Platinum-group-metal free catalysts have been widely studied in the last decade as an alternative to Pt, employed in fuel cells. Several carbon precursors have been investigated as carbon matrix for ...iron-nitrogen-carbon (Fe–N–C) catalysts, characterized by a large amount of micropores, fundamental to create Fe-Nx-C active sites. Nonetheless, it is also acknowledged that wider pores are needed to facilitate mass transfer of oxygen/water (reagent/product of fuel cells) towards/from the active sites. Organic xerogels are known as easily tunable materials, that allow doping with a variety of heteroatoms. The present manuscript presents an investigation on the use of organic xerogels combined with iron and nitrogen in a single-step to obtain Fe–N-CXG electro-catalysts for the oxygen reduction reaction (ORR) of proton exchange membrane fuel cells. Several features of both organic xerogels and catalysts on the ORR activity are assessed: the textural properties of the organic xerogel, the iron loading of the Fe–N–C catalysts and the effect of acid-leaching of the catalysts. The present study proves the feasibility of using organic xerogels as carbon precursor to obtain PGM-free catalysts in an easy manner and scalable single-step synthesis. Catalysts obtained from organic xerogels synthesized at mildly acid pHs (5.8 and 6), with a nominal iron loading of 2 wt%, and subjected to two sets of acid leaching/thermal treatments, present enhanced catalytic activity towards the ORR.
•Organic carbon xerogels are investigated as carbon matrix for Fe–N–C catalysts.•One-step and template-free synthesis of Fe–N–C catalysts is proposed.•Balanced iron doping creates enough active sites without impacting porosity.•Acid/thermal treatments enhance catalysts improving chemical properties.•High mesopore volume organic xerogels (pH 5.8) yield highly active ORR catalysts.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The present research aims to assess the durability of a single cell formed by a commercial high-temperature membrane electrode assembly (MEA) and Al bipolar plates (Al-BPPs) coated with Ni-P. To this ...end, an accelerated degradation test based on voltage load cycles is carried out, and the effects of the degradation on the MEA and its impact on the Al-coated bipolar plates are analyzed. They are compared with the results obtained testing a similar cell formed by the same MEA with graphite plates. MEAs from both cells were analyzed by different characterization techniques before and after the degradation tests (XRD, SEM, TEM). The performance of the Al-based cell is initially better, but it suffers a faster deterioration mainly due to the degradation of the Ni-P surface coating. A green deposit is formed, probably due to the chemical reaction of the phosphoric acid leached from the MEA. These deposits cause an increase in the contact resistance of the plates, local channel blockages and, eventually, a larger degradation. This work proves that PBI membranes still need to be improved to ensure their long-term durability.
•Ni-P-coated Al bipolar plates are assessed for High Temperature PEM fuel cells.•MEA degradation is induced by accelerated stress tests based on voltage load cycles.•Graphite bipolar plates are also tested for the sake of comparison.•Cell with Al-plates presented a better initial performance but a higher degradation.•Acid leaching from the MEA is responsible for both MEA and Al-plates degradation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•Degradation caused by a moderate starvation of the reactant gases in a cell is reversible.•Damages produced by a severe gas starvation are irreversible.•MEA degradation caused by gas starvation ...increases the loss of phosphoric acid from the polymer.•The effects of gas starvation on a cell do not propagate to the neighboring ones.•A PEM fuel cell stack can still work with a MEA severely damaged due to gas starvation.
Fuel and oxidant starvation are amongst the most critical phenomena affecting fuel cell durability. Reactant starvation during proton exchange membrane fuel cell operation can cause serious irreversible damages. In the present research, the effect of a selective induced starvation of reactant gases on the performance and degradation of a high-temperature PEM fuel cell is studied. A specifically designed 5-cell stack is used, which enables varying the gas supplied to any of the individual cells. The particularity of selectively starving only one cell in a controlled manner is one of the novelties of this study. Two different tests are performed actuating on the central cell (cell 3). They are denoted as moderate and severe starvation, depending on the intensity of the limitation imposed to the gases flowrate. Some relevant and novel results are obtained. It is verified that the performance degradation caused by a moderate starvation of the reactant gases in a cell is reversible. On the contrary, the damages caused by an aggressive gas starvation, which is also maintained in time (30 min), are irreversible. However, the behavior of the rest of the cells is barely affected by the gas starvation to cell 3. Thus, the other major novelty of the present work is the evidence/proof of the ability of a stack with a starved and highly degraded cell, to continue operating, although with a drastic reduction in the total generated current.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Platinum group metal-free catalysts have been intensively investigated in the last decades as an alternative to platinum with the aim of lowering the cost of polymer electrolyte fuel cells. In ...particular, iron-nitrogen-carbon (Fe-N-C) has proved to be the most active towards the oxygen reduction reaction. For practical application, a hierarchical pore structure is required, with micropores favouring the creation of active sites and larger pores (meso- and macropores) facilitating the mass transport. In this work, carbon xerogels are investigated to hosting iron and nitrogen species obtained by a template-free method. The introduction of nitrogen in a one-step polymerization of urea with resorcinol and formaldehyde is investigated for the first time in this field by varying the relative content of reactants. The urea/resorcinol ratio greatly influences the pore structure of the Fe-N-C catalyst and the ORR electrocatalytic activity thereof. The ORR activity is favored for a balanced urea/resorcinol ratio where porosity is well developed and relatively high iron and nitrogen contents are incorporated to the carbon xerogel. In acid (0.5 M H2SO4), the onset potential is 0.82 V vs. RHE, with a number of exchanged electrons very close to 4 (i.e. full conversion to water) and low Tafel slope of 71 mV dec−1, for the most active catalyst of the series, possessing the best compromise of iron and nitrogen active sites. Fuel cell tests corroborate that the catalyst with the most developed porous structure shows the best performance.
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•N-doped carbon xerogels serve as carbon matrix for Fe-N-C catalysts.•Urea is introduced during gel polymerization to dope CXG with nitrogen.•A balanced urea amount leads to proper porosity including both micro and mesopores.•Pyridinic nitrogen and Fe concentration rely on N/C ratio.•High content of pyridinic N and Fe are key for enhanced ORR catalytic activity.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Toxicity is an important factor in failed drug development, and its efficient identification and prediction is a major challenge in drug discovery. We have explored the potential of microscopy images ...of fluorescently labeled nuclei for the prediction of toxicity based on nucleus pattern recognition. Deep learning algorithms obtain abstract representations of images through an automated process, allowing them to efficiently classify complex patterns, and have become the state-of-the art in machine learning for computer vision. Here, deep convolutional neural networks (CNN) were trained to predict toxicity from images of DAPI-stained cells pre-treated with a set of drugs with differing toxicity mechanisms. Different cropping strategies were used for training CNN models, the nuclei-cropping-based Tox_CNN model outperformed other models classifying cells according to health status. Tox_CNN allowed automated extraction of feature maps that clustered compounds according to mechanism of action. Moreover, fully automated region-based CNNs (RCNN) were implemented to detect and classify nuclei, providing per-cell toxicity prediction from raw screening images. We validated both Tox_(R)CNN models for detection of pre-lethal toxicity from nuclei images, which proved to be more sensitive and have broader specificity than established toxicity readouts. These models predicted toxicity of drugs with mechanisms of action other than those they had been trained for and were successfully transferred to other cell assays. The Tox_(R)CNN models thus provide robust, sensitive, and cost-effective tools for in vitro screening of drug-induced toxicity. These models can be adopted for compound prioritization in drug screening campaigns, and could thereby increase the efficiency of drug discovery.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Fe−N−C catalysts are an interesting option for polymer electrolyte fuel cells due to their low cost and high activity towards the oxygen reduction reaction (ORR). Since Fe−N−C active sites are ...preferentially formed in the micropores of the carbon matrix, increasing the microporosity is highly appealing. In this work, carbon xerogels (CXG) were activated by physical and chemical methods to favor the formation of micropores, used as carbon matrices for Fe−N−C catalysts, and investigated for the ORR. The catalysts were characterized by solid‐state techniques to determine chemical composition and pore structure. Physical activation increased microporosity up to 2‐fold leading to catalysts with a larger density of active sites (more than twice iron and nitrogen uptake, pyridinic N and Nx−Fe). This entailed a higher ORR intrinsic activity determined in a 3‐electrode cell (80 mV better half‐wave potential). At the cathode of a fuel cell, the catalysts based on activated carbon materials showed 26 % lower power density ascribed to a more hydrophilic surface, causing a larger extent of flooding of the electrode that counterbalances the higher intrinsic activity. Interestingly, a more stable behavior was observed for the activated catalysts, with up to 2‐fold better relative power density retention after 20‐hour operation.
Activated carbon xerogels were studied as matrix for Fe−N−C catalysts. The increased microporosity lead to catalysts with a larger density of active sites, achieving up to more than twice iron and nitrogen uptake, and consequently, a higher ORR intrinsic activity. Whereas, fuel cell power density is negatively affected by a more hydrophilic character, but stability enhances with activation.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Atomically dispersed Fe-N-C catalysts for the oxygen reduction reaction (ORR) have been synthesized with a template-free method using carbon xerogels (CXG) as a porous matrix. The porosity of the ...CXGs is easily tunable through slight variations in the synthesis procedure. In this work, CXGs are prepared by formaldehyde and resorcinol polymerization, modifying the pH during the process. Materials with a broad range of porous structures are obtained: from non-porous to micro-/meso-/macroporous materials. The porous properties of CXG have a direct effect on Fe-N-CXG activity against ORR in an acidic medium (0.5 M H
SO
). Macropores and wide mesopores are vital to favor the mass transport of reagents to the active sites available in the micropores, while narrower mesopores can generate additional tortuosity. The role of microporosity is investigated by comparing two Fe-N-C catalysts using the same CXG as the matrix but following a different Fe and N doping procedure. In one case, the carbonization of CXG occurs rapidly and simultaneously with Fe and N doping, whereas in the other case it proceeds slowly, under controlled conditions and before the doping process, resulting in the formation of more micropores and active sites and achieving higher activity in a three-electrode cell and a better durability during fuel cell measurements. This work proves the feasibility of the template-free method using CXG as a carbon matrix for Fe-N-C catalysts, with the novelty of the controlled porous properties of the carbon material and its effect on the catalytic activity of the Fe-N-C catalyst. Moreover, the results obtained highlight the importance of the carbon matrix's porous structure in influencing the activity of Fe-N-C catalysts against ORR.
The present study was aimed at analysing the main atmospheric dynamic mechanisms associated with the occurrence of intense rainfall events above the Huancayo observatory (12.05°S, 75.32°W, 3313 m ...asl) in the central Andes of Perú (Mantaro valley) from January 2018 to April 2019. To identify the rainfall events, we used a set of instruments from the laboratory of physics, microphysics and radiation (LAMAR) composed by in-situ pluviometric observations, satellite remote sensing data (GPM), Cloud Radar (MIRA-35c), Boundary Layer Tropospheric Radar (BLTR) and downscaling model simulations with WRF (resolutions: 18 km, 6 km and 2 km) and ARPS (0.5 km) models to analyse the dynamics of the atmosphere for the synoptic, meso and local processes that control the occurrence of these rainfall events. The results showed that all intense rainfall events are associated with the presence of thermal meso-scale circulations that transport moisture fluxes through passes with gentle slopes along both sides of the Andes. The easterly moisture fluxes come in from the South America Low Level Jet (SALLJ) and the westerly moisture fluxes from the Pacific Ocean. The arrival of these moisture flows to regions within the Mantaro valley depends on their coupling with the circulations at medium and high levels of the atmosphere. At the synoptic scale, the results show that the rainfall events can be separated into two groups: the first one associated with westerly circulations (WC) at the mid and upper levels of the atmosphere, generated by the weakening and eastern displacement of the anticyclonic Bolivian high-North east low (BH-NE) system, and the second associated with easterly circulations (EC) at the mid and upper levels of the atmosphere, generated by the intensification of the BH-NE system. The observed and simulated results showed that multicell convective systems of WC events are more extensive and deeper than EC events. This situation can be explained as the convergence of moisture fluxes from opposite directions occurred within the Mantaro basin for WC events. In contrast, for EC events, the convergence develops at the east Andes mountain range, following which the multicell storm system propagates westward, driven by easterly circulations. The EC events occur mostly in the summer months, while the WC events occur mostly in the autumn and spring months. Moreover, apparently the inertia gravity waves (IGWs) formed in the Amazon basin transport moisture and energy to the central Andes plateau and intensify the convection processes.
•The study analyzes the main atmospheric dynamic conditions that generate intense rainfall events in the Peruvian central Andes.•All intense rainfall events are associated with thermal meso-scale circulations that transport moisture fluxes.•Easterly moisture fluxes coming from the South America Low Level Jet and the westerlies from the Pacific Ocean.•Rainfall events were separated into two groups: events with easterly circulations (EC) and with westerly circulations (WC)•The WC events were more extensive and deeper than EC events
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
The present study presents a detailed analysis of the diurnal and monthly cycles the surface boundary layer and of surface energy balance in a sparse natural vegetation canopy on Huancayo observatory ...(12.04 ∘ S, 75.32 ∘ W, 3313 m ASL), which is located in the central Andes of Perú (Mantaro Valley) during an entire year (May 2018–April 2019). We used a set of meteorological sensors (temperature, relative humidity, wind) installed in a gradient tower 30 m high, a set of radiative sensors to measure all irradiance components, and a set of tensiometers and heat flux plate to measure soil moisture, soil temperatures and soil heat flux. To estimate turbulent energy fluxes (sensible and latent), two flux–gradient methods: the aerodynamic method and the Bowen-ratio energy-balance method were used. The ground heat flux at surface was estimated using a molecular heat transfer equation. The results show minimum mean monthly temperatures and more stable conditions were observed in June and July before sunrise, while maximum mean monthly temperatures in October and November and more unstable conditions in February and March. From May to August inverted water vapor profiles near the surface were observed (more intense in July) at night hours, which indicate a transfer of water vapor as dewfall on the surface. The patterns of wind direction indicate well-defined mountain–valley circulation from south-east to south-west especially in fall–winter months (April–August). The maximum mean monthly sensible heat fluxes were found in June and September while minimum in February and March. Maximum mean monthly latent heat fluxes were found in February and March while minimum in June and July. The surface albedo and the Bowen ratio indicate semi-arid conditions in wet summer months and extreme arid conditions in dry winter months. The comparisons between sensible heat flux ( Q H ) and latent heat flux ( Q E ), estimated by the two methods show a good agreement (R 2 above 0.8). The comparison between available energy and the sum of Q E and Q H fluxes shows a good level of agreement (R 2 = 0.86) with important imbalance contributions after sunrise and around noon, probably by advection processes generated by heterogeneities on the surface around the Huancayo observatory and intensified by the mountain–valley circulation.
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