has been successfully realized for environmental remediation in laboratory and on pilot-plant scale, its commercialization attempts still lack significant technology improvement in order to reach the economic feasibility.

A significant number of biosorption studies on the removal of heavy metal from aqueous solutions have been conducted worldwide. Nearly all of them have been directed towards optimizing biosorption parameters to obtain the highest removal efficiency while the rest of them are concerned with the biosorption mechanism. Combinations of FTIR, SEM-EDX, TEM as well as classical methods such as titrations are extremely useful in determining the main processes on the surfaces of biosorbents. Diverse functional groups represented by carboxyl, hydroxyl, sulfate and amino groups play significant roles in the biosorption process. Solution pH normally has a large impact on biosorption performance. In brief, ion exchange and complexation can be pointed out as the most prevalent mechanisms for the biosorption of most heavy metals.

Titanium zirconium phosphate and organic polymer hybrid (poly-vinyl alcohol, (3-glycidoxypropyl)-trimethoxysilane and ethylene glycol) based membranes were investigated for their potential application as proton conductors. The hybrid materials were characterized by XRD, FTIR, SEM, TGA and impedance spectroscopy analysis. It was found that embedding of functionalised inorganic particles (TiZrP) into composite polymer matrix allowed for some crystallinity formation, and cross-linking of hydroxyl groups during annealing or reactions within the organic and inorganic phases during synthesis. A complex structure was formed, as many FTIR peaks were masked by more defined peaks assigned to P-O-R bonds. The high concentration of phosphorus in the TiZrP (1:1:9 molar ratio) samples resulted in more hydrophilic particles. This was further reflected in the hybrid membranes as the water losses increased from 13 to 25 wt.% as a function of the TiZrP content changing from 10 to 50 wt.% in the final hybrid membrane, respectively. As a result, proton conductivity increased by two to three orders of magnitude from blank (organic phase only) membranes (2.61 x 10(-5) S cm(-1)) to TiZrP hybrid membrane (2.41 x 10(-2) S cm(-1)) at 20 degrees C. Proton conduction changed as a function of temperature and the Ti1Zr1P9 particles content, mainly attributed to the membrane ability to retain water, thus complying with the Grotthus mechanism.

Increasing energy demands have stimulated intense research activity on cleaner energy conversion such as regenerative fuel cells and reversible metal-air batteries. It is highly challenging but desirable to develop low-cost bifunctional catalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), the lack of which is currently one of the major limiting components towards commercialization of these technologies. Here, we have conducted a systematic study on the OER and ORR performances of the Ruddlesden-Popper family of La(n+1)Ni(n) O(3n+1) (n=1, 2, 3, and ∞) in an alkaline medium for the first time. It is apparent that the Ni-O bond lengths and the hyperstoichiometric oxides in the rock-salt layers correlate with the ORR activities, whereas the OER activities appear to be influenced by the OH(-) content on the surface of the compounds. In our case, the electronic configuration fails to predict the electrocatalytic activity of these compounds. This work provides guidelines to develop new electrocatalysts with improved performances.

Bacterial cellulose (BC) is often used as a carbon source for in situ carbonization into carbon nanofibers (CNFs). The main challenge for such CNFs lies in the low yield and very low apparent density of the product, which hamper their applications as electrode materials in batteries and fuel cells. Herein, BC pellicles (8 wt%) are simultaneously employed as a substrate and a sacrificial microreactor, thus allowing the carbonization in its unique porous network. Ethylenediaminetetraacetic acid serves as a carbon source and a nitrogen source, while cobalt plays the role of a recyclable pore-creating template to create a 3D nitrogen-doped graphite carbon with hierarchically porous structure (HPGC). The resultant HPGC exhibits a large specific surface area, high porosity, and large amount of structural defects, which translate into very high oxygen reduction reaction (ORR) activity and stability. The synthesis route, the catalyst structure, and the proposed mechanism open novel avenue and insights to develop next-generation metal-free ORR catalysts.

Technological and scientific challenges coupled with environmental considerations have attracted a search for robust, green and energy-efficient synthesis and processing routes for advanced functional nanomaterials. In this article, we demonstrate a high-energy ball milling technique for large-scale synthesis of nitrogen doped carbon nanoparticles, which can be used as an electro-catalyst for oxygen reduction reactions after a structural refinement with controlled thermal annealing. The resulting carbon nanoparticles exhibited competitive catalytic activity (5.2 mA cm(-2) kinetic-limiting current density compared with 7.6 mA cm(-2) on Pt/C reference) and excellent methanol tolerance compared to a commercial Pt/C catalyst. The proposed synthesis route by ball milling and annealing is an effective process for carbon nanoparticle production and efficient nitrogen doping, providing a large-scale production method for the development of highly efficient and practical electrocatalysts.

This work reports the voltammetric behaviour of decamethylcobaltocenium, DmCc(+), in different ionic liquids for the first time. Its redox potential was studied relative to that of decamethylferrocene, DmFc, and it is shown that the difference in the mid-point potential between these two permethylated transition-metal sandwich complexes is independent of the ionic liquid composition. A variable difference in mid-point potential, in contrast, was observed for ferrocene and cobaltocenium relative to that of DmFc in similar ionic liquids. In addition, different limitations in the application of DmFc(0/+) and DmCc(+/0) couples as internal reference redox systems in ILs are discussed. From these, the observed spontaneous reaction between DmFc and oxygen leads to important implications toward the establishment of particular conditions for DmFc applications.

The vital role of ethylenediaminetetraacetic acid on the structure and the oxygen reduction reaction activity of the non‐precious‐metal‐based pyrolyzed catalyst is reported and elaborated. The resultant catalyst can overtake the performance of commercial Pt/C catalyst in an alkaline medium.

Oxygen production by air separation is of great importance in both environmental and industrial processes as most large scale clean energy technologies require oxygen as feed gas. Currently the conventional cryogenic air separation unit is a major economic impediment to the deployment of these clean energy technologies with carbon capture (i.e. oxy-fuel combustion). Dense ceramic perovskite membranes are envisaged to replace the cryogenics and reduce O2 production costs by 35% or more; which can significantly cut the energy penalty by 50% when integrated in oxy-fuel power plant for CO2 capture. This paper reviews the current progress in the development of dense ceramic membranes for oxygen production. The principles, advantages or disadvantages, and the crucial problems of all kinds of membranes are discussed. Materials development, optimisation guidelines and suggestions for future research direction are also included. Some areas already previously reviewed are treated with less attention.

Bi-functional oxygen electrodes are an enabling component for rechargeable metal-air batteries and regenerative fuel cells, both of which are regarded as the next-generation energy devices with zero emission. Nonetheless, at the present, no single metal oxide component can catalyze both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high performance which leads to large overpotential between ORR and OER. This work strives to address this limitation by studying the bi-functional electrocatalytic activity of the composite of a good ORR catalyst compound (e.g. palladium oxide, PdO) and a good OER catalyst compound (e.g. ruthenium oxide, RuO2) in alkaline solution (0.1M KOH) utilizing a thin-film rotating disk electrode technique. The studied compositions include PdO, RuO2, PdO/RuO2 (25wt.%/75wt.%), PdO/RuO2 (50wt.%/50wt.%) and PdO/RuO2 (75wt.%/25wt.%). The lowest overpotential (e.g. E (2 mA cm−2) - E (-2 mA cm−2)) of 0.82 V is obtained for PdO/RuO2 (25wt.%/75wt.%) (versus Ag|AgCl (3M NaCl) reference electrode).

International audience; Abstract View references (35)La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) hollow fibres were prepared by a phase inversion/sintering method using polyetherimide as a binder. In order to overcome surface exchange kinetics limitation, LSCF hollow fibres were coated with ∼200nm palladium (Pd) nanoparticles. The O2 flux of best performing membranes increased by up to 350% in comparison to unmodified LSCF hollow fibres. Optimal enhancement was achieved with a single Pd coating. Additional coatings resulted in reduced O2 fluxes, thus counter acting the beneficial spill-over effect of the catalyst. Long term stability testing in atmospheric air at 850°C showed that a LSCF membrane modified with a single Pd coating continually outperformed a pure LSCF hollow fibre for over 400h, though the level of enhancement was reduced over time. A dramatic reduction in performance of more than 45% occurred within the first 24h of testing, which was attributed to the coalescence and aggregation of Pd catalyst particles to ∼1000nm size at the LSCF grain boundaries. This greatly reduced the available area for the oxygen species to spill-over onto the LSCF surface and thus reduced the overall O2 flux. © 2011 Elsevier B.V.

in situ high-temperature X-ray diffraction and thermal gravimetric−differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba2Bi0.1Sc0.2Co1.7O6−x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-depende...

Double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x (BBSC) demonstrates low polarization resistance between 600 and 750 °C due to the high oxygen reduction rate of BBSC as reflected by its large DV and k values, which are derived from the face centered cubic structure and high cobalt content.

Polysulfone (PSF) membranes are broadly applied in many fields owing to good physicochemical stability, resistance to oxidation and chlorine. But when treated with wastewater containing oil, PSF membranes are easy to be contaminated for its hydrophobicity, which can result in the declining of flux and lifespan of the membrane and limit their application in large scale. To enhance the capability of PSF membrane in the above circumstances, phosphorylated Zr-doped hybrid silica particles (SZP particles) were firstly prepared. SZP particles have various point defects inside their structure and lots of hydroxide radicals on their surface. SZP particles were added to the porous matrix of PSF to prepare a novel composite membrane (SZP/PSF) through a phase inversion process. Finally, the optimum preparation conditions of SZP/PSF composite membranes were determined. The optimum conditions are: the mass ratio of PSF, PEG400 and SZP is 12:10:10; ultrasound 10 min inside each 30 min; the pre-evaporating time is 10 s. Optimized SZP/PSF composite membrane was characterized by scanning electron microscope (SEM) and ultrafiltration experiment. The results indicate that SZP particles can be uniformly dispersed in SZP/PSF composite membranes with excellent hydrophilic property, antifouling capability and tensile strength. Therefore, it can be concluded that the optimized SZP/PSF composite membrane is desirable in the treatment of wastewater containing oil and wastewater.

Distinctive adsorption equilibria and kinetic models are of extensive use in explaining the biosorption of heavy metals, denoting the need to highlight and summarize their essential issues, which is the main purpose of this paper. As a general trend, up until now, most studies on the biosorption of heavy metal ions by miscellaneous biosorbent types have been directed toward the uptake of single metal in preference to multicomponent systems. In particular, Langmuir and Freundlich models are the most common isotherms for correlating biosorption experimental data though other isotherms, which were initially established for gas phase applications, can also be extended onto biosorption system. In kinetic modeling, the pseudo-first and -second order equations are considered as the most celebrated models.

Layered oxides of Sr4Fe4Co2O13 (SFC2) which contains alternating perovskite oxide octahedral and polyhedral oxide double layers are attractive for their mixed ionic and electronic conducting and oxygen reduction reaction properties. In this work, we used the EDTA–citrate synthesis technique to prepare SFC2 and vary the calcination temperature between 900 and 1100 °C to obtain SFC2, containing different phase content of perovskite (denoted as SFC-P) and (Fe,Co) layered oxide phases (SFC-L). Rietveld refinements show that the SFC-P phase content increased from ∼39 wt% to ∼50 wt% and ∼61 wt% as the calcination temperature increased from 900 °C (SFC2-900) to 1000 °C (SFC2-1000) and 1050 °C (SFC2-1050). At 1100 °C (SFC2-1100), SFC-P became the dominant phase. The oxygen transport properties (e.g. oxygen chemical diffusion coefficient and oxygen permeability), electrical conductivity and oxygen reduction reaction activity is enhanced in the order of SFC2-1000, SFC2-1100 and SFC2-1050. The trend established here therefore negates the hypothesis that the perovskite phase content correlates with the oxygen transport property enhancement. The results suggest instead that there is an optimum composition value (e.g. 61 wt% of SFC-L for SFC2-1050 in this work) on which synergistic effects take place between the SFC-P and SFC-L phase.

Ceramic–metal composites (cermets) of yttria-stabilized zirconia, YSZ and Ni particles are largely utilized as the anode material in solid oxide fuel cells (SOFCs). In this work, three methods were applied to prepare Ni-YSZ cermets: NiO-coated YSZ, YSZ-coated NiO and mechanically mixed NiO-YSZ powders which were finally reduced by H2. The structure and sintering properties of the cermets were characterized using thermal gravimetric-differential scanning calorimetry (TG-DSC), X-ray diffraction (XRD), transferring electron microscopy (TEM), energy dispersive spectroscopy (EDS) and 4-probe direct-current (4-DC) conductivity measurements, respectively. The crystalline of the cermets was identified to be the composite of cubic fluorite YSZ and cubic NiO structure. The NiO-coated YSZ cermet had the highest density and the lowest porosity. It also exhibited the highest electrical conductivity (e.g. 14,000 S/cm) at room temperature but the lowest ionic conductivity. LSSM-YSZ|YSZ|Ni-YSZ solid oxide fuel cells were prepared by a co-pressing method. The fuel cell made from the NiO-coated YSZ cermet exhibited the highest output performance with a maximum peak power density of 433 mW cm at 750°C and in H2/air atmosphere. This demonstrated the remarkable potential of NiO-coated YSZ cermets as the anode material for H2-fueled SOFCs.

Here we report the production of novel high performance BaBi0.05Sc0.1Co0.85O3−δ (BaBiScCo) hollow fibres delivering oxygen fluxes of 11.4 ml cm−2 min−1 at 950 °C. The doping of bismuth, a highly ionic conductor, at the B-site of a barium based perovskite overcame oxygen ionic transport limitations even at temperatures as low as 600 °C.

Oxygen production by air separation is of great importance in both environmental and industrial processes as most large scale clean energy technologies require oxygen as feed gas. Currently the conventional cryogenic air separation unit is a major economic impediment to the deployment of these clean energy technologies with carbon capture (i.e. oxy-fuel combustion). Dense ceramic perovskite membranes are envisaged to replace the cryogenics and reduce O2 production costs by 35% or more; which can significantly cut the energy penalty by 50% when integrated in oxy-fuel power plant for CO2 capture. This paper reviews the current progress in the development of dense ceramic membranes for oxygen production. The principles, advantages or disadvantages, and the crucial problems of all kinds of membranes are discussed. Materials development, optimisation guidelines and suggestions for future research direction are also included. Some areas already previously reviewed are treated with less attention.

In this work the oxygen reduction reaction on Bi0.5Sr0.5FeO3-delta (BSF) and La0.5Sr0.5FeO3-delta (LSF) as cathodes for intermediate temperature solid oxide fuel cells (600-750 degrees C) is compared in detail. Partial substitution of Sr in SrFeO3-delta with 50 mole % of Bi or La results in the distinct structural features which strongly impact its electrochemical characteristics due to the presence of a lone electron pair in Bi3+, which is not available in La3+. Cubic structure for BSF favours higher ionic conductivity and enhanced formation of oxygen vacancies relative to rhombohedral structure for LSF. Large oxygen nonstoichiometry for BSF, nevertheless, leads to the dominance of Fe3+ and subsequent low electronic conductivity relative to LSF. It was found that upon cathodic polarization, the oxygen vacancies are created on LSF which helps reducing its interfacial resistance afterward, which is not the case for BSF. Overall, BSF demonstrates good electrochemical performance which can be further optimized by enhancing its electronic conductivity. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3521316] All rights reserved.

In this work, we investigate and contrast the perovskite structure of La1-xSrxCoO3-delta and La1-xSrxCo0.9Nb0.1O3-delta (both for x = 0.5, 0.7, 0.9, and 1.0) as well as their oxygen nonstoichiometry, oxygen bulk-diffusion, and surface exchange coefficients to describe their distinct performance as ceramic oxygen ionic transport membranes. Le Bail refinements of x-ray diffraction data demonstrate that except for SrCoO3-delta, the structure for all title compounds at room temperature can be fitted adequately using rhombohedrally distorted perovskite structure. The presence of lanthanum is found to reduce the solubility of niobium in perovskite lattice. Aside from SrCo0.9Nb0.1O3-delta, structure deterioration or transformation occurs for all title compounds upon subjected to modest reducing atmosphere of nitrogen. Oxygen permeation testing reveals that Sr0.9Co0.9Nb0.1O3-delta membrane exhibits the largest fluxes among all the title compounds, followed by La0.1Sr0.9Co0.9Nb0.1O3-delta and La0.1Sr0.9Co0.9Nb0.1O3-delta and La0.1Sr0.9CoO3-delta. The oxygen permeation values exhibit exact the same trend as a function of composition with the bulk-diffusion and surface exchange coefficients values indicating both bulk-diffusion and surface exchange limits the oxygen transport through title compounds. In addition, 300-hour permeation testing on the best doped compounds, La0.1Sr0.9Co0.9Nb0.1O3-delta and La0.1Sr0.9CoO3-delta demonstrates that La0.1Sr0.9CoO3-delta has better performance stability, e. g. lower degradation percentage with time relative to its non niobium doped counterpart. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3533904] All rights reserved.

Bi doping of SrFeO3−δ results in the formation of a structure with high symmetry and extraordinary electrochemical performance for Bi0.5Sr0.5FeO3-δ, which is capable of competing effectively with the current Co-based cathode benchmark with additional advantages of lower thermal expansion and cost.

In this work we investigated the synthesis of composite organic and inorganic membranes for proton conduction. Particles derived from metal alkoxides (M(OR)n) sol-gel processes (Ti, Zr, W with phosphoric acid) were embedded in polymeric matrices of poly-vinyl alcohol, (3-glycidoxypropyl)-trimethoxysilane and ethylene glycol. The structure of the composite membranes was complex as several IR peaks were convoluted, indicating the assignment of several functional groups. However, the peaks assigned to OH groups reduced in intensity in the composite membranes, indicating that cross-linking of hydroxyl groups in the organic and inorganic phases of the membrane may have occurred. The particles allowed for re-arrangement of the polymer matrix, as crystallinity was reduced compared to a polymer blank membrane. The composite membrane process resulted in homogeneous dispersion of nanoparticles into the polymer film. Proton conduction of the inorganic phase was mainly dominated by titania. Binary mixtures of titania phosphate (sample name TiP) resulted in proton conduction of 7.15 ? 10−2 S.cm−1, one order of magnitude higher than zirconia phosphate (ZrP). The addition of Zr and W to TiP forming ternary or quaternary phases also led to lower proton conduction as compared to TiP. Similar trends were also observed for the composite membranes, though the TiP composite membrane proton conduction reduced after several hours of testing at 50?C, which was mainly attributed to acid leaching.

A membrane reactor allows for simultaneous separation and reaction, and thus, can play a good role to produce value-added chemicals. In this work, we demonstrated such a membrane reactor based on fluorite oxide samarium-doped ceria (SDC) using an external short-circuit concept for oxygen permeation. The fluorite phase was employed to impart its high structural stability, while its limited electronic conductivity was overcome by the application of an external short circuit to function the SDC membrane for oxygen transport. On one side of the membrane, i.e., feed side, carbon dioxide decomposition into carbon monoxide and oxygen was carried out with the aid of a Pt or Ag catalyst. The resultant oxygen was concurrently depleted on the membrane surface and transported to the other side of the membrane, favorably shifting this equilibrium-limited reaction to the product side. The transported oxygen on the permeate side with the aid of a GdNi/Al2O3 catalyst was then consumed by the reaction with methane to form...