Chemical hydrogen storage and release properties using redox reaction over the Cu-added Fe/Ce/Zr mixed oxide medium

The chemical hydrogen storage (hydrogen reduction) and release (water-splitting oxidation) properties of the Cu-added Fe/Ce/Zr mixed oxide medium were investigated. The media with Cu content ranging from 0 to 5 wt% were prepared by a co-precipitation method using urea as a precipitant. The hydrogen reduction and the water-splitting oxidation on the medium were tested by temperature programmed reduction/oxidation (TPR/TPO) and repeated isothermal redox cycles at 550 °C for reduction and 350 °C for oxidation. The initial reduction rates and oxidation rates of the media increased with increasing the amount of the Cu additive. In addition, the reactivity of the medium for water-splitting oxidation was enhanced as the CeO₂/ZrO₂ ratio increased. Especially, the Fe-based mixed oxide medium with Cu/CeO₂/ZrO₂ contents of 3/30/10 wt% (Cu(3%)-Fe-CeO₂/ZrO₂(3/1)) showed superior performance in chemical hydrogen storage and release. As the results of isothermal redox cycles using the medium, the total amount of hydrogen evolved in water-splitting oxidation was maintained at ca. 8.5 mmol g^?1-medium (ca. 1.8 wt% hydrogen storage amounts on the basis of the total medium) over 15 repeated redox cycles.     

Thermally stable ceria–zirconia catalysts for soot oxidation by O2

Ce–Zr mixed oxides calcined at 1000 °C are more active catalysts for soot oxidation than pure CeO₂ calcined at the same temperature, both in loose and tight contact between soot and catalyst. 1000 °C sinterised-CeO₂ presents a very low surface area (2 m²/g), a large crystal size (110 nm) and a lack of surface redox properties. Ce–Zr mixed oxides present higher BET surface areas (typically 17–19 m²/g), smaller crystal sizes and enhanced redox properties. The Zr molar fraction does not affect appreciably the catalytic activity of Ce–Zr mixed oxides in the range studied (Zr molar fraction from 0.11 to 0.51).     

Effect of PyC interphase thickness on mechanical behaviors of SiBC matrix modified C/SiC composites fabricated by reactive melt infiltration

A dense carbon fiber reinforced silicon carbide matrix composites modified by SiBC matrix (C/SiC-SiBC) was prepared by a joint process of chemical vapor infiltration, slurry infiltration and liquid silicon infiltration. The effects of pyrolytic carbon (PyC) interphase thickness on mechanical properties and oxidation behaviors of C/SiC-SiBC composites were evaluated. The results showed that C/SiC-SiBC composites with an optimal PyC interphase thickness of 450 nm exhibited flexural strength of 412 MPa and fracture toughness of 24 MPa m^1/2, which obtained 235% and 300% improvement compared with the one with 50 nm-thick PyC interphase. The enhanced mechanical properties of C/SiC-SiBC composites with the increase of interphase thickness was due to the weakened interfacial bonding strength and the decrease of matrix micro-crack amount associated with the reduction of thermal residual stress. With the decrease in matrix porosity and micro-crack density, C/SiC-SiBC composites with 450 nm-thick interphase exhibited excellent oxidation resistance. The residual flexural strength after oxidized at 800, 1000 and 1200 °C in air for 10 h was 490, 500 and 480 MPa, which increased by 206%, 130% and 108% compared with those of C/SiC composites.     

Inorganic polymers from laterite using activation with phosphoric acid and alkaline sodium silicate solution: Mechanical and microstructural properties

Geopolymers from laterite, an iron-rich soil available in developing countries, have great potential as building materials. In this work, laterite from Togo (Africa) was used to prepare geopolymers using both phosphoric acid and alkaline sodium silicate solution. Microstructural properties were investigated by scanning electron microscopy, X-ray powder diffraction and mercury porosimetry, whereas thermal properties were evaluated by thermal analyses. The local environment of iron was studied by X-ray Absorption Spectroscopy (XANES region). The mechanical properties were determined. Modulus of Rupture and Young's modulus fell in the ranges 3.3–4.5 MPa and 12–33 GPa, respectively, rendering the materials good candidates for construction purposes. Heating above 900 °C results in weight-gain, presumably due to iron redox reactions. X-ray Absorption Spectroscopy data evidence changes in the chemical and structural environments of iron following thermal treatment of geopolymers. These changes indicate interaction between the geopolymer structure and iron during heating, possibly leading to redox properties.     

Promoting effect of the addition of Ce and Fe on manganese oxide catalyst for 1,2-dichlorobenzene catalytic combustion

Mn-based mixed-oxide (MnO_x) catalysts were modified with Fe, Ce, and Ce + Fe, and its catalytic oxidation activity was tested by using 1,2-dichlorobenzene (o-DCB) as models of chlorinated volatile organic compounds. Addition of Ce or Ce + Fe into MnO_x promoted their crystals to turn into amorphous powder, enhanced their specific surface area and changed their redox property. The catalytic activity of MnO_x improved remarkably by adding Ce or Ce + Fe indicating Ce plays an important role. Both Mn-Ce and Mn-Ce-Fe catalysts exhibited good stability for catalytic oxidation of o-DCB, indicating that the introduction of promoter is an important method to improve the catalytic performance.     

High temperature thermoelectric properties of Ca3Co4O9+δ by auto-combustion synthesis and spark plasma sintering

A rapid method for the synthesis of Ca₃Co₄O_9+δ powder is introduced. The procedure is a modification of the conventional citric-nitrate sol–gel method where an auto-combustion process is initiated by a controlled thermal oxidation–reduction reaction. The resulting powders inherit the advantages of a wet chemical synthesis, such as morphological and compositional homogeneity, and fine, well-defined particle sizes coming from the controlled nature of the auto-combustion. Optimized spark plasma sintering (SPS) processing conditions were determined and used to fabricate dense and highly c-axis oriented samples. The microstructure and thermoelectric transport properties were determined both parallel (||) and perpendicular (⊥) to the SPS pressure axis in order to investigate any possible anisotropy variations in the transport properties. At 800 °C, power factors of 506 μW/m K² (⊥) and 147 μW/m K² (||), thermal conductivities values of 2.53 W/m K (⊥) and 1.25 W/m K (||), and resulting figures-of-merit, ZT, of 0.21 (⊥) and 0.13 (||) were observed.     

Tailoring the surface chemistry and porosity of activated carbons: Evidence of reorganization and mobility of oxygenated surface groups

An activated carbon with developed porosity and surface area (S_BET = 2387 m² g⁻¹) was prepared by chemical activation and then oxidized with ammonium peroxydisulfate. The oxidation treatment destroyed mesopore walls leading to a severe surface area reduction. Specific thermal treatments were carried out in different portions of the oxidized sample to selectively remove the oxygenated surface complexes. The combination of different techniques revealed that thermal treatment between 300 and 500 °C produces a strong reorganization of oxygenated groups on the chemical structure of carbons. CO₂-evolving groups (around 75 wt.%) are selectively transformed into CO-evolving groups. These processes only occur inside the pores, and involve CO₂ desorption and re-adsorption in this temperature range. At a higher treatment temperature (700 °C), re-oxidation is prevented and the surface chemistry becomes quite similar to the original activated carbon.     

Storage of small samples of coking coal for thermal rheological tests

A study was undertaken with the aim of finding the best practical way of storing small coal samples in a laboratory setting to limit their extent of oxidation for maintaining good thermal rheological properties. Samples of a Canadian medium-volatile bituminous coal of Cretaceous age (‘as received’ and < 0.42 mm sizes) were stored under various media (open trays in laboratory, in an oven, under water and under vacuum) and temperatures (− 15, 4, 20 and 40 °C) for up to 60 weeks. Samples were analyzed for Chemical changes including O content, O / C, H / O, H / C, Volatile Matter, and Calorific Value; Thermal Rheological changes in Fluidity, Plastic range, Dilatation, Free-Swelling Index and Alkali Light Transmittance. Coke Quality changes in Coke Cake Contraction, Coke Reactivity and Coke Strength indices as well as Coke Optical Textures were also examined. For chemistry related changes, the most obvious ones due to oxidation are in atomic oxygen, which increases, and calorific value, which decreases. Concerning thermal rheology changes, fluidity and dilatation were found to decrease the most whereas Free-Swelling Index and Alkali Light Transmittance do not appear to be sensitive indicators of early stages of oxidation for the examined coal. Pertaining to coke quality, coke cake contraction remains essentially unchanged, Coke Strength after Reaction decreases and Coke Reactivity Index increases, and textures reveal a significant increase in coke inerts.This work has found coal oxidation to be mainly influenced by the storage temperature, with rate of oxidation increasing with temperature, and to a lesser extent by particle size, with oxidation being more likely the smaller the particle size.Of the different storage conditions tested in this investigation, keeping coal at cold temperatures (< − 15 °C) was found to be the most favourable for limiting its oxidation and thereby maintaining good thermal rheological properties.     

Low-temperature catalytic oxidation of chlorobenzene over MnOX/TiO2–CNTs nano-composites prepared by wet synthesis methods

Catalytic oxidation of chlorobenzene (CB) was studied over MnO_X/TiO₂–CNTs (carbon nanotube) nano-composites prepared by the solvothermal and sol–gel methods. Microstructures and redox properties of these composites were characterized by X-ray diffraction, electron microscopy, and temperature-programmed reduction. The catalytic activity for CB oxidation was promoted with the introduction of CNTs into MnO_X/TiO₂, and CB oxidation efficiencies of 90% and almost 100% could be obtained at 150 °C and 300 °C, respectively, under a gas hour space velocity of 36,000 h^− 1.The high catalytic performance could be attributed to the good dispersion of active component and the selective adsorption of CB by CNTs.     

Thermal cyclic life and failure mechanism of nanostructured 13 wt%Al2O3 doped YSZ coating prepared by atmospheric plasma spraying

Nanostructured 13 wt%Al₂O₃ doped nanostructured 8 wt% yttria stabilized zirconia (nano-13AlYSZ) coatings were deposited by atmospheric plasma spray (APS). The isothermal oxidation and thermal cyclic life of the nano-13AlYSZ coating at 1100 °C were investigated. The isothermal oxidation test results indicate that the oxidation kinetics of nano-13AlYSZ follows a parabolic law. The parabolic rate constant at 1100 °C is calculated 0.04365 mg² cm^?4 h^?1. The thermal cyclic life of nano-13AlYSZ coating is about 953 times at 1100 °C. The failure of the nano-13AlYSZ coating occurs at the interface between the nano-13AlYSZ coating and the thermal growth oxide (TGO). A finite element method is employed to analyze the stress distribution in the nano-13AlYSZ coating. The results show that maximum stresses occur at the top coat/TGO interface.     

Activity and stability of Pd/MMnOx (M = Co,Ni, Fe and Cu) supported on cordierite as CO oxidation catalysts

Several catalysts of the general formula, MMnO_x (M = Co, Ni, Fe and Cu), were synthesised through the impregnation method; their activities were shown to be enhanced by the addition of a small amount of Pd (0.01–0.1 wt%). These catalysts exhibit different activities for the catalytic oxidation of CO, due to the different valence states of various transition metal oxides. The introduction of Pd prominently enhanced both the reduction and oxidation capabilities of the catalysts. These catalysts were optimised for oxidation activities by designing orthogonal experiments. Based upon the catalysts’ properties, the stability of these samples and their ability to resist steam over Pd/CoMnO_x/cordierite were investigated.     

Thermal conductivity of porous SiC composite ceramics derived from paper precursor

Biomorphic porous SiC composite ceramics were produced by chemical vapor infiltration and reaction (CVI-R) technique using paper precursor as template. The thermal conductivity of four samples with different composition and microstructure was investigated: (a) C-template, (b) C-SiC, (c) C-SiC–Si₃N₄ and (d) SiC coated with a thin layer of TiO₂. The SiC–Si₃N₄ composite ceramic showed enhanced oxidation resistance compared to single phase SiC. However, a key property for the application of these materials at high temperatures is their thermal conductivity. The later was determined experimentally at defined temperatures in the range 293–373 K with a laser flash apparatus. It was found that the thermal conductivity of the porous ceramic composites increases in the following order: C-template < C-SiC < C-SiC–Si₃N₄ < SiC–TiO₂. The results were interpreted in regard to the porosity and the microstructure of the ceramics.     

A double layer nanostructure SiC coating for anti-oxidation protection of carbon/carbon composites prepared by chemical vapor reaction and chemical vapor deposition

A double layer nanostructure SiC coating was prepared by chemical vapor reaction and chemical vapor deposition to protect carbon/carbon composites from oxidation. The obtained dense coating reveals a typical crystalline structure and combines well with the substrate. The outer layer of the coating consists of SiC nanocrystals and nanowires, whereas the inner layer is mainly composed of SiC microcrystals, nanocrystals and nanowires. The oxidation and cyclic thermal shock test performed at 1400 °C in air demonstrates that the prepared dense nanostructure coating has excellent anti-oxidation behavior and thermal shock resistance at high temperature. After 400 h oxidation and 34 cycles of thermal shock from 1400 °C to room temperature, the weight loss of the coated sample is only 1.67%. In the oxidation process, the amorphous silica formed at the beginning of the oxidation crystallizes to cristobalite as oxidation time increased. The formation of cristobalite resulted in micro-cracks formed along grain boundaries in the cyclic thermal shock test. As only cracks are formed on the coating surface, it can be concluded that the formation of the penetration cracks may be the reason for the weight loss of the SiC coated composite.     

Electrochemical reduction and oxidation pathways for Reactive Black 5 dye using nickel electrodes in divided and undivided cells

The cathodic reduction and anodic OH-mediated oxidation of the azo dye Reactive Black 5 (RB5) have been studied potentiostatically by using undivided and divided cells with a Ni-polyvinylchloride (Ni-PVC) composite cathode and a Ni wire mesh anode. Solutions of 50–100 cm³ of 20–80 mg dm^?3 RB5 in 0.1 mol dm^?3 KOH were degraded to assess the effect of electrolysis time and electrode potentials on the infrared and absorbance spectra, as well as on the decay of the total organic carbon and chemical oxygen demand. Reversed-phase high performance liquid chromatography (RP-HPLC) with ion-pairing and diode array detection (ion pair chromatography), along with coupling to tandem mass spectrometry (LC–MS/MS), were used for the identification of the aromatic degradation by-products and monitoring their time course. These analyses revealed the progressive conversion of the RB5 dye to simpler molecules with m/z 200, 369.5 and 547 under the direct action of the electron at the cathode and the formation of polar compounds such as alkylsulfonyl phenol derivatives with m/z 201, 185 and 171 by the OH mediation at the anode. From these results, the electrochemical reduction and oxidation pathways for the RB5 dye were elucidated.     

Sintered esseneite–wollastonite–plagioclase glass–ceramics from vitrified waste

Dense sintered esseneite–wollastonite–plagioclase glass–ceramics have been successfully prepared from a vitrified mixture of important inorganic waste (Bayer process red mud, fly ash from lignite combustion and residues from the polishing of porcelain stoneware tiles). The enhanced nucleation activity of fine glass powders, favoured by particular oxidation conditions, caused a substantial crystallisation, even in the case of very rapid thermal treatments at 900 °C, which led to remarkable mechanical properties (bending strength and Vickers micro-hardness exceeding 130 MPa and 7 GPa, respectively) and a promising chemical durability.     

Syntheses,characterizations, and redox behaviors of new self-assembled metal complexes with bridging ligands incorporating chalcogen sites

Three new complexes, [Zn(dbsf)₂(dmf)₂] · 5.5dmf (dbsf = 4,4′-sulfonyldibenzoate) (1β), [Cu(tdsa)(phen)₂] · 1.5EtOH (tdsa = 5,5′-thiodisalicylate, phen = 1,10-phenanthroline) (2), and [Cu(sdp)(phen) · Cu(Hsdp)(phen)(CH₃COO)] · 3EtOH (sdp = 4,4′-sulfonyldiphenolate) (3) were prepared and structurally characterized. Complex 1β shows a one-dimensional coordination framework constructed from bridges between Zn(II) centers with two ligands. Complex 2 is a monomeric complex, which assembles by π–π interactions. Complex 3 shows a unique two-dimensional coordination framework that is constructed from two Cu(II) centers, sdp, and Hsdp. The redox properties of these three complexes were characterized by solid-state cyclic voltammetry. Complexes 1β and 3 show irreversible reduction waves because of the reduction of their sulfone sites. Complex 2 shows an irreversible oxidation wave because of oxidation of the sulfide site.     

Oxidation treatments for SiC particles and its compatibility with glass

Different thermal treatments were performed to produce a protective coating on the surface of SiC particles in order to allow their incorporation in a glass matrix. These oxidation treatments were carried out in air at different temperatures ranging from 800 °C to 1500 °C and different times at 1200 °C (10 min–48 h). The oxidation kinetics followed the Deal–Grove model and the thickness of the protective coating increased with temperature and SiC particle size. Protected SiC particles with different particle sizes were incorporated in a borosilicate glass. With small particles sizes foam glasses were obtained, whereas particles with higher grain size, i.e., higher coating thickness, were stable in the glass matrix and a smooth glass was obtained.     

Inorganic ceramic fiber separator for electrochemical and safety performance improvement of lithium-ion batteries

A separator based on ceramic fibers with excellent properties, utilized for powerful laminated lithium ion batteries, was prepared by low-cost production process. Physical and chemical characteristics of the separator and the electrochemical as well as the safety performance of lithium ion batteries were extensively investigated, and compared to commercialized polyethylene (PE) and ceramic-coating PE (C-PE) separators. The results demonstrated that inorganic ceramic fiber (CF) membrane exhibited higher porosity (85%), higher electrolyte uptake (381%) and higher ionic conductivity (1.48 mS/cm). Moreover, CF separator did not display thermal shrinkage at 160 °C for 1 h, manifesting that the separator possession of high thermal stability. The lithium nickel cobalt manganese oxide LiNi_0.5Co_0.2Mn_0.3O₂/ graphite battery employing the CF membrane displayed superior rate capability, which delivered the discharge capacities of 13.206 A h (0.2 C), 12.729 A h (0.5 C), and 12.074 A h (1 C), respectively. In addition, this battery improved cycle stability, with the capacity retention of 101.4% following 100 cycles at 1 C rate. Results of safety tests presented that batteries with CF separator passed both nail penetration and extrusion tests, implying that the safety performance was remarkably improved. Additionally, CF membrane had only 20 cents in cost for 1 Ah cells, which was ten times lower than commercial PE and C-PE separators. The perfect combination of good properties and low cost made it possible for the CF separator to be a promising separator for laminated lithium-ion batteries, which are especially used in electric vehicles.     

Thermal conductivity of individual carbon nanofibers

In the present paper, we present results of thermal conductivity measurements in commercially-available, chemical vapor deposition grown, heat-treated and non-heat-treated individual carbon nanofibers (CNFs). The thermal conductivity measurements are made using the T-type probe experimental configuration using a Wollaston wire probe inside a high resolution scanning electron microscope. The results show a significant increase in the thermal conductivity of CNFs that are annealed at 2800 °C for 20 h when compared with the non-heat-treated CNF samples. When adjusted for thermal contact resistance, the highest measured thermal conductivity is 449 ± 39 W/m-K. The average thermal conductivity of the heat-treated samples is 163 W/m-K, while the average thermal conductivity of the non-heat-treated samples is 4.6 W/m-K. The results demonstrate the importance of the quality of the CNFs, in particular their heat treatment (high temperature annealing), in controlling their thermal conductivity for thermal management applications.     

TiO2 photocatalysis in cementitious systems: Insights into self-cleaning and depollution chemistry

The present work offers a general overview about application of titanium dioxide (or titania), TiO₂, photocatalysis to concrete technology in relation to enhanced aesthetic durability and depollution properties achieved by implementing TiO₂ into cement. Chemistry of degradation of Rhodamine B (RhB), a red dye used to assess self-cleaning performances of concretes containing TiO₂, as well as oxidation of nitrogen oxides (NOx), gaseous atmospheric pollutants responsible for acid rains and photochemical smog, is investigated using two commercial titania samples in cement and mortar specimens: a microsized, m-TiO₂ (average particle size 153.7 nm ± 48.1 nm) and a nanosized, n-TiO₂ (average particle size 18.4 nm ± 5.0 nm). Experimental data on photocatalytic performances measured for the two samples are discussed in relation to photocatalyst properties and influence of the chemical environment of cement on titania particles. Impacts on applications in construction concrete are also discussed.