Average turn-over frequency of O2 electro-reduction for Fe/N/C and Co/N/C catalysts in PEFCs

This work aims to evaluate the average turn-over frequency of O₂ electro-reduction for the catalytic sites resulting from the heat-treatment of iron- or cobalt-acetate and carbon black in ammonia at high temperature. This task is complex because at least three factors may control the activity of such catalysts: their metal content, nitrogen content and micropore specific area. In this work, the activity was measured for metal contents from 0.005 to 5 wt.%. The time of heat-treatment was tuned to keep the micropore specific area constant. At Fe content ≤0.2 wt.% the activity increases linearly with Fe content, thus enabling the average turn-over frequency of the Fe/N/C site to be determined. At Co content ≤1.0 wt.% the activity increases approximately as the square root of the Co content. Because no linear relation was found, the turn-over frequency of the Co/N/C site could not be determined. For both Fe and Co catalysts, the activity drops dramatically at contents >1 wt.%. This is concurrent with a drop in the micropore specific area of the catalysts.     

A mass spectrometry method for quantitative and kinetic analysis of gas release from nuclear materials and its application to helium desorption from UO2 and fission gas release from irradiated fuel

A new system has been developed to determine absolute quantities of gas (mainly noble gases) released during thermal desorption in the range from 10^?12 to 10^?5 mol with a precision of few percent. The system is actually designed for simultaneous measurement of gaseous elements like He, Xe, Kr, thermally released from nuclear fuel samples and also allows the determination of the release kinetics as a function of time. This system, called Quantitative GAs MEasurement System (Q-GAMES), is based on the principle of collecting, purifying and spiking the sample gas in a “high-pressure” chamber, and continuous sampling of the gas for mass spectrometric analysis without sample depletion during the experiment. It is equipped with its own spike generator and with different gas purification systems. It is shown that this system fulfills the requirement to work with two existing very high-temperature gas desorption facilities for nuclear materials. This paper describes the Q-GAMES principle, the spiking system, its calibration, its operative mode, the different quantification techniques, as well as its technical data, in combination with some examples of typical application.     

Application of iron-based cathode catalysts in a microbial fuel cell

Catalysts for the oxygen reduction reaction (ORR) in a microbial fuel cell (MFC) were prepared by the impregnation on carbon black of Fe^II acetate (FeAc), Cl–Fe^III tetramethoxyphenyl porphyrin (ClFeTMPP), and Fe^II phthalocyanine (FePc). These materials were subsequently pyrolyzed at a high temperature. The ORR activity of all Fe-based catalysts was measured at pH 7 with a rotating disk electrode (RDE) and their performance for electricity production was then verified in a continuous flow MFC. Catalysts prepared with FeAc and pyrolyzed in NH₃ showed poor activity in RDE tests as well as a poor performance in a MFC. The ORR activity and fuel cell performance for catalysts prepared with ClFeTMPP and FePc and pyrolyzed in Ar were significantly higher and comparable for both precursors. The iron loading was optimized for FePc-based catalysts. With a constant catalyst load of 2 mg cm⁻² in a MFC, the highest power output (550–590 mW/m²) was observed when the Fe content was 0.5–0.8 wt%, corresponding to only 0.01–016 mg Fe/cm². A similar power output was observed using a Pt-based carbon cloth cathode containing 0.5 mg Pt/cm². Long-term stability of the Fe-based cathode (0.5 wt% Fe) was confirmed over 20 days of MFC testing.     

Fe-based catalysts for oxygen reduction in proton exchange membrane fuel cells with cyanamide as nitrogen precursor and/or pore-filler

Fe/N/C catalysts for oxygen reduction reaction were synthesized via impregnation or ballmilling. The role of cyanamide (CM) as nitrogen precursor and/or pore-filler for a highly microporous carbon (Black Pearls 2000) was investigated. The use of CM in this work resulted in two main differences compared with phenanthroline from our previous work; (i) ballmilling the precursors did not result in improved activity of the resulting catalysts, and (ii) the activity after the first pyrolysis in argon was relatively high, but did not increase after a second pyrolysis in NH₃. These differences may be explained by TGA measurements of both pore-fillers, where complete gasification of CM is observed at temperatures above 750 °C in Ar, while pyrolysis of phenanthroline in Ar results in 20 wt% residual carbon-based material. Consequently, when using CM as pore-filler with a highly microporous carbon support, the maximum microporous surface area and nitrogen content is reached after only a single pyrolysis in Ar. The most active catalyst prepared with CM was obtained by pyrolysing in Ar at 950 °C a catalyst precursor containing 1 wt% Fe, 80 wt% CM and Black Pearls 2000. This catalyst possessed about 1/6th the catalytic activity of best reported using phenanthroline as a pore-filler. Changing the carbon support had effects on the activity and stability of the catalysts. The catalysts made with a non-porous furnace black (N330) or carbon nanotubes as a carbon support were more stable but less performing than those using carbon supports having high microporous surface area like Black Pearls 2000 or Ketjenblack. The desirable properties for a pore-filler molecule used in the synthesis of Fe/N/C-catalysts by the pore-filling method are discussed.     

Electrogeneration of Hydrogen Peroxide in Acid Medium using Pyrolyzed Cobalt-based Catalysts: Influence of the Cobalt Content on the Electrode Performance

Cobalt tetramethoxyphenyl porphyrin (CoTMPP) adsorbed on a high area carbon support (Vulcan XC72-R) and heat-treated at 900 °C under inert atmosphere was studied as electrocatalyst for the reduction of O₂ to H₂O₂ in acid medium. Experiments performed on rotating ring-disc electrode (RRDE) and gas diffusion electrode (GDE) show that the catalyst performance depends on the cobalt loading, going through a maximum at 0.2 wt. % Co. For higher cobalt loadings, a growing part of oxygen is reduced into water, decreasing therefore the selectivity of the catalyst. These results are interpreted in terms of a further reduction of H₂O₂ on Co-based catalytic sites before leaving the catalytic layer. For a GDE polarized at −150 mV vs. saturated calomel electrode (SCE) and loaded with 0.9 μg cm⁻² of 0.2 wt. % Co-based catalyst, a H₂O₂ production rate of 300 μmol h⁻¹ cm⁻² was obtained which is five times higher than the H₂O₂ production rate measured with Vulcan. In these conditions, the selectivity of the Co-based catalyst for H₂O₂ production is 92%. The good agreement observed between RRDE and GDE results confirms the relevance of using RRDE experiment for screening these non-precious metal catalysts for further GDE applications.     

High energy ball-milled Pt and Pt–Ru catalysts for polymer electrolyte fuel cells and their tolerance to CO

High energy ball milling, an industrially amenable technique, has been used to produce CO tolerant unsupported Pt–Ru based catalysts for the oxidation of hydrogen in polymer electrolyte fuel cells. Nanocrystalline Pt_0.5–Ru_0.5 alloys are easily obtained by ball-milling but their performances as anode catalysts are poor because nanocrystals composing the material aggregate during milling into larger particles. The result is a low specific area material. Improved specific areas were obtained by milling together Pt, Ru and a metal leacheable after the milling step. The best results were obtained by milling Pt, Ru, and Al in a 1:1:8 atomic ratio. After leaching Al, this catalyst (Pt_0.5–Ru_0.5 (Al₄)) displays a specific area of 38 m²g^–1. Pt_0.5–Ru_0.5 (Al₄) is a composite catalyst. It consists of two components: (i) small crystallites (4 nm) of a Pt–Al solid solution (1–3 Al wt%) of low Ru content, and (ii) larger Ru crystallites. It shows hydrogen oxidation performance and CO tolerance equivalent to those of Pt_0.5–Ru_0.5 Black from Johnson Matthey, the commercial catalyst which was found to be the most CO tolerant one in this study.     

Improvement of the high energy ball-milling preparation procedure of CO tolerant Pt and Ru containing catalysts for polymer electrolyte fuel cells

Ball-milling has been used to prepare performing CO tolerant polymer electrolyte fuel cell anode catalysts that contain Pt and Ru. The catalyst precursors are obtained by milling together Pt, Ru and a dispersing agent in the atomic ratio 0.5, 0.5 and 4.0. This precursor is not easily recovered after milling because it sticks to the walls of the vial and on the grinding balls. However, the precursor is recovered as a powder when a process control agent (PCA) is added during the milling step. Various PCAs have been used. The PCA should not interfere with the electrocatalytic activity of the catalysts obtained by leaching the precursor. The best preparation of catalyst precursors are obtained by milling: (i) Pt, Ru and Al (dispersing agent) in the atomic ratio 0.5, 0.5, 4.0 + 10 wt% NaF (PCA) or (ii) Pt , Ru and MgH₂ in the 0.5, 0.5, 4.0 atomic or molecular ratio. In this case, MgH₂ plays at the same time the role of a dispersing agent and that of a PCA. The catalysts are obtained by leaching Al and NaF in (i) or MgH₂ in (ii). The CO tolerance of these catalysts is equivalent to that of Pt_0.5Ru_0.5 Black from Johnson Matthey. The ball-milled catalysts have a surface area comprised between 30 and 44 m² g^–1. As-prepared catalysts are mainly made of metallic Pt and metallic plus oxidized Ru. After fuel cell tests, Pt is completely metallic while the oxidized Ru content decreases but does not disappear. These catalysts are composed of particles with crystallites of two different sizes: in (i) nanocrystallites (4 nm) that contain essentially Pt alloyed with Al and perhaps some Ru, and larger (30 nm) crystallites that contain essentially Ru; in (ii) Pt nanocrystalline particles that may contain some Ru and larger particles that contain essentially either Ru or Pt.     

Pt-Ru catalysts prepared by high energy ball-milling for PEMFC and DMFC: Influence of the synthesis conditions

High energy ball-milling was used to prepare several unsupported Pt-Ru anode catalysts for PEM- and direct methanol fuel cells. Pt and Ru with a 50:50 nominal Pt/Ru ratio were ball-milled at various ball-to-powder weight ratios (from 4/1 to 12/1) and with various Pt:Ru:MgH₂ proportions (from 1:1:2 to 1:1:10), where MgH₂ is a leacheable dispersive agent. The presence of MgH₂ is necessary to obtain unsupported catalysts with a specific surface area of between 50 and 75 m² g⁻¹. The ball-milling parameters greatly affected the relative proportions of the three phases constituting the catalysts. These phases are: Pt(Ru) alloy nanocrystallites, unalloyed Ru crystallites and nanocrystallites. The best CO tolerant catalyst is obtained by using a 12/1 ball-to-powder ratio and a 1:1:8 Pt:Ru:MgH₂ proportion of dispersive agent. It is made of 57 at.% of a nanocrystalline (3 nm) Pt₈₀Ru₂₀ alloy, 42 at.% of a nanocrystalline (3 nm) Ru phase and 1 at.% of a crystalline (∼40 nm) Ru phase. This catalyst has the lowest Pt/Ru surface ratio (0.9), the highest content in nanocrystalline Ru, and the highest ratio of oxidized/metallic Ru (3.3). Both Pt-Ru alloy and nanocrystalline Ru participate to the CO tolerance. The best CO tolerant catalyst is, however, not the best catalyst in DMFC. The latter is obtained by using a 4/1 ball-to-powder ratio and a 1:1:6 Pt:Ru:MgH₂ proportion. Within the starting 50:50 Pt-Ru nominal atomic ratio, no specific correlation was found between catalyst performance in DMFC and atomic surface Pt/Ru ratio, nor nanocrystalline Ru content, nor oxidized/metallic Ru ratio. Performances of the best ball-milled catalysts are compared to those of commercial unsupported catalysts in PEMFC and DMFC.     

Increasing the activity of Fe/N/C catalysts in PEM fuel cell cathodes using carbon blacks with a high-disordered carbon content

Fe/N/C catalysts for the reduction of oxygen in PEM fuel cells were prepared by pyrolyzing three series of iron acetate-impregnated developmental carbon blacks at 950 °C. The carbon supports used were derived from the N234, N330, and N650 commercial furnace grades. In this study, we tried to increase the performance of Fe/N/C-based cathode of PEM fuel cells by using the following two approaches: (1) increasing the number of catalytic sites on the carbon black either by optimizing the structural parameters of the pristine carbon supports or by increasing the initial metal content above 0.2 wt% Fe on the carbon support; (2) increasing the catalyst loading in the cathodic layer of a PEM fuel cell. For (1), we show, on the one hand, that optimizing the structural parameters of the pristine carbon support, in order to increase the number of catalytic sites, has its limits and that these limits have been reached for the present synthesis method of Fe/N/C catalysts. On the other hand, increasing the initial metal content above 0.2 wt% Fe leads to a decrease in catalytic activity. For (2), it is shown that increasing the catalyst loading per cm² of cathode well improves the performance of a cathode based on Fe/N/C catalysts in the kinetic region of the polarization curve. At lower potentials, a large improvement in the performance of these non-precious metal cathodes would occur if the mass transport properties in these electrodes were significantly increased.