In situ spectroelectrochemical measurements during the electro-oxidation of ethanol on WC-supported Pt-black. Part II: Monitoring of catalyst aging by in situ Fourier transform infrared spectroscopy

As a continuation of a project on the spectroelectrochemical analysis of long-term behaviour of WC-supported Pt electrocatalysts (for SFG results, see part I: [1]), in this paper we report in situ FT-IR spectroscopy experiments, carried out during prolonged electro-oxidation of ethanol on Pt-black. From the analytical point of view, as expected, FT-IR spectra showed the presence of adsorbed acetic acid and ethanol, in addition to the well-known, dominant species: linearly adsorbed CO (2044-2063 cm⁻¹) and solution-phase CO₂ (2345 cm⁻¹). As far as quantitative spectroscopic results are concerned, a notable sensitivity of the interfacial chemistry to catalyst aging could be highlighted by this approach. The spectra recorded in three subsequent series of potential-cycling experiments showed a clear-cut dependence of spectral patterns and peak intensities, on the applied potential and on the oxidation duration. Qualitative spectral changes seem to suggest - coherently with in situ SFG results obtained with the same system [1] - that electrocatalyst aging correlates with a higher surface coverage with ethanol as compared with acetic acid. Quantitative analysis, based on fitting with Lorentzian lineshapes, yields information that can be used as a molecular-level diagnostic of the modification of the catalyst-adsorbate structure.     

In vitro digestibility of Bacillus fermented soya bean

Bacillus fermented legume products include among others dawadawa and soumbala made from African locust bean, and natto and kinema made from soya bean. Bacillus subtilis is the dominant species involved in the fermentation. During Bacillus fermentation for 48 h of autoclaved soya bean the quantity of soluble and dialyzable matter increased from 22% and 6% up to 65% and 40%, respectively. Protein and carbohydrate degradation during fermentation of soya bean with several Bacillus spp. was investigated and appeared to be substantial during the first 18 h of fermentation resulting in the release of high levels of peptides and oligosaccharides. In vitro digestibility was increased from 29% up to 33–43% after Bacillus fermentation for 48 h. It was shown that Bacillus spp. were able to degrade soya bean macromolecules to a large extent resulting in water-soluble low molecular weight compounds. In vitro digestion of Bacillus fermented soya bean using gastrointestinal enzymes only slightly increased the amount of dialyzable matter, which clearly demonstrated the beneficial effect of Bacillus fermentation on food nutrient availability.     

Degradation of semiconducting polymers by concentrated sunlight

A lens based sunlight concentration setup was used to accelerate the degradation of semiconducting polymers. Sunlight was collected outdoor and focused into an optical fiber bundle allowing for indoor experimental work. Photo-degradation of several polymers was studied by UV-vis absorbance spectroscopy and infra-red spectroscopy. This showed that the degradation rate is significantly increased by increasing illumination intensity. Acceleration factors exceeding 100 compared to standard 1 sun illumination were observed for solar concentration of 200 suns in the case of P3HT. A comparison between infra-red spectra of MEH-PPV degraded at 1 sun intensity and at high solar concentration only showed minor deviations in degradation mechanisms. The acceleration factor was found to vary linearly with the solar concentration. Finally, a comparison of the degradation rates at 1 sun and 100 suns was carried out in a materials study employing five different conjugated polymers relevant to polymer solar cells for which acceleration factors in the range 19-55 were obtained.     

The corrosion of PEM fuel cell catalyst supports and its implications for developing durable catalysts

Studying the corrosion behavior of catalyst support materials is significant for understanding the degradation of polymer electrolyte membrane (PEM) fuel cell performance and developing durable electrocatalysts. The oxidation of Vulcan carbon black (the most widely used catalyst support for PEM fuel cells) was investigated using various electrochemical stressing methods (fixed-potential holding vs. potential-step cycling), among which the potential-step cycling was considered to mimic more closely the real drive-cycle operation of vehicle PEM fuel cells. The oxidation of carbon was accelerated under potential-step conditions as compared with the fixed-potential holding condition. Increasing the potential-step frequency or decreasing the lower potential limit in the potential-step can further accelerate the corrosion of carbon. The accelerated corrosion of carbon black was tentatively attributed to the cycle of consumption/regeneration of some easily oxidized species. These findings are being employed to develop a test protocol for fast-screening durable catalyst support.     

Identification and analysis of Swiss National Road tunnels pathologies

In order to evaluate the general conditions (i.e. safety, serviceability and durability) of tunnels, a detailed analysis of the lining structure and surrounding rock mass is required. During the service life of the tunnel, regular survey activities should be performed to check the tunnel conditions and regular conservation practices are necessary to preserve the tunnel’s structural integrity and guarantee safety and serviceability during operation. The collection of data about tunnels since their construction and during their service life may help in the assessment of tunnel conditions and improve the understanding of tunnel degradation with time. The long term behaviour of the Swiss National Road tunnels has been studied and a specific data base has been developed. Based on detailed literature review and analysis of principal inspections results collected in the data base, the main pathologies that affect the Swiss road tunnels have been identified. In addition, by means of a specific data analysis, both degradation potential and rate have been investigated and the main influence factors involved have been selected. The obtained results confirm what was expected according to observations in the past. After a brief introduction about the tunnels of the National Roads network, this paper describes the main steps of the data analysis, different methods used and main results of the analysis. Due to the fact that the tunnels within Swiss National Roads were developed during the 60s, attention has been focused only on concrete lined tunnels.     

γ辐照后TBP—煤油对^95Zr的萃取和保留

研究了用不同浓度HNO_3预平衡和经γ辐照不同剂量后的TBP-煤油对~(95)Zr的萃取行为。测定了0.01mol/1HNO_3,5%Na_2CO_3洗涤后的有机相中~(95)Zr的保留百分率。比较了辐照后的TBP-煤油用碱和水萃洗分离得到的三个组份以及HDBP等7种辐解产物对~(95)Zr的萃取和洗涤后有机相中的保留情况。结果表明~(95)Zr的萃取和洗涤后的保留与溶剂所受的辐照剂量和预平衡酸度均有关系。在辐解产物中,单烷基长链酸性磷酸酯和异羟肟酸对Zr的萃取影响都较严重。前者在碱洗时容易产生乳化,而后者在碱洗后对Zr的保留更为严重。     

褐煤催化降解生烃过程的动力学研究

利用微量热天平模拟装置，对山西繁峙褐煤进行了热降解模拟实验，考察了作为催化剂介质的粘土矿牧无机盐类对褐煤生烃过程的影响，求得了催化生烃过程的动力学参数。结果表明：催化剂介质不同程度也降低了热降解反应的表观活化能，从而加速了反应的进行。     

Effect of Biotrickling Filter Operating Parameters on Chlorobenzenes Degradation

In this paper the effect of operating parameters on biotrickling filter performance degrading chlorobenzene and o-dichlorobenzene mixture were studied. The large laboratory scale biofilter, total volume 40 L, filled with inert packing material was used. The biomass adaptation and cultivation were performed in a batch fermentor and were used to inoculate the biotrickling filter. After a starting period, the influence of the substrate load increase, liquid recirculation flow rate, and empty bed retention time on elimination capacity and removal efficiency were found. The most important recirculation liquid parameters were analyzed every day, that is: concentration of metabolites, dissolved organic carbon, nitrate, chloride, and biomass. A good correlation was found between intermediate concentration and the removal efficiency of the biotrickling filter. The measurements of the absorbance, very easy and rapid, can be used as a control parameter of the biofiltration efficiency.