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The energy efficiency of polymer electrolyte membrane fuel cells is mainly limited by overpotentials related to the oxygen reduction reaction (ORR). In this paper, we present new platinum alloys which are active for the ORR and based on alloying Pt with very abundant elements, such as Ca. Theoretical calculations suggested that Pt5Ca and Pt5Sr should be active for the ORR. Electrochemical measurements show that the activity of sputter-cleaned polycrystalline Pt5Ca and Pt5Sr electrodes is enhanced by a factor of 5–7 relative to polycrystalline Pt. Accelerated stability testing shows that after 10,000 electrochemical cycles, the alloys still retain over half their activity. The stability is thus not quite on par with the similar Pt-lanthanide alloys, possibly due to the somewhat lower heat of formation.

Electrolysis could enable the large-scale conversion of CO2 to fuels and small molecules. This perspective discusses the state-of-the-art understanding of CO2 and CO reduction electrocatalysis and provides an overview of the most promising approaches undertaken thus far. We set to explore “bifunctional” catalysts using Au–Cd based alloys inspired by theoretical modelling. Density functional theory calculations suggest more favourable thermodynamics for CO2 reduction to CO and methanol on mixed Au–Cd sites on Au3Cd relative to similar values on Au. We use various tools to test the bulk and surface alloys experimentally. We find that Au3Cd in neutral media exhibits lower CO evolution activity than Au, and Au–Cd alloys also show negligible activity for CO reduction in alkaline media. This indicates that the mixed Cd–Au sites predicted to be catalytically active are not present in the sample. The catalytic performance is most consistent with Au-terminated step surface on a bulk alloy, possibly formed through adsorbate-induced restructuring. We highlight that future bimetallic catalysts must consider potential-dependent surface restructuring effects caused by reaction intermediates.

PtxY and PtxGd exhibit exceptionally high activity for oxygen reduction, both in the polycrystalline form and the nanoparticulate form. In order to understand the origin of the enhanced activity of these alloys, we have investigated thin films of these alloys on bulk Pt(111) crystals, i.e. Y/Pt(111) and Gd/Pt(111). These surfaces exhibit a 4-fold improvement over Pt(111). We observe the formation of a thick Pt overlayer after the electrochemical measurements, both on Y/Pt(111) and Gd/Pt(111). Using surface sensitive X-ray diffraction we revealed that crystalline closely packed Pt overlayers were formed. The diffraction experiments showed that the strain and crystallinity of the overlayers are strongly dependent on the electrochemical treatment, and in general show lateral compression.

The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of low-temperature fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)-lanthanide and Pt-alkaline earth electrodes, Pt5M, where M is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycrystalline Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR activity versus the bulk lattice parameter follows a high peaked "volcano" relation. We demonstrate how the lanthanide contraction can be used to control strain effects and tune the activity, stability, and reactivity of these materials.

Water splitting is hindered by the sluggish kinetics of the oxygen evolution reaction (OER). The choice of materials for this reaction in acid is limited to the platinum group metals; high loading required of these scarce and expensive elements severely limit the scalability of such technology. Ruthenium oxide is among the best catalysts for OER, however the reported activity and stability can vary tremendously depending on the preparation conditions and pre-treatment. Herein, we investigate the effect of oxidation treatment on mass-selected Ru nanoparticles in the size range between 2 and 10 nm. The effect of two distinct oxidation pre-treatments on the activity and stability have been investigated: (1) thermal oxidation; and (2) oxidation with an oxygen plasma under vacuum. We report that activity and stability can be tuned by using different oxidation pre-treatments. Thermally oxidized particles exhibited the lowest activity, although over an order of magnitude higher than the state of the art, and the highest stability. Plasma-treated particles showed intermediate performance between as-deposited and thermally oxidized NPs.

Mass-selected platinum–gadolinium alloy nanoparticles (PtxGd NPs) are synthesized for the first time as oxygen reduction reaction (ORR) electrocatalysts using the gas aggregation technique, under ultrahigh vacuum (UHV) conditions. The morphology of the PtxGd catalysts is characterized, and their catalytic performance toward the ORR is assessed in acidic media using a half-cell configuration. The PtxGd 8-nm catalyst shows a high activity (3.6 A (mg Pt)−1), surpassing the highest activity reached so far with PtxY NP catalysts. In addition, the optimum PtxGd catalyst also presents high stability, as suggested by the accelerated stability tests under ORR potential cycling. Extended X-ray absorption fine structure (EXAFS) spectroscopy measurements confirm that as-prepared PtxGd NPs are compressively strained, relative to pure Pt, and that a PtxGd core/Pt-rich shell structure is adopted after partial Gd leaching. The activity correlates strongly with the compressive strain. On that basis, we propose that the ORR enhancement is due to the compressive strain within the Pt shell induced by the alloy core. The results herein confirm the suitability of PtxGd NPs as cathode nanocatalysts for proton exchange membrane fuel cells (PEMFCs).

Stabilizing efficient photoabsorbers for solar water splitting has recently shown significant progress with the development of various protection layers. Suitable protection layers for tandem devices should be conductive, transparent, and stable in strongly acidic or alkaline solutions. This paper shows that under certain conditions n-type semiconductors, such as TiO2, can be used as protection layers for Si-based photoanodes. It also provides evidence that even in a photoanode assembly TiO2 is conducting only electrons (not holes as in p-type protection layers), and therefore TiO2 can be described as a simple ohmic contact. This renders n-type semiconductors, such as TiO2, to be versatile and simple protection layers, which can be used for photoanodes and as previously shown for photocathodes. The ohmic behavior of n-type TiO2 in a Si/TiO2–photoanode assembly is demonstrated under dark and illuminated conditions by performing the oxygen evolution reaction (OER) and using the Fe(II)/Fe(III) redox couple. ...

The high precious metal loading and high overpotential of the oxygen evolution reaction (OER) prevents the widespread utilization of polymer electrolyte membrane (PEM) water electrolyzers. Herein we explore the OER activity and stability in acidic electrolyte of a combined IrOx/RuO2 system consisting of RuO2 thin films with sub-monolayer (1, 2 and 4 Å) amounts of IrOx deposited on top. Operando extended X-ray absorption fine structure (EXAFS) on the Ir L-3 edge revealed a rutile type IrO2 structure with some Ir sites occupied by Ru, IrOx being at the surface of the RuO2 thin film. We monitor corrosion on IrOx/RuO2 thin films by combining electrochemical quartz crystal microbalance (EQCM) with inductively coupled mass spectrometry (ICP-MS). We elucidate the importance of sub-monolayer surface IrOx in minimizing Ru dissolution. Our work shows that we can tune the surface properties of active OER catalysts such as RuO2, aiming to achieve higher electrocatalytic stability in PEM electrolyzers.

The high precious metal loading and high overpotential of the oxygen evolution reaction (OER) prevents the widespread utilization of polymer electrolyte membrane (PEM) water electrolyzers. Herein we explore the OER activity and stability in acidic electrolyte of a combined IrO

Because of the rising need for energy storage, potentially facilitated by electrolyzers, improvements to the catalysis of the oxygen evolution reaction (OER) become increasingly relevant. Standardized protocols have been developed for determining critical figures of merit, such as the electrochemical surface area, mass activity and specific activity. Even so, when new and more active catalysts are reported, the catalyst stability tends to play a minor role. In this work, we monitor corrosion on RuO2 and MnOx by combining the electrochemical quartz crystal microbalance (EQCM) with inductively coupled plasma mass spectrometry (ICP–MS). We show that a meaningful estimation of the stability cannot be achieved based on purely electrochemical tests. On the catalysts tested, the anodic dissolution current was four orders of magnitude lower than the total current. We propose that even if long-term testing cannot be replaced, a useful evaluation of the stability can be achieved with short-term tests by using EQCM or ICP–MS.

Low-temperature fuel cells are limited by the oxygen reduction reaction, and their widespread implementation in automotive vehicles is hindered by the cost of platinum, currently the best-known catalyst for reducing oxygen in terms of both activity and stability. One solution is to decrease the amount of platinum required, for example by alloying, but without detrimentally affecting its properties. The alloy PtxY is known to be active and stable, but its synthesis in nanoparticulate form has proved challenging, which limits its further study. Herein we demonstrate the synthesis, characterization and catalyst testing of model PtxY nanoparticles prepared through the gas-aggregation technique. The catalysts reported here are highly active, with a mass activity of up to 3.05 A mgPt−1 at 0.9 V versus a reversible hydrogen electrode. Using a variety of characterization techniques, we show that the enhanced activity of PtxY over elemental platinum results exclusively from a compressive strain exerted on the platinum surface atoms by the alloy core. The widespread use of fuel cells requires improved catalysts to reduce oxygen efficiently at the cathode. It is shown that model, well-characterized size-selected PtxY nanoparticles can be synthesized by the gas aggregation technique, and that they are highly active for this reaction.

Mass-selected nanoparticles can be conveniently produced using magnetron sputtering and aggregation techniques. However, numerous pitfalls can compromise the quality of the samples, e.g. double or triple mass production, dendritic structure formation or unpredicted particle composition. We stress the importance of transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) for verifying the morphology, size distribution and chemical composition of the nanoparticles. Furthermore, we correlate the morphology and the composition of the PtxY nanoparticles with their catalytic properties for the oxygen reduction reaction. Finally, we propose a completely general diagnostic method, which allows us to minimize the occurrence of undesired masses.

We have studied the electrochemical reduction of CO2 on Cu overlayers on Pt(111) and Pt(211) surfaces. These systems were chosen to investigate the effect of strain on the catalytic activity of Cu surfaces and to obtain information about the role of steps in this process. The selectivity toward hydrocarbons on the copper overlayers is much lower than on polycrystalline copper due to a higher selectivity for hydrogen evolution. With the aim of understanding the lower activity toward CO2 electroreduction of the Cu overlayers, we also studied the surfaces under reaction condition using electrochemical scanning tunneling microscopy (EC-STM). In the presence of CO, the Cu overlayer changes from a flat to a granular structure exposing part of the Pt surface. The exposed Pt surface accounts for the high selectivity of these structures toward hydrogen evolution. These results illustrate the dynamic nature of the surface under reaction conditions and that in situ measurements are crucial to understand catalytic ac...

The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of low-temperature fuel cells in automotive vehicles. We have studied the ORR on eight platinum (Pt)–lanthanide and Pt-alkaline earth electrodes, Pt5M, where M is lanthanum, cerium, samarium, gadolinium, terbium, dysprosium, thulium, or calcium. The materials are among the most active polycrystalline Pt-based catalysts reported, presenting activity enhancement by a factor of 3 to 6 over Pt. The active phase consists of a Pt overlayer formed by acid leaching. The ORR activity versus the bulk lattice parameter follows a high peaked “volcano” relation. We demonstrate how the lanthanide contraction can be used to control strain effects and tune the activity, stability, and reactivity of these materials.

The activity and stability of Pt(5)Gd for the oxygen reduction reaction (ORR) have been studied, using a combination of electrochemical measurements, angle-resolved X-ray photoelectron spectroscopy (AR-XPS), and density functional theory calculations. Sputter-cleaned, polycrystalline Pt(5)Gd shows a 5-fold increase in ORR activity, relative to pure Pt at 0.9 V, approaching the most active in the literature for catalysts prepared in this way. AR-XPS profiles after electrochemical measurements in 0.1 M HClO(4) show the formation of a thick Pt overlayer on the bulk Pt(5)Gd, and the enhanced ORR activity can be explained by means of compressive strain effects. Furthermore, these novel bimetallic electrocatalysts are highly stable, which, in combination with their enhanced activity, makes them very promising for the development of new cathode catalysts for fuel cells.

The increasing need for shifting to renewable feedstocks in the chemical industry has driven research toward using green aerobic, selective oxidation reactions to produce bulk chemicals. Here, we report the use of a ruthenium mixed oxide/hydroxide (RuO x ) on different support materials for the selective aerobic oxidation of ethanol to acetic acid. The RuO x was deposited onto different oxide supports using a new gas-phase reaction, which in all cases resulted in homogeneous nanoparticulate films. The RuO x particle size ranged from 0.3 to 1.5 nm. The catalytic activity was evaluated on TiO 2 , Mg 6 Al 2 (CO 3 )(OH) 16 · 4(H 2 O), MgAl 2 O 4 , Na 2 Ti 6 O 13 nanotubes, ZnO, γ -Al 2 O 3 , WO 3 , CeO 2 , and Ce 0.5 Zr 0.5 O 2 supports. The CeO 2 supported RuO x had the highest activity, and selectivity toward acetic acid, of all the materials when normalized with respect to Ru-loading. This high activity was independent of the surface area of the support and the loading of RuO x under the tested conditions. This was attributed to the highly uniform size of the RuO x deposits, demonstrating that the deposition is suitable for producing small nanoparticles at high loadings. To elucidate the reason for the promotional effect of CeO 2 , Ce 0.5 Zr 0.5 O 2 was investigated as a high oxygen storage capacity support, however, this did not result in higher catalytic activity. The high activity of CeO 2 supports compared to the low activity ZnO appear correlated to the presence of high valence Ru(VI) species analogous to that observed in literature.

Size-selected 9 nm PtxY nanoparticles have recently shown an outstanding catalytic activity for the oxygen reduction reaction, representing a promising cathode catalyst for proton exchange membrane fuel cells (PEMFCs). Studying their electrochemical dealloying is a fundamental step towards the understanding of both their activity and stability. Herein, size-selected 9 nm PtxY nanoparticles have been deposited on the cathode side of a PEMFC specifically designed for in situ ambient pressure X-ray photoelectron spectroscopy (APXPS). The dealloying mechanism was followed in situ for the first time. It proceeds through the progressive oxidation of alloyed Y atoms, soon leading to the accumulation of Y3+ cations at the cathode. Acid leaching with sulfuric acid is capable of accelerating the dealloying process and removing these Y3+ cations which might cause long term degradation of the membrane. The use of APXPS under near operating conditions allowed observing the population of oxygenated surface species as a function of the electrochemical potential. Similar to the case of pure Pt nanoparticles, non-hydrated hydroxide plays a key role in the ORR catalytic process., Danish Council for Strategic Research's project NACORR; Danish National Research Foundation's Center for Individual Nanoparticle Functionality; Joint Center for Artificial Photosynthesis Award; Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST)

We have prepared an yttrium modified Pt(111) single crystal under ultra-high vacuum conditions, simulating a bulk alloy. A Pt overlayer is formed upon annealing the crystal above 800 K. The annealed structure binds CO weaker than Pt(111), with a pronounced peak at 295 K in the temperature programmed desorption of CO. When depositing a large amount of yttrium at 1173 K, a (1.88 × 1.88)R30° structure relative to Pt(111) was observed by low energy electron diffraction. Such an electron diffraction pattern could correspond to a (2 × 2)R30° structure under 6% compressive strain. This structure is in agreement with the structure of the vacancies in a Pt Kagome layer in Pt5Y rotated 30° with respect to the bulk of the Pt(111). The Pt overlayer is relatively stable in air; however, after performing oxygen reduction activity measurements in an electrochemical cell, a thick Pt overlayer was measured by the angle resolved X-ray photoelectron spectroscopy depth profile. The activity of the annealed Y/Pt(111) for the oxygen reduction reaction was similar to that of polycrystalline Pt3Y.

The direct electrochemical synthesis of hydrogen peroxide is a promising alternative to currently used batch synthesis methods. Its industrial viability is dependent on the effective catalysis of the reduction of oxygen at the cathode. Herein, we study the factors controlling activity and selectivity for H2O2 production on metal surfaces. Using this approach, we discover two new catalysts for the reaction, Ag–Hg and Pd–Hg, with unique electrocatalytic properties both of which exhibit performance that far exceeds the current state-of-the art.

A new MoS2 protected n(+)p-junction Si photocathode for the renewable H2 evolution is presented here. MoS2 acts as both a protective and an electrocatalytic layer, allowing H2 evolution at 0 V vs. RHE for more than 5 days. Using a MoSx surface layer decreases the overpotential for H2 evolution by 200 mV.

Future generations require more efficient and localized processes for energy conversion and chemical synthesis. The continuous on-site production of hydrogen peroxide would provide an attractive alternative to the present state-of-the-art, which is based on the complex anthraquinone process. The electrochemical reduction of oxygen to hydrogen peroxide is a particularly promising means of achieving this aim. However, it would require active, selective and stable materials to catalyse the reaction. Although progress has been made in this respect, further improvements through the development of new electrocatalysts are needed. Using density functional theory calculations, we identify Pt-Hg as a promising candidate. Electrochemical measurements on Pt-Hg nanoparticles show more than an order of magnitude improvement in mass activity, that is, A g(-1) precious metal, for H2O2 production, over the best performing catalysts in the literature.

Polymer Electrolyte Membrane Fuel Cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the Oxygen Reduction Reaction (ORR) at the PEMFC cathode prevents the commercialisation of this technology. Improving the activity of Pt by alloying it with other metals could decrease the loading of Pt at the cathode to a level comparable to Pt-group metal loading in internal combustion engines. PtxY and PtxGd exhibit exceptionally high activity for oxygen reduction, both in the polycrystalline form and the nanoparticulate form. [1,2,3,4]. Moreover, their negative alloying energy may make them inherently less prone to degradation via dealloying than the more commonly investigated alloys of Pt and late transition metals such as Ni, Co, Fe and Cu. In order to understand the origin of the enhanced activity of these alloys, we have investigated Y/Pt(111) [5] and Gd/Pt(111) single crystals, formed by depositing large amounts of Y and Gd on Pt(111) single crystals under Ultra-High Vacuum (UHV) conditions and annealing to high temperatures. We subsequently characterised the surface using low energy electron diffraction, ion scattering spectroscopy and temperature programmed desorption of CO. After the characterization in UHV, the ORR activity was measured. Angle resolved X-ray photoelectron spectroscopy measurements were carried out after the electrochemical measurements. These experiments revealed, that thick platinum overlayers had been formed, and that the structure formed under reaction conditions was significantly different from our initial expectations. The structures of the overlayers were investigated using surface sensitive X-ray diffraction using synchrotron radiation, and correlated to the oxygen reduction activity. [1] M. Escudero-Escribano, A. Verdaguer-Casadevall, P. Malacrida, U. Grønbjerg, B. P. Knudsen, A. K. Jepsen, J. Rossmeisl, I. E. L. Stephens, and I. Chorkendorff, Journal of the American Chemical Society, 134(40):16476–16479, Oct 10 2012. [2] J. Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T.F. Jaramillo, J. Rossmeisl, I. Chorkendorff, J.K. Nørskov, Nature Chemistry, 1 (2009) 552-556. [3] A. Velázquez-Palenzuela, F. Masini, A. F. Pedersen, M. Escudero-Escribano, D. Deian, P. Malacrida, T. W. Hansen, D. Friebel, A. Nilsson, I. E. L. Stephens, I. Chorkendorff, J. Catal. 2015, in press. [4] Hernandez-Fernandez, P., Masini F., McCarthy D. N., Strebel C. E., Friebel D., Deiana D., Malacrida P., Nierhoff A., Bodin A., Wise A. M., Nielsen J. H., Hansen T. W., Nilsson A., Stephens I. E. L., and Chorkendorff I. Nat Chem, 6(8): 732-738, Aug 2014 [5] T. P. Johansson, E. T. Ulrikkeholm, P. Hernandez-Fernandez, M. Escudero-Escribano,P. Malacrida, I. E. L. Stephens, and I. Chorkendorff. Physical Chemistry Chemical Physics, 16(27):13718–13725, 2014.

The sluggish kinetics of the oxygen reduction reaction (ORR) hinders the commercialization of proton exchange membrane fuel cells (PEMFC). The ORR activity is enhanced by alloying Pt with late transition 3d metals (i.e. Fe, Co, Ni, and Cu)1. However, these compounds tend to degrade in a fuel cell by dealloying. An alternative approach is to alloy Pt with rare-earth elements. Their highly negative alloying energy may provide them with kinetic stability against dealloying under reaction conditions. A recent publication from our group reported the high ORR activity and stability of polycrystalline Pt5Gd2. In this work, we present the experimental results of mass-selected PtxGd nanoparticles synthesized by gas aggregation after sputtering of an alloy target in an ultrahigh vacuum (UHV)3. PtxGd nanoparticles with nominal sizes of 3, 5, 7, and 9 nm were selected using time-of-flight mass filtering and deposited on glassy carbon (GC) disk electrodes. Rotating ring disk electrode (RRDE) measurements in 0.1 M HClO4 were used to measure the activity in comparison to pure Pt 4. The ORR specific activity increases with the nanoparticle size; a maximum mass activity is achieved with the 7 nm sample, ~3.6 A/mg Pt at 0.9 V. X-ray absorption spectroscopy measurements suggest that the high ORR activity is due to a compressive strain exerted by the alloy core onto the Pt overlayer at the surface. The structure formed on these types of alloys2 is further elucidated using a Gd/Pt(111) single crystal. The alloy was prepared in UHV by depositing 150 Å of Gd followed by annealing, thus simulating a bulk single crystal. It was characterized in vacuo using low energy electron diffraction, ion scattering spectroscopy, X-ray photoelectron spectroscopy and temperature programmed desorption of CO. Subsequently, the crystal was transferred to an electrochemical cell, where a 1 nm thick Pt overlayer was formed; this constitutes the active phase for oxygen reduction. Using synchrotron based grazing X-ray diffraction, we determine the structure of the alloy and the Pt overlayer. The diffraction contributions from the Pt overlayer is separated from the Pt5Gd alloy, and the analysis of both diffraction patterns are presented. By investigating such well-defined structures, we gain valuable scientific insight into the relationship between their structure and functionality. On the basis of this insight, we can develop even better catalysts for oxygen electroreduction. References 1. Chen, C. et al. Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces. Science 343, 1339–1343 (2014). 2. Escudero-Escribano, M. et al. Pt5Gd as a Highly Active and Stable Catalyst for Oxygen Electroreduction. J. Am. Chem. Soc. 134, 16476–16479 (2012). 3. Velazquez-Palenzuela, A. et al. The enhanced activity of mass-selected PtxGd nanoparticles for oxygen electroreduction. J. Catal. [in press] (2015). doi:10.1016/j.jcat.2014.12.012 4. Perez-Alonso, F. J. et al. The Effect of Size on the Oxygen Electroreduction Activity of Mass-Selected Platinum Nanoparticles. Angew. Chem. Int. Ed. 51, 4641–4643 (2012).

One of the main obstacles to the commercialisation of low-temperature fuel cells is the slow kinetics of the oxygen reduction reaction (ORR). In order to decrease the ORR overpotential and reduce the Pt loading we need to develop more active and stable electrocatalysts. A fruitful strategy for enhancing the cathode activity is to alloy Pt with transition metals [1-2]. However, alloys of Pt and late transition metals are typically unstable under fuel-cell conditions. Herein, we present experimental and theoretical studies showing the trends in activity and stability of novel cathode catalysts based on alloys of Pt and lanthanides. Sputter-cleaned, polycrystalline Pt5Gd shows a five-fold increase in ORR activity [3], relative to Pt at 0.9 V in 0.1 M HClO4. The rest of the Pt5Ln (Ln = lanthanide) tested present at least a 3-fold enhancement in activity [4,5]. In all cases, a Pt overlayer with a thickness of few Pt layers is formed. Accordingly, the effect of alloying Pt is to impose strain onto the Pt overlayer [3,4]. It is likely that this strain would be relaxed by defects [6]. Moreover, the activity of the Pt5Ln catalysts vs. the Pt-Pt distance shows a volcano relationship (Fig. A) [5]. Pt5Ln electrocatalysts are highly stable, as shown in Fig. B [4]. We show, for the first time, that the Pt-Pt distance not only controls the activity, but also the stability of these catalysts [5]. [1] H.A. Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, Appl. Catal. B 2005, 56, 9. [2] I.E.L. Stephens, A.S. Bondarenko, U. Grønbjerg, J. Rossmeisl, I. Chorkendorff, Energy Environ. Sci. 2012, 5, 6744. [3] M. Escudero-Escribano, et al. J. Am. Chem. Soc. 2012, 130, 16476. [4] P. Malacrida, M. Escudero-Escribano, A. Verdaguer-Casadevall, I.E.L. Stephens, I. Chorkendorff, J. Mater. Chem. A 2014, 2, 4234. [5] M. Escudero-Escribano, et al., in preparation, 2014. [6] P. Strasser, et al. Nature Chem., 2010, 2, 454. Fig. (A) ORR kinetic current density at 0.9 V vs. RHE as a function of the lattice parameter and the Pt-Pt distance for Pt5Ln and Pt. (B) Kinetic current density of Pt5Ln and Pt before and after a stability test consisting of 10 000 cycles between 0.6 V and 1.0 V vs. RHE in an O2-saturated 0.1 M HClO4 electrolyte.

Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this technology. Improving the activity of Pt by alloying it with other metals could decrease the loading of Pt. An earlier theoretical study conducted at our laboratory identified PtxY as an active and stable catalyst for oxygen reduction. Experiments conducted on sputter-cleaned polycrystalline Pt3Y confirmed that it showed exceptional activity for the ORR [1]. Later studies also revealed that Pt5Y, prepared in the same manner also showed similar high activity, as shown in Figure (a) below. However, our X-ray photoelectron spectroscopy measurements revealed that the structure formed under reaction conditions was significantly different from our initial expectations. In order to understand this phenomenon, we investigated a Y/Pt(111) single crystal, formed by depositing large amounts of Y om Pt(111) under ultra-high vacuum (UHV) conditions and annealing to high temperatures. We subsequently characterised the surface using electrochemical measurements, low energy electron diffraction, ion scattering spectroscopy, angle resolved X-ray photoelectron spectroscopy, temperature programmed desorption of CO, and synchrotron based X-ray absorption spectroscopy and surface sensitive X-ray diffraction. These measurements were supported by DFT calculations. From the experimental investigations of the crystal structure, it could be concluded that we have obtained a Pt5Y structure with a 5.5 % compressive strain compared to Pt. Electrochemical measurements show that the activity approximates that of sputter-cleaned Pt3Y, as shown in Figure A. Since there is no Y in the first few atomic layers, we attribute the high activity to the compressive strain exerted onto the surface by the alloy bulk. [1] J. Greeley, I.E.L. Stephens, A.S. Bondarenko, T.P. Johansson, H.A. Hansen, T.F. Jaramillo, J. Rossmeisl, I. Chorkendorff, J.K. Nørskov, Nature Chemistry, 1 (2009) 552-556.

Three different Pt–lanthanide metal alloys (Pt5La, Pt5Ce and Pt3La) have been studied as oxygen reduction reaction (ORR) electrocatalysts. Sputter-cleaned polycrystalline Pt5La and Pt5Ce exhibit more than a 3-fold activity enhancement compared to polycrystalline Pt at 0.9 V, while Pt3La heavily corrodes in 0.1 M HClO4 electrolyte. Angle Resolved X-ray Photoelectron Spectroscopy (AR-XPS) and Low Energy Ion Scattering (LEIS) have been extensively combined with electrochemical techniques to follow the chemical and structural changes at the surface. The highly reactive lanthanide atoms are not stable in the presence of oxygen and readily oxidize. The surface oxides are completely dissolved in the electrolyte. In Pt5La and Pt5Ce the so formed Pt overlayer provides kinetic stability against the further oxidation and dissolution. At the same time, it ensures a very high stability during ORR potential cycling, suggesting that these alloys hold promise as cathode catalysts in Proton Exchange Membrane Fuel Cells (PEMFCs).

The 2-photon tandem device for photocatalytic water splitting has been theoretically shown to provide a higher efficiency than a single photon device(1). This increased efficiency can be achieved by having one material optimized to absorb high energy photons (large bandgap) and another material optimized to absorb low energy photons (small bandgap). To a large degree this approach has been hindered by corrosion issues. In this talk I will first discuss how our computational screening of 2,400 materials showed that very few materials can efficiently absorb light without corroding in water splitting conditions.(2) I will follow this up by discussing how protection layers bypass the corrosion issue by creating a buffer layer.(3) Finally I will show how we integrated a photocatalyst/protection layer/(co-catalyst) scheme to produce highly efficient H2 evolution photocathodes and O2 evolution photoanodes.(3, 4) 1. A. B. Laursen, S. Kegnaes, S. Dahl and I. Chorkendorff, Energy & Environmental Science, 5 (2012). 2. B. Seger, I. E. Castelli, P. C. K. Vesborg, K. W. Jacobsen, O. Hansen and I. Chorkendorff, Energy & Environmental Science, 7, 2397 (2014). 3. B. Seger, T. Pedersen, A. B. Laursen, P. C. K. Vesborg, O. Hansen and I. Chorkendorff, Journal of the American Chemical Society, 135, 1057 (2013). 4. B. Mei, A. A. Permyakova, R. Frydendal, D. Bae, T. Pedersen, P. Malacrida, O. Hansen, I. E. L. Stephens, P. C. K. Vesborg, B. Seger and I. Chorkendorff, The Journal of Physical Chemistry Letters, 5, 3456 (2014). Figure 1

The high platinum loadings required to compensate for the slow kinetics of the oxygen reduction reaction (ORR) impede the widespread uptake of polymer electrolyte membrane fuel cells. In order to improve the ORR kinetics and reduce the Pt loading, we can tailor the electronic properties of the Pt surface atoms by means of alloying Pt with other metals. Researchers have intensively studied alloys of Pt with late transition metals such as Ni and Co during the last decades. However, these compounds typically degrade under fuel cell reaction conditions, due to dealloying. In contrast, alloys of Pt and lanthanides present very negative enthalpy of formation [1,2], which should increase their resistance to degradation. Herein we present eight novel Pt-lanthanide and Pt-alkaline earth ORR electrocatalysts: Pt5La, Pt5Ce, Pt5Sm, Pt5Gd, Pt5Tb, Pt5Dy, Pt5Tm and Pt5Ca [3]. All the materials are highly active, presenting a 3 to 6-fold activity enhancement over Pt. Pt5Tb is the most active polycrystalline Pt-based catalyst reported in the literature. A Pt overlayer with a thickness of few Pt layers is formed onto the bulk alloys by acid leaching [1-3]. Notably, the experimental ORR activity as a function of the bulk lattice parameter and the Pt-Pt distance follows a “volcano” relation [3], with Pt5Tb presenting the highest initial activity while Pt5Gd is the most active after 10 000 cycles stability test between 0.6 and 1.0 V versus the reversible hydrogen electrode. We use the lanthanide contraction to control strain effects and tune the electrocatalytic activity, stability and reactivity of Pt [3]. References [1] M. Escudero-Escribano, A. Verdaguer-Casadevall, P. Malacrida, U. Grønbjerg, B.P. Knudsen, A.K. Jepsen, J. Rossmeisl, I.E.L. Stephens, I. Chorkendorff, J. Am. Chem. Soc. 2012, 130, 16476. [2] P. Malacrida, M. Escudero-Escribano, A. Verdaguer-Casadevall, I.E.L. Stephens, I. Chorkendorff, J. Mater. Chem. A 2014, 2, 4234. [3] M. Escudero-Escribano, P. Malacrida, M.H. Hansen, U.G. Vej-Hansen, A. Velázquez-Palenzuela, V. Tripkovic, J. Schiøtz, J. Rossmeisl, I.E.L. Stephens, I. Chorkendorff, Science 2016, 352, 73.

In order to make low-temperature fuel cells commercially viable, it is crucial to develop oxygen reduction catalysts based on more active, stable and abundant materials. A fruitful strategy for enhancing the oxygen reduction reaction (ORR) activity is to alloy Pt with transition metals [1]. However, commercial alloys of Pt and late transition metals such as Ni, Co or Fe are typically unstable under fuel-cell conditions [2]. The very negative enthalpy of formation of alloys of Pt and lanthanides could provide them with greater long term stability than Pt and late transition metals. Herein, we show the trends in activity and stability novel Pt-lanthanide (Pt-Ln) alloys as efficient ORR catalysts. Sputter-cleaned, polycrystalline Pt5Gd shows a 5-fold increase in ORR activity [3], relative to Pt. All the Pt-lanthanide alloys are at least 3 times more active than Pt for the ORR [3-5]. A compressed Pt overlayer is formed onto the bulk alloy. Accordingly, the effect of alloying Pt is to impose strain onto the Pt overlayer [3-5]. It is likely that this strain would be relaxed by defects [6]. The activity of the Pt-based electrocatalysts versus the lattice parameter in the bulk shows a volcano relationship (Fig. 1A). The lattice parameter is presented as a new descriptor that controls both the activity and stability of these materials [5]. The best performance (activity-stability) is achieved by Pt5Gd. Furthermore, mass-selected PtxGd nanoparticles synthesised by the gas aggregation technique present a significant ORR activity enhancement as compared to pure Pt nanoparticles, PtxGd 8 nm showing 3.6 A (mg Pt)-1 mass activity (Fig. 1B) [7], surpassing the highest activity reached with PtxY nanoparticles [8]. The activity of PtxGd nanoparticles also correlates strongly with compressive strain. Our results demonstrate that we can engineer both the activity and stability by tuning the Pt-Pt distance. References [1] I.E.L. Stephens, A.S. Bondarenko, U. Grønbjerg, J. Rossmeisl, I. Chorkendorff, Energy Environ. Sci. 2012, 5, 6744. [2] S. Chen, H.A. Gasteiger, K. Hayakawa, T. Tada, Y. Shao-Horn, J. Electrochem. Soc. 2010, 1571, A82. [3] M. Escudero-Escribano, et al., J. Am. Chem. Soc. 2012, 130, 16476. [4] P. Malacrida, M. Escudero-Escribano, A. Verdaguer-Casadevall, I.E.L. Stephens, I. Chorkendorff, J. Mater. Chem. A 2014, 2, 4234. [5] M. Escudero-Escribano, et al., to be submitted, 2014. [6] P. Strasser, et al., Nature Chem. 2010, 2, 454. [7] A. Velázquez-Palenzuela, et al., J. Catal., accepted, 2014. [8] P. Hernández-Fernández, et al., Nature Chem. 2014, 6, 732. Fig 1. (A) ORR kinetic current density as a function of the lattice parameter and the Pt-Pt distance for Pt5Ln and Pt. (B) Mass activity of PtxGd, PtxY and Pt nanoparticles. All activity values were taken at 0.9 V vs. RHE, from cyclic voltammetry recorded at 50 mV s-1 and 1600 rpm in O2-saturated 0.1M HClO4. Figure 1

In order to reduce the Pt loading at the cathode of proton exchange membrane fuel cells (PEMFCs) more active and stable catalysts are needed to drive the oxygen reduction reaction. Most research has focussed on achieving this by alloying Pt with Fe, Co, Ni or Cu [1,2]. However, these compounds typically degrade under PEMFC conditions, due to dealloying. Alloys of Pt and lanthanides may be inherently less prone to dealloying under reactions conditions, due to their negative enthalpy of formation [2-4]. Herein we present a systematic study on the trends in activity of seven novel Pt-lanthanide electrodes (Pt5La, Pt5Ce, Pt5Sm, Pt5Gd, Pt5Tb, Pt5Dy and Pt5Tm). The materials are highly active, presenting a 3 to 6-fold activity enhancement over Pt [3-5], amongst the most active polycrystalline Pt-based catalyst ever reported. Moreover, our recent study showed that Pt x Gd is highly active in the nanoparticulate form [6]. On the bulk alloys, a Pt overlayer with a thickness of few Pt layers is formed onto the bulk alloys by acid leaching (Fig. 1A) [3-5]. The ORR activity versus the lattice parameter obtained by X-ray diffraction measurements follows a volcano relationship (Fig. 1B). Furthermore, we explain the trends in stability, and present the lattice parameter as a new descriptor that controls both the activity and stability of these materials. Using the lanthanide contraction we demonstrate that the electrocatalytic performance can be engineered by tuning the Pt-Pt distance. References [1] H. A. Gasteiger, S.S. Kocha, B. Sompalli, F.T. Wagner, Appl. Catal. B 2005, 56, 9. [2] I.E.L. Stephens, A.S. Bondarenko, U. Grønbjerg, J. Rossmeisl, I. Chorkendorff, Energy Environ. Sci. 2012, 5, 6744. [3] M. Escudero-Escribano, A. Verdaguer-Casadevall, P. Malacrida, U. Grønbjerg, B.P. Knudsen, A.K. Jepsen, J. Rossmeisl, I.E.L. Stephens, I. Chorkendorff, J. Am. Chem. Soc. 2012, 130, 16476. [4] P. Malacrida, M. Escudero-Escribano, A. Verdaguer-Casadevall, I.E.L. Stephens, I. Chorkendorff, J. Mater. Chem. A 2014, 2, 4234. [5] M. Escudero-Escribano, et al., to be submitted, 2015. [6] A. Velázquez-Palenzuela, F. Masini, A.F. Pedersen, M. Escudero-Escribano, D. Deiana, P. Malacrida, T.W. Hansen, D. Friebel, A. Nilsson, I.E.L. Stephens, I. Chorkendorff, J. Catal., in press., 2015, DOI: 10.1016/j.jcat.2014.12.012 Fig 1. (A) Schematic three-dimensional views of the Pt5M (M = lanthanide) structure during sputter-cleaning and after electrochemistry. (B) Experimental ‘activity-lattice parameter’ volcano plot: ORR kinetic current density measured at 0.9 V vs. RHE as a function of the lattice parameter and the Pt-Pt distance for polycrystalline Pt5M electrocatalysts after initial ORR activity (dark grey squares) and after 10 000 cycles between 0.6 and 1.0 V vs. RHE (grey circles). Figure 1

Sputter deposition of 50 nm thick NiO films on p(+)-n-Si and subsequent treatment in an Fe-containing electrolyte yielded highly transparent photoanodes capable of water oxidation (OER) in alkaline media (1 M KOH) with high efficiency and stability. The Fe treatment of NiO thin films enabled Si-based photoanode assemblies to obtain a current density of 10 mA/cm(2) (requirement for10% efficient devices) at 1.15 V versus RHE (reversible hydrogen electrode) under red-light (38.6 mW/cm(2)) irradiation. Thus, the photoanodes were harvesting ∼80 mV of free energy (voltage), which places them among the best-performing Si-based photoanodes in alkaline media. The stability was proven by chronoamperometry at 1.3 V versus RHE for 300 h. Furthermore, measurements with electrochemical quartz crystal microbalances coupled with ICP-MS showed minor corrosion under dark operation. Extrapolation of the corrosion rate showed stability for more than 2000 days of continuous operation. Therefore, protection by Fe-treated NiO films is a promising strategy to achieve highly efficient and stable photoanodes.