Tribochemically driven dehydrogenation of undoped sodium alanate under room temperature.

An application of mechanical energy was explored as a new non-thermal method to drive H2 emission from undoped sodium alanate at room temperature. It was found that mild rubbing of NaAlH4 pellets under vacuum led to intensive and almost instantaneous gas emission. The dominating species in the emitted gases was H2 (>99%). Traces of mono- and polyalanes, NaAlH4 vapours, CO2 and other non-identified gases were registered. H2 emission involved several first-order processes, whose characteristic time constants ranged widely from 0.6 to 465 s. None of the dehydrogenation reactions could be connected to either the thermal effect of friction or the direct coupling of mechanical forces to the energy landscape of chemical reactions. In turn, it was suggested that the tribochemical reactions can be triggered by plastic deformation and shearing. A linked diffusion-wear model of NaAlH4 triboinduced dehydrogenation, which consistently explains all empirical findings, was put forward.

Assessment of urban air pollution related to potential nanoparticle emission from photocatalytic pavements.

The main objective was to evaluate whether wearing and weathering of nanofunctionalized photocatalytic pavement in real urban environment can lead to undesirable emission of potentially toxic nanoparticle aerosols in urban air. The photocatalytic material was thoroughly tested before its application for conformity criteria in terms of photocatalytic effectiveness, intrinsic performance and undesired secondary effects, and then applied on a pilot scale in downtown Madrid. The aerosol monitoring on the pilot street before the coating applications as well as on the neighbouring streets during 10 months was used as a benchmark for evaluation of spatial and temporal variations. Analysis of the experimental data did not reveal any statistically significant variations in the aerosol concentrations on the pilot street in comparison with the benchmark. The concentration of Ti-containing particles was assessed by aerosol sampling and yielded values below 10 cm-3 that is more than three orders of magnitude below the toxicological limits. A theoretical model was developed to assess the upper bound of nanoparticle aerosol concentration in air. These findings indicated that photocatalytic pavement materials, which comply with conformity criteria under laboratory tests, can have low impact on the particulate contamination of urban air.

Unconventional Approaches to Hydrogen Sorption Reactions: Non-Thermal and Non-Straightforward Thermally Driven Methods.

In the last decades, a broad family of hydrides have attracted attention as prospective hydrogen storage materials of very high gravimetric and volumetric capacity, fast H2 -sorption kinetics, environmental friendliness and economical affordability. However, constraints due to their high activation energies of the different H2 -sorption steps and the Gibbs energy of their reaction with H2 has led to the need of high thermal energy to drive H2 uptake and release. High heat leads to significant degradation effects (recrystallization, phase segregation, nanoparticles agglomeration…) of the hydrides. In this context, this short review aims to summarize alternative non-thermal methods and non-straightforward thermally driven methods to overcome the previous constraints. The phenomenology lying behind these methods, i. e. tribological activation, sonication, and electromagnetic radiation, and the effect of these processes on hydrogen sorption properties of hydrides are described. These non-usual approaches could boost the capability of the next generation of solid-hydride materials for hydrogen conversion in energy sector, in mobile devices and as hydrogen reservoirs.

Primary and Secondary Emissions of VOCs and PAHs in Indoor Air from a Waterproof Coal-Tar Membrane: Diagnosis and Remediation.

Primary and secondary emissions of volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) from a waterproof coal tar membrane and their effect on the indoor air quality were investigated through a case study in a residential building situated in Madrid, Spain. The air contaminants were analyzed in situ using photoionization method and several samples of contaminants were taken using three sorbents: activated carbon, XAD2 and Tenax GR. It was found that various VOCs such as toluene, p- and m-Xylene, PAHs such as naphthalene, methyl-naphthalenes, acenaphthene, acenaphthylene, phenanthrene and fluorine, volatile organic halogens including chloroform and trichlorofluoromethane, and alkylbenzene (1,2,4-trimethylbenzene) were found at concentrations, which exceeded the limits established by international and national agencies (WHO, EPA, OSHA). Some of the above organic compounds were found also in the samples of construction and building materials, which were obtained at different heights and places. The analysis of possible sources of the contaminants pointed at the original coal-tar membrane, which was applied on the terrace to be waterproof. During a posterior reparation the membrane was coated with a new one that hindered dissipation of emitted contaminants. The contaminants leached out and were absorbed by construction materials down in the dwelling. These materials then acted as secondary emission sources. To remediate the emission problem as the contaminated materials were removed and then a ventilation system was installed to force the gasses being emitted from the rest of contaminated slab outside. Follow-up has validated the success of the remediation procedure.

Unusual photodegradation reactions of Asteraceae and Poaceae grass pollen enzymatic extracts on P25 photocatalyst.

In previous studies, it was demonstrated that photocatalysis by TiO2 nanoparticles can be effective for decomposition of pollen grains and pollen allergen extracts (PAEs) for Cupressus arizonica and Platanus hybrida species. In this work, the chemical and photochemical processes of five types of PAEs belonging to family Asteraceae, tribe Astereae, and family Poaceae, tribes Poeae and Triticea, were studied. It was confirmed that the PAEs suffered almost complete decomposition, which likely led to gaseous final products. For the species of Poeae tribe, i.e., Poa pratensis, Festuca pratensis, and Avena sativa, an unusual surface chemical modification of the photocatalyst consisting in the appearance of new bands on fine core level spectra of Ti 2p, C 1s, and O 1s was observed. These changes were associated with possible doping of TiO2 with C and N by pollen extracts. This was accompanied by a red shift of absorption spectra. The results suggest that some components of Poeae pollen can be grafted on TiO2 surface and they can activate the photocatalyst in the visible range. These findings can open a new pathway to eco-friendly chemical engineering of photocatalysts using organic biological compounds.

High-capacity adsorbents from stainless steel slag for the control of dye pollutants in water.

Adsorbent materials for the control of dye pollutants in water were synthetized from stainless steel slag (SSS) using different acid-base treatments. Using HCl (SS-Cl) and HNO3 (SS-NO3) produced high-capacity adsorbents, with BET areas of 232 m2/g and 110 m2/g respectively. Specifically, the SS-Cl had a structure of amorphous silica sponge. Treatment with H2SO4 (SS-SO4) did not enhance the adsorption capabilities with respect to the raw sample (SSS). Activated carbon (AC) was also tested as reference. The materials were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 adsorption-desorption isotherms, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) zeta potential, and infrared spectroscopy (FTIR). Batch adsorption experiments with methylene blue (MB) showed that the maximum sorption capacities were 9.35 mg/g and 8.97 mg/g for SS-Cl and SS-NO3 at 240 h, respectively. These values, even at slower rate, were close to the adsorption capacity of the AC (9.72 mg/g). This behavior has been attributed to the high porosity in the range of nanopores (0.6-300 nm) and the high-surface area for both samples. Preferential involvement of certain functional groups in the adsorption of dye ions on their surface indicative of chemisorption has been found. Although optimization, repeatability, and reproducibility of the process and environmental assessment have to be done before practical applications, these preliminary results indicate that application of these cost-effective adsorbents from raw SSS may be used in water pollution treatment and contribute to the sustainable development of the steel manufacturing industry.

New Holistic Conceptual Framework for the Assessment of the Performance of Photocatalytic Pavement.

Despite serious health and environmental burdens associated with air pollution by NOx, the emission ceilings have been systematically exceeded in big European cities for several years. Photocatalytic technology can be an efficient solution for the removal of chemical air pollutants. Because diesel engine exhaust is the main source of NOx emissions, the application of a photocatalyst onto road pavement appears to be an effective NOx abatement method due to the large surface area, proximity to the emission source, and relatively good solar irradiance. Several laboratory-scale studies provided evidence demonstrating that most harmful contaminants can be readily mineralized. Furthermore, several projects were aiming to scale up this technology to pilot and real scales. Although the photocatalytic performances of selected materials in real urban environments were determined in some of these studies, the data are not conclusive for evaluating the overall performance because other material characteristics relevant to their functionality were not assessed. The lack of conformity criteria suitable for the evaluation of the overall performance of photocatalytic pavement under real operational conditions has generated skepticism and mistrust among public authorities and relevant stakeholders, which constrains the widespread implementation of this promising technology. In this context, the project LIFE-Photoscaling was focused on developing a new holistic conceptual framework to assess the photocatalytic pavement performance using the decision tool "Photoscaling Decision Maker" based on a set of quantitative indicators. For this purpose, a large volume of data obtained for 10 types of photocatalytic pavement materials was systemized on both the laboratory and pilot plant scales and three main indicators were defined: (1) photocatalytic performance effectiveness, (2) intrinsic performance, and (3) undesired secondary effects. Each top-level indicator includes several low-level subindicators associated with specific material characteristics. Finally, the ranges of the main indicators and subindicators and methods for their assessment were determined. These methods include standard, adopted, and original characterization techniques, which were selected based on the criteria such as simplicity, cost- and time-effectiveness, and relevance regarding the operational conditions.

Tribochemical Decomposition of Light Ionic Hydrides at Room Temperature.

Tribochemical decomposition of magnesium hydride (MgH2) induced by deformation at room temperature was studied on a micrometric scale, in situ and in real time. During deformation, a near-full depletion of hydrogen in the micrometric affected zone is observed through an instantaneous (t < 1 s) and huge release of hydrogen (3-50 nmol/s). H release is related to a nonthermal decomposition process. After deformation, the remaining hydride is thermally decomposed at room temperature, exhibiting a much slower rate than during deformation. Confocal-microRaman spectroscopy of the mechanically affected zone was used to characterize the decomposition products. Decomposition was enhanced through the formation of the distorted structure of MgH2 with reduced crystal size by mechanical deformation.

A study of hydrogenated carbon fibers by scanning electron microscopy and confocal laser scanning microscopy.

The hydrogen absorption process is studied in carbonaceous fibers produced from a mixture of methane and hydrogen. The absorption of the hydrogen was examined in two types of fibers, in "as-grown" state and after a process of desorption during an annealing to 1.473 K under vacuum. Later to its production process, the fibers withstand an oxidation in air to 973 K. The fibers were examined by means of scanning electron microscopy (SEM) and confocal microscopy by reflection. Differences in the behavior during the oxidation were observed between the fibers in as-grown state and those subjected to a further annealing. It could be verified that the fibers were really constituted by two different phases. In one of the phases, the storage of the hydrogen absorbed took place, whereas in the other phase there was no alteration. The process of annealing prior to the absorption of the hydrogen has an appreciable effect on the desorption rate of the hydrogen.