Juan Herranz

Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells

H(2)-air polymer-electrolyte-membrane fuel cells are electrochemical power generators with potential vehicle propulsion applications. To help reduce their cost and encourage widespread use, research has focused on replacing the expensive Pt-based electrocatalysts in polymer-electrolyte-membrane fuel cells with a lower-cost alternative. Fe-based cathode catalysts are promising contenders, but their power density has been low compared with Pt-based cathodes, largely due to poor mass-transport properties. Here we report an iron-acetate/phenanthroline/zeolitic-imidazolate-framework-derived electrocatalyst with increased volumetric activity and enhanced mass-transport properties. The zeolitic-imidazolate-framework serves as a microporous host for phenanthroline and ferrous acetate to form a catalyst precursor that is subsequently heat treated. A cathode made with the best electrocatalyst from this work, tested in H(2)-O(2,) has a power density of 0.75 W cm(-2) at 0.6 V, a meaningful voltage for polymer-electrolyte-membrane fuel cells operation, comparable with that of a commercial Pt-based cathode tested under identical conditions.

Cross-Laboratory Experimental Study of Non-Noble-Metal Electrocatalysts for the Oxygen Reduction Reaction

Nine non-noble-metal catalysts (NNMCs) from five different laboratories were investigated for the catalysis of O(2) electroreduction in an acidic medium. The catalyst precursors were synthesized by wet impregnation, planetary ball milling, a foaming-agent technique, or a templating method. All catalyst precursors were subjected to one or more heat treatments at 700-1050 degrees C in an inert or reactive atmosphere. These catalysts underwent an identical set of electrochemical characterizations, including rotating-disk-electrode and polymer-electrolyte membrane fuel cell (PEMFC) tests and voltammetry under N(2). Ex situ characterization was comprised of X-ray photoelectron spectroscopy, neutron activation analysis, scanning electron microscopy, and N(2) adsorption and its analysis with an advanced model for carbonaceous powders. In PEMFC, several NNMCs display mass activities of 10-20 A g(-1) at 0.8 V versus a reversible hydrogen electrode, and one shows 80 A g(-1). The latter value corresponds to a volumetric activity of 19 A cm(-3) under reference conditions and represents one-seventh of the target defined by the U.S. Department of Energy for 2010 (130 A cm(-3)). The activity of all NNMCs is mainly governed by the microporous surface area, and active sites seem to be hosted in pore sizes of 5-15 A. The nitrogen and metal (iron or cobalt) seem to be present in sufficient amounts in the NNMCs and do not limit activity. The paper discusses probable directions for synthesizing more active NNMCs. This could be achieved through multiple pyrolysis steps, ball-milling steps, and control of the powder morphology by the addition of foaming agents and/or sulfur.

Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells

Fe-based catalytic sites for the reduction of oxygen in acidic medium have been identified by (57)Fe Mössbauer spectroscopy of Fe/N/C catalysts containing 0.03 to 1.55 wt% Fe, which were prepared by impregnation of iron acetate on carbon black followed by heat-treatment in NH(3) at 950 °C. Four different Fe-species were detected at all iron concentrations: three doublets assigned to molecular FeN(4)-like sites with their ferrous ions in a low (D1), intermediate (D2) or high (D3) spin state, and two other doublets assigned to a single Fe-species (D4 and D5) consisting of surface oxidized nitride nanoparticles (Fe(x)N, with x≤ 2.1). A fifth Fe-species appears only in those catalysts with Fe-contents ≥0.27 wt%. It is characterized by a very broad singlet, which has been assigned to incomplete FeN(4)-like sites that quickly dissolve in contact with an acid. Among the five Fe-species identified in these catalysts, only D1 and D3 display catalytic activity for the oxygen reduction reaction (ORR) in the acid medium, with D3 featuring a composite structure with a protonated neighbour basic nitrogen and being by far the most active species, with an estimated turn over frequency for the ORR of 11.4 e(-) per site per s at 0.8 V vs. RHE. Moreover, all D1 sites and between 1/2 and 2/3 of the D3 sites are acid-resistant. A scheme for the mechanism of site formation upon heat-treatment is also proposed. This identification of the ORR-active sites in these catalysts is of crucial importance to design strategies to improve the catalytic activity and stability of these materials.

New insights into the electrochemical hydrogen oxidation and evolution reaction mechanism

The effect of pH on the hydrogen oxidation and evolution reaction (HOR/HER) rates is addressed for the first time for the three most active monometallic surfaces: Pt, Ir, and Pd carbon-supported catalysts. Kinetic data were obtained for a proton exchange membrane fuel cell (PEMFC; pH ≈ 0) using the H2-pump mode and with a rotating disk electrode (RDE) in 0.1 M NaOH. Our findings point toward: (i) a similar ≈100-fold activity decrease on all these surfaces when going from low to high pH; (ii) a reaction rate controlled by the Volmer step on Pt/C; and (iii) the H-binding energy being the unique and sole descriptor for the HOR/HER in alkaline electrolytes. Based on a detailed discussion of our data, we propose a new mechanism for the HOR/HER on Pt-metals in alkaline electrolytes.

Unveiling N-protonation and anion-binding effects on Fe/N/C-catalysts for O2 reduction in PEM fuel cells

The high cost of proton-exchange-membrane fuel cells would be considerably reduced if platinumbased catalysts were replaced by iron-based substitutes, which have recently demonstrated comparable activity for oxygen reduction, but whose cause of activity decay in acidic medium has been elusive. Here, we reveal that the activity of Fe/N/C-catalysts prepared through a pyrolysis in NH3 is mostly imparted by acid-resistant FeN4-sites whose turnover frequency for the O2 reduction can be regulated by fine chemical changes of the catalyst surface. We show that surface N-groups protonate at pH 1 and subsequently bind anions. This results in decreased activity for the O2 reduction. The anions can be removed chemically or thermally, which restores the activity of acid-resistant FeN4-sites. These results are interpreted as an increased turnover frequency of FeN4-sites when specific surface N-groups protonate. These unprecedented findings provide new perspective for stabilizing the most active Fe/N/C-catalysts known to date.

Electrochemical CO2 Reduction - A Critical View on Fundamentals, Materials and Applications.

The electrochemical reduction of CO(2) has been extensively studied over the past decades. Nevertheless, this topic has been tackled so far only by using a very fundamental approach and mostly by trying to improve kinetics and selectivities toward specific products in half-cell configurations and liquid-based electrolytes. The main drawback of this approach is that, due to the low solubility of CO(2) in water, the maximum CO(2) reduction current which could be drawn falls in the range of 0.01-0.02 A cm(-2). This is at least an order of magnitude lower current density than the requirement to make CO(2)-electrolysis a technically and economically feasible option for transformation of CO(2) into chemical feedstock or fuel thereby closing the CO(2) cycle. This work attempts to give a short overview on the status of electrochemical CO(2) reduction with respect to challenges at the electrolysis cell as well as at the catalyst level. We will critically discuss possible pathways to increase both operating current density and conversion efficiency in order to close the gap with established energy conversion technologies.

Nanosized Carbon‐Supported Manganese Oxide Phases as Lithium–Oxygen Battery Cathode Catalysts

The poor discharge and recharge efficiency demonstrated by lithium–air batteries renders the search for highly active and inexpensive oxygen reduction and evolution catalysts crucial to the development of these energy‐storage and conversion devices. Previous works have shown that manganese oxides are promising lithium–oxygen cathode catalysts, which is in agreement with their remarkable activities for the reduction and evolution of oxygen in aqueous media. Motivated by these resembling catalytic behaviors, we prepared and characterized a number of manganese oxide modifications directly on carbon black and attempted to correlate their oxygen reduction and evolution activities in aprotic and aqueous electrolytes. Although our results cannot confirm this correlation, they provide valuable insight into the reaction mechanisms at play in each medium. More precisely, in 0.1 M potassium hydroxide, the reduction of oxygen is related to the reduction of a manganese(III) intermediate whereas the oxidation of hydrogen peroxide (which was regarded as a mimic of the lithium peroxide produced upon lithium–oxygen battery discharge) correlates with the transition between manganese(II) and manganese(III) phases. In the aprotic medium, manganese oxide cathodes prefilled with lithium peroxide showed a strong catalytic effect but were not active in the oxidation of lithium peroxide produced in the previous discharge. This discrepancy is thought to arise from the stark differences in the sizes and morphologies of the lithium peroxide involved in each test, which implies that the catalytic activity of a material for the oxidation of lithium peroxide prefilled on electrodes is not indicative of its behavior in the charging of a real lithium–oxygen cell.

Metal-Precursor Adsorption Effects on Fe-Based Catalysts for Oxygen Reduction in PEM Fuel Cells

Fe-based electrocatalysts for the reduction of oxygen in polymer electrolyte membrane (PEM) fuel cells have been prepared by adsorbing either Fe 2+ or Fe(CN) 4- 6 ions on two carbon blacks to determine if their maximum activity is limited by (i) the maximum number of micropores available to host catalytic sites in the support or by (ii) the maximum number of ions able to be adsorbed on the carbon. The two carbon supports having the same microporous surface area, one etched in air and the other in NH 3 , were derived from the same carbon black (N234). Air-etched N234 is more acidic in nature as it possesses carboxylic functionalities that can adsorb Fe 2+ , while NH 3 -etched N234 possesses both pyridinic and carboxylic functionalities that can adsorb either Fe(CN) 4- 6 or Fe 2+ . Catalysts were prepared by heat-treating, in pure NH 3 , the materials resulting from Fe 2+ or Fe(CN) 4- 6 adsorption on both etched carbons. It is concluded that, when catalysts are prepared in pure NH 3 , the catalytic activity is only governed by the number of micropores, having a size between 0.8 and 2.0 nm, that are available to host the catalytic sites in the porous volume of the carbon support, because Fe ion uptake by adsorption is never the limiting factor.

Unsupported Pt-Ni Aerogels with Enhanced High Current Performance and Durability in Fuel Cell Cathodes

Highly active and durable oxygen reduction catalysts are needed to reduce the costs and enhance the service life of polymer electrolyte fuel cells (PEFCs). This can be accomplished by alloying Pt with a transition metal (for example Ni) and by eliminating the corrodible, carbon-based catalyst support. However, materials combining both approaches have seldom been implemented in PEFC cathodes. In this work, an unsupported Pt-Ni alloy nanochain ensemble (aerogel) demonstrates high current PEFC performance commensurate with that of a carbon-supported benchmark (Pt/C) following optimization of the aerogels catalyst layer (CL) structure. The latter is accomplished using a soluble filler to shift the CLs pore size distribution towards larger pores which improves reactant and product transport. Chiefly, the optimized PEFC aerogel cathodes display a circa 2.5-fold larger surface-specific ORR activity than Pt/C and maintain 90 % of the initial activity after an accelerated stress test (vs. 40 % for Pt/C).

Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis

Tuning the surface structure at the atomic level is of primary importance to simultaneously meet the electrocatalytic performance and stability criteria required for the development of low-temperature proton-exchange membrane fuel cells (PEMFCs). However, transposing the knowledge acquired on extended, model surfaces to practical nanomaterials remains highly challenging. Here, we propose ‘surface distortion’ as a novel structural descriptor, which is able to reconciliate and unify seemingly opposing notions and contradictory experimental observations in regards to the electrocatalytic oxygen reduction reaction (ORR) reactivity. Beyond its unifying character, we show that surface distortion is pivotal to rationalize the electrocatalytic properties of state-of-the-art of PtNi/C nanocatalysts with distinct atomic composition, size, shape and degree of surface defectiveness under a simulated PEMFC cathode environment. Our study brings fundamental and practical insights into the role of surface defects in electrocatalysis and highlights strategies to design more durable ORR nanocatalysts.Tuning surface structure is key for electrocatalytic performance and stability of proton-exchange membrane fuel cells. Surface distortion as a structural descriptor can help to clarify the role of surface defects and to design enhanced nanocatalysts.