Preparation of Pt electrocatalyst supported by novel, Ti(1−x)MoxO2-C type of composites containing multi-layer graphene

Ball milling is a relative simple and promising technique for preparation of inorganic oxide–carbon type of composites. Novel TiO2-C and Ti0.8Mo2O2-C type of composites containing multi-layer graphene were prepared by ball milling of graphite in order to get electrocatalyst supports for polymer electrolyte membrane fuel cells. Starting rutile TiO2 was obtained from P25 by heat treatment. Carbon-free Ti0.8Mo2O2 mixed oxide, prepared using our previously developed multistep sol–gel method, does not meet the requirements for materials of electrocatalyst support, therefore parent composites with Ti0.8Mo2O2/C = 75/25, 90/10 and 95/5 mass ratio were prepared using Black Pearls 2000. XRD study of parent composites proved that the oxide part existed in rutile phase which is prerequisite of the incorporation of oxophilic metals providing CO tolerance for the electrocatalyst. Ball milling of TiO2 or parent composites with graphite resulted in catalyst supports with enhanced carbon content and with appropriate specific surface areas. XRD and Raman spectroscopic measurements indicated the changes of graphite during the ball milling procedure while the oxide part remained intact. TEM images proved that platinum existed in the form of highly dispersed nanoparticles on the surface of both the Mo-free and of Mo-containing electrocatalyst. Electrocatalytic performance of the catalysts loaded with 20 wt% Pt was studied by cyclic voltammetry, COads-stripping voltammetry done before and after the 500-cycle stability test, as well as by the long-term stability test involving 10,000 polarization cycles. Enhanced CO tolerance and slightly lower stability comparing to Pt/TiO2-C was demonstrated for Pt/Ti0.8Mo2O2-C catalysts.

Dynamic Load Cycle Effects on PEMFC Stack CO Tolerance under Fuel Recirculation and Periodic Purge

This work presents first experimental evidence on the effects of dynamic load cycle on PEM fuel cell system CO tolerance, a topic which to date has not been comprehensively investigated. The experiments were performed with a 1 kW fuel cell system employing components, design, and operation conditions corresponding to automotive applications. To distinguish between the load cycle and other factors affecting the CO tolerance, the experiments were repeated with static and dynamic load cycles, as well as with pure and CO contaminated fuel. The measurement data showed that dynamic load cycle improves the CO tolerance in comparison to static load with the same average current density. Moreover, the cell voltage deviation data indicated that the difference could be explained by higher electrochemical CO oxidation rate under the dynamic load cycle. These results allow us to estimate the effect of the load cycle on CO tolerance and understand its origins, thus giving valuable input for fuel quality standardization and fuel cell system development work.

Modifications on Promoting the Proton Conductivity of Polybenzimidazole-Based Polymer Electrolyte Membranes in Fuel Cells

Hydrogen-air proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are excellent fuel cells with high limits of energy density. However, the low carbon monoxide (CO) tolerance of the Pt electrode catalyst in hydrogen-air PEMFCs and methanol permanent in DMFCs greatly hindered their extensive use. Applying polybenzimidazole (PBI) membranes can avoid these problems. The high thermal stability allows PBI membranes to work at elevated temperatures when the CO tolerance can be significantly improved; the excellent methanol resistance also makes it suitable for DMFCs. However, the poor proton conductivity of pristine PBI makes it hard to be directly applied in fuel cells. In the past decades, researchers have made great efforts to promote the proton conductivity of PBI membranes, and various effective modification methods have been proposed. To provide engineers and researchers with a basis to further promote the properties of fuel cells with PBI membranes, this paper reviews critical researches on the modification of PBI membranes in both hydrogen-air PEMFCs and DMFCs aiming at promoting the proton conductivity. The modification methods have been classified and the obtained properties have been included. A guide for designing modifications on PBI membranes for high-performance fuel cells is provided.

Tolerance of soil bacterial community to tetracycline antibiotics induced by As, Cd, Zn, Cu, Ni, Cr and Pb pollution

The widespread use of both heavy metals and antibiotics in livestock farming and their subsequent arrival on agricultural soils through manure/slurry spreading has become a problem of vital importance for human health and the environment. In the current research, a laboratory experiment was carried out for 42 days to study co-selection for tolerance of three tetracycline antibiotics (tetracycline, TC; oxytetracycline, OTC; chlortetracycline, CTC) in soils polluted with heavy metals (As, Cd, Zn, Cu, Ni, Cr and Pb) at high concentration levels (1000 mg kg−1 of each one, separately). Pollution Induced Community Tolerance (PICT) of the bacterial community was estimated using the leucine incorporation technique. The Log IC50 (logarithm of the concentration causing 50 % inhibition in bacterial community growth) values obtained in uncontaminated soil samples for all the heavy metals tested showed the following toxicity sequence: Cu > As > Cr ≥ Pb ≥ Cd > Zn > Ni. However, in polluted soil samples the toxicity sequence was: Cu > Pb ≥ As ≥ Cd ≥ Cr ≥ Ni ≥ Zn. Moreover, at high metal concentrations the bacterial communities show tolerance to the metal itself, this taking place for all the metals tested in the long term. The bacterial communities of the soil polluted with heavy metals showed also long-term co-tolerance to TC, OTC, and CTC. This kind of studies, focusing on the eventual increases of tolerance and co-tolerance of bacterial communities in agricultural soil, favored by the presence of other pollutants, is of crucial importance, mostly bearing in mind that the appearance of antibiotic resistance genes in soil bacteria could be transmitted to human pathogens.

Carbon-Monoxide-Tolerant Pt-Based Electrocatalysts for H2-PEMFC Applications: Current Progress and Challenges

The activity degradation of hydrogen-fed proton exchange membrane fuel cells (H2-PEMFCs) in the presence of even trace amounts of carbon monoxide (CO) in the H2 fuel is among the major drawbacks currently hindering their commercialization. Although significant progress has been made, the development of a practical anode electrocatalyst with both high CO tolerance and stability has still not occurred. Currently, efforts are being devoted to Pt-based electrocatalysts, including (i) alloys developed via novel synthesis methods, (ii) Pt combinations with metal oxides, (iii) core–shell structures, and (iv) surface-modified Pt/C catalysts. Additionally, the prospect of substituting the conventional carbon black support with advanced carbonaceous materials or metal oxides and carbides has been widely explored. In the present review, we provide a brief introduction to the fundamental aspects of CO tolerance, followed by a comprehensive presentation and thorough discussion of the recent strategies applied to enhance the CO tolerance and stability of anode electrocatalysts. The aim is to determine the progress made so far, highlight the most promising state-of-the-art CO-tolerant electrocatalysts, and identify the contributions of the novel strategies and the future challenges.