Search

CO molecules can be efficiently oxidized over Pt/CeO2 catalysts, but the stability and reactivity of different states of Pt in the catalysts are still unclear. Here we combine experimental and computational methods to characterize Pt/CeO2 catalysts subjected to reductive and oxidative pre-treatments and exposed to CO oxidation reaction conditions. Particles of metallic Pt, known to be catalytically active at elevated temperature, are shown to be precursors for the formation, under operando conditions, of more stable PtOx particles that enable CO oxidation below room temperature. These PtOx particles are also similarly stable to - but more active than - atomically dispersed Pt2+ species. The results and approaches presented in this study illustrate the complex response of catalytic materials to reaction conditions and pave the way for future efforts to improve Pt/CeO2 and similar catalysts using dedicated pre-treatment strategies.

Understanding how reaction conditions affect metal-support interactions in catalytic materials is one of the most challenging tasks in heterogeneous catalysis research. Metal nanoparticles and their supports often undergo changes in structure and oxidation state when exposed to reactants, hindering a straightforward understanding of the structure-activity relations using only ex situ or ultrahigh vacuum techniques. Overcoming these limitations, we explored the metal-support interaction between gold nanoparticles and ceria supports in ultrahigh vacuum and after exposure to CO. A combination of in situ methods (on powder and model Au/CeO2 samples) and theoretical calculations was applied to investigate the gold/ceria interface and its reactivity toward CO exposure. X-ray photoelectron spectroscopy measurements rationalized by first-principles calculations reveal a distinctly inhomogeneous charge distribution, with Au+ atoms in contact with the ceria substrate and neutral Au0 atoms at the surface of the Au nanoparticles. Exposure to CO partially reduces the ceria substrate, leading to electron transfer to the supported Au nanoparticles. Transferred electrons can delocalize among the neutral Au atoms of the particle or contribute to forming inert Auδ− atoms near oxygen vacancies at the ceria surface. This charge redistribution is consistent with the evolution of the vibrational frequencies of CO adsorbed on Au particles obtained using diffuse reflectance infrared Fourier transform spectroscopy.

Ru evaporation from the surface of a Ru/CeO2 catalyst is demonstrated.

Solution-processed In2Se3 nanosheets exhibit exceptional selectivity and sensitivity to NO2 gas, making them a promising candidate for gas detection systems.

Stabilization of cathode catalysts in hydrogen-fueled proton-exchange membrane fuel cells (PEMFCs) is paramount to their widespread commercialization. Targeting that aim, Pt-Au alloy catalysts with various compositions (Pt

Single-atom catalysts represent an essential and ever-growing family of heterogeneous catalysts. Recent studies indicate that besides the valuable catalytic properties provided by single-atom active sites, the presence of single-atom sites on the catalyst substrates may significantly influence the population of supported metal nanoparticles coexisting with metal single atoms. Treatment of ceria-based single-atom catalysts in oxidizing or reducing atmospheres was proven to provide precise experimental control of the size of the supported Pt nanoparticles, and, correspondingly, control of catalyst activity and stability. Based on dedicated surface science experiments, ab-initio calculations and kinetic Monte-Carlo simulations we demonstrate that the morphology of Pt nanoparticle population on ceria surface is a result of a competition for Pt atoms between Pt single-atom sites and Pt nanoparticles. In oxidizing atmosphere, Pt single-atom sites provide strong bonding to single Pt atoms and Pt nanoparticles shrink. In reducing atmosphere, Pt single atom sites are depopulated and Pt nanoparticles grow. We formulate a generic model of Pt redispersion and coarsening on ceria substrates. Our model provides a unified atomic-level explanation for a variety of metal nanoparticle dynamic processes observed in single-atom catalysts under stationary or alternating oxidizing/reducing atmospheres, and allows to classify the conditions when nanoparticle ensembles on single-atom catalysts substrates can be stabilized against Ostwald ripening.

The oxidation state and stability of Pd nanoparticles supported on well-ordered Co3O4(111) films prepared on Ir(100) have been investigated in UHV and under both oxidizing and humid conditions by m...

Electrochemical impedance spectroscopy, photoelectron spectroscopy, and Kelvin probe measurements on various TiO2 single-crystal surfaces show that the position of the Fermi level and the conductio...

The electrochemical activity of modern Fe-N-C electrocatalysts in alkaline media is on par with that of platinum. For successful application in fuel cells (FCs), however, also high durability and longevity must be demonstrated. Currently, a limited understanding of degradation pathways, especially under operando conditions, hinders the design and synthesis of simultaneously active and stable Fe-N-C electrocatalysts. In this work, using a gas diffusion electrode half-cell coupled with inductively coupled plasma mass spectrometry setup, Fe dissolution is studied under conditions close to those in FCs, that is, with a porous catalyst layer (CL) and at current densities up to -125 mA·cm

For several years, scientists have been trying to understand the mechanisms that reduce the long‐term stability of perovskite solar cells. In this work, we examined the effect of water and photon flux on the stability of CH3NH3PbI3 perovskite films and solar cells using in situ near‐ambient pressure X‐ray photoelectron spectroscopy (NAP‐XPS), field emission scanning electron microscopy (FESEM), and current density–voltage (J–V) characterization. The used amount of water vapor (up to 1 mbar) had a negligible impact on the perovskite film. The higher the photon flux, the more prominent were the changes in the NAP‐XPS and FESEM data; also, a faster decline in power conversion efficiency (PCE) and a more substantial hysteresis in the J‐V characteristics were observed. Based on our results, it can be concluded that the PCE decrease originates from the creation of Frenkel pair defects in the perovskite film under illumination. The stronger the illumination, the higher the number of Frenkel defects, leading to a faster PCE decline and more substantial hysteresis in the J‐V sweeps., Solar cell deactivation: For similar exposures, the soaking of light proves more detrimental to the perovskite film than water vapor. Absorbed photons create Frenkel defects in the perovskite crystal. The number of created Frenkel defects depends strongly on the used illumination. The higher the photon flux, the higher the creation of Frenkel defects, and thus the stronger the degradation of power conversion efficiency and the stronger the hysteresis in the J–V characteristics.

Currently, platinum is the most widely used catalyst for low temperature proton exchange membrane fuel cells (PEMFC). However, the kinetics at the cathode are slow, and the price of platinum is high. To improve oxygen reduction reaction (ORR) kinetics at the cathode, platinum can be alloyed with rare earth elements, such as yttrium. We report that Pt3Y has the potential to be over 2 times more active for the ORR compared with Pt inside a real fuel cell. We present detailed photoemission analysis into the nature of the sputtered catalyst surface, using synchrotron radiation photoelectron spectroscopy (SRPES) to examine if surface adsorbates or impurities are present and can be removed. Pretreatment removes most of the yttrium oxide in the surface leaving behind a Pt overlayer which is only a few monolayers thick. Evidence of a substochiometric oxide peak in the Y 3d core level is presented, this oxide extends into the surface even after Ar+ sputter cleaning in-situ. This information will aid the development of new highly active nanocatalysts for employment in real fuel cell electrodes.

Comprehensive understanding of the catalyst corrosion dynamics is a prerequisite for the development of an efficient cathode catalyst in proton-exchange membrane fuel cells. To reach this aim, the behavior of fuel cell catalysts must be investigated directly under reaction conditions. Herein, we applied a strategic combination of in situ/online techniques: in situ electrochemical atomic force microscopy, in situ grazing incidence small angle X-ray scattering, and electrochemical scanning flow cell with online detection by inductively coupled plasma mass spectrometry. This combination of techniques allows in-depth investigation of the potential-dependent surface restructuring of a PtNi model thin film catalyst during potentiodynamic cycling in an aqueous acidic electrolyte. The study reveals a clear correlation between the upper potential limit and structural behavior of the PtNi catalyst, namely, its dealloying and coarsening. The results show that at 0.6 and 1.0 VRHE upper potentials, the PtNi catalyst essentially preserves its structure during the entire cycling procedure. The crucial changes in the morphology of PtNi layers are found to occur at 1.3 and 1.5 VRHE cycling potentials. Strong dealloying at the early stage of cycling is substituted with strong coarsening of catalyst particles at the later stage. The coarsening at the later stage of cycling is assigned to the electrochemical Ostwald ripening process.

Control of metal–support interactions is one of the major challenges in heterogeneous catalysis. In this study, we explored the effect of Eu doping on the metal–support interactions in Au/Ce1–xEuxO...

Localization and migration of highly mobile and extremely efficient bismuth promoter in iron Fischer–Tropsch catalysts were elucidated using in situ methods., Liquid metals are a new emerging and rapidly growing class of materials and can be considered as efficient promoters and active phases for heterogeneous catalysts for sustainable processes. Because of low cost, high selectivity and flexibility, iron-based catalysts are the catalysts of choice for light olefin synthesis via Fischer–Tropsch reaction. Promotion of iron catalysts supported by carbon nanotubes with bismuth, which is liquid under the reaction conditions, results in a several fold increase in the reaction rate and in a much higher light olefin selectivity. In order to elucidate the spectacular enhancement of the catalytic performance, we conducted extensive in-depth characterization of the bismuth-promoted iron catalysts under the reacting gas and reaction temperatures by a combination of cutting-edge in situ techniques: in situ scanning transmission electron microscopy, near-atmospheric pressure X-ray photoelectron spectroscopy and in situ X-ray adsorption near edge structure. In situ scanning transmission electron microscopy conducted under atmospheric pressure of carbon monoxide at the temperature of catalyst activation showed iron sintering proceeding via the particle migration and coalescence mechanism. Catalyst activation in carbon monoxide and in syngas leads to liquid bismuth metallic species, which readily migrate over the catalyst surface with the formation of larger spherical bismuth droplets and iron–bismuth core–shell structures. In the working catalysts, during Fischer–Tropsch synthesis, metallic bismuth located at the interface of iron species undergoes continuous oxidation and reduction cycles, which facilitate carbon monoxide dissociation and result in the substantial increase in the reaction rate.

Platinum is the most widely used and best performing sole element for catalyzing the oxygen reduction reaction (ORR) in low-temperature fuel cells. Although recyclable, there is a need to reduce the amount used in current fuel cells for their extensive uptake in society. Alloying platinum with rare-earth elements such as yttrium can provide an increase in activity of more than seven times, reducing the amount of platinum and the total amount of catalyst material required for the ORR. As yttrium is easily oxidized, exposure of the Pt-Y catalyst layer to air causes the formation of an oxide layer that can be removed during acid treatment, leaving behind a highly active pure platinum overlayer. This paper presents an investigation of the overlayer composition and quality of Pt3Y films sputtered from an alloy target. The Pt3Y catalyst surface is investigated using synchrotron radiation X-ray photoelectron spectroscopy before and after acid treatment. A new substoichiometric oxide component is identified. The oxide layer extends into the alloy surface, and although it is not completely removed with acid treatment, the catalyst still achieves the expected high ORR activity. Other surface-sensitive techniques show that the sputtered films are smooth and bulk X-ray diffraction reveals many defects and high microstrain. Nevertheless, sputtered Pt3Y exhibits a very high activity regardless of the film's oxide content and imperfections, highlighting Pt3Y as a promising catalyst. The obtained results will help to support its integration into fuel cell systems.

By means of electrocatalytic tests, surface-science techniques and density functional theory, we unveil the physicochemical mechanisms ruling the electrocatalytic activity of recently discovered mitrofanovite (Pt3Te4) mineral. Mitrofanovite represents a very promising electrocatalyst candidate for energy-related applications, with a reduction of costs by 47% compared to pure Pt and superior robustness to CO poisoning. We show that Pt3Te4 is a weak topological metal with the invariant, exhibiting electrical conductivity (∼4 × 106 S/m) comparable with pure Pt. In hydrogen evolution reaction (HER), the electrode based on bulk Pt3Te4 shows a very small overpotential of 46 mV at 10 mA cm–2 and a Tafel slope of 36–49 mV dec–1 associated with the Volmer–Heyrovsky mechanism. The outstanding ambient stability of Pt3Te4 also provides durability of the electrode and long-term stability of its efficient catalytic performances.

Metal nanoparticles on the surface of porous supports have found numerous applications in different areas of science. Fischer-Tropsch synthesis, which proceeds on the surface of cobalt metal nanoparticles, is an efficient way to convert renewables and fossil feedstocks into alternative fuels. The stability of cobalt catalysts is an essential and even crucial parameter and can be significantly improved by promotion. In this paper, a combination of operando Quick-XAS, NAP-XPS, high resolution electron microscopy imaging, DFT modeling alongside with Fischer-Tropsch catalytic experiments has provided deep insights into the evolution of bismuth promoter and structure of cobalt-bismuth nanoparticles in the catalysts supported by carbon nanotubes. We uncovered noticeable migration of metallic bismuth occurring during the reduction step, which leads to bismuth redispersion over the surface of cobalt nanoparticles. Cobalt reduction is facilitated in the presence of bismuth. The working Fischer-Tropsch catalyst contains cobalt-bismuth bimetallic nanoparticles, with bismuth located in the nanoparticle shell. The promotion with bismuth has resulted in a noticeable increase in catalyst stability. Characterization and DFT modeling suggest preferential localization of bismuth mobile promoter at the steps and edges of cobalt nanoparticles, which hinders cobalt sintering and carbon deposition and improves the catalyst stability.

This article presents an investigation of the sensing properties of chemiresistors based on Cu2O/CuO core–shell nanowires containing p–p′ heterojunctions. The nanowires were synthesized by a conven...

This work presents the investigation of Bi-modified MoVNbTeO catalysts for oxidative dehydrogenation of ethane (ODE) using the combination of NAP-XPS, in situ XRD and XANES/EXAFS techniques. It was found that introduction of Bi improves the tolerance of catalysts toward severe reaction conditions (high temperature and/or enhanced ethane/oxygen ratio) resulting in a significant decrease in the degree of deactivation. In accordance with NAP-XPS data, the surface/subsurface Te concentration was maintained for Bi-containing MoVNbTeO catalysts even after treatment with a reducing reaction mixture (C2H6/O2 >3) at temperatures up to 460 °C. In the case of the unmodified catalyst, such treatment resulted in the surface/subsurface depletion of Te due to the reduction into the Te° state followed by its sublimation into the gas phase. The incorporation of Bi within extended six-membered channels of the M1 structure was suggested based on XANES/EXAFS data. Such incorporation probably influences the mobility of Te within channels, resulting in the limitation of Te diffusion from the particle bulk to the surface. The improved tolerance of catalytically active M1 phase toward severe reaction conditions was confirmed by in situ XRD data during heating in a mixture of 8 wt % C2H6/He.

A feasible sonochemical approach is described for the preparation of copper/iron-modified graphene oxide nanocomposites through ultrasonication (20 kHz, 18 W cm-2 ) of an aqueous solution containing copper and iron ion precursors. Unique copper-, copper/iron- and iron-modified graphene oxide nanocomposites have a submicron size that is smaller than that of pristine GO and a higher surface area enriched with Cu2 O, CuO, and Fe2 O3 of multiform phases (α-, β-, ϵ-, or γ), FeO(OH), and sulfur- or carbon-containing compounds. These nanocomposites are sonochemically intercalated with the nonsteroidal anti-inflammatory drug ketorolac, which results in the formation of nanoscale carriers. Ketorolac monotonically disintegrates from these nanoscale carriers in aqueous solution upon adjustment of the pH from 1 to 8. The disintegration of ketorolac proceeds at a slower rate from the copper/iron-modified graphene oxide at increased pH, but at a faster rate from the iron-modified graphene oxide under acidic conditions.

Achieving high stability of supported noble metal nanoparticles with respect to sintering is one of the major challenges in electrocatalysis. In this study, we explored the role of metal–support interaction in stabilizing the morphology of a well-defined model electrode consisting of Pt nanoparticles supported on well-ordered Co3O4(111) films on Ir(100). We employed X-ray photoelectron spectroscopy coupled with an electrochemical cell to analyze changes in the oxidation states of both the supported Pt nanoparticles and Co3O4(111) support as a function of electrode potential. We found that immersion into the aqueous electrolyte at pH 10 (phosphate buffer) has no effect on the integrity and chemical composition of the Co3O4(111) film in a potential window between 0.5 and 1.4 VRHE. At lower potentials, reduction of the Co3O4(111) to Co(OH)2 and metallic Co is accompanied by rapid dissolution of the film. In the presence of supported Pt particles, metal–support interaction gives rise to the formation of parti...

The effect of ZnO and the preparation method of ZnO/ZrO2–SiO2 catalysts on their acid–base properties and catalytic performances in the conversion of diluted ethanol mixtures into 1,3-butadiene (BD) is presented. Based on the results of the temperature-programmed desorption (TPD) of NH3/CO2, near-ambient pressure X-ray photoelectron spectrometry (NAP-XPS) with O2/ethanol + H2O, adsorption of pyridine and deuterated chloroform followed by Fourier-transform infrared (FTIR) spectroscopy, and catalytic experiments, it has been concluded that the differences in activities and selectivities of the prepared catalysts can be attributed to the formation of different amounts of Zn-containing acidic or basic active sites. A wet-kneading procedure facilitates the preparation of a more active/selective catalyst as compared to that obtained using the incipient wetness impregnation of ZrO2–SiO2 with an aqueous solution of zinc salt. Dependencies between the acid–base capacity ratio of zinc oxides, calculated from the NH3/CO2-TPD and NAP-XPS data as well as the initial reaction rate of BD formation have been observed for ZnO/ZrO2–SiO2 catalysts. In the presence of a catalytic system with a predominance of acidic sites on the surface, higher ethanol conversion and BD selectivity can be achieved as opposed to systems involving a predominance of basic sites. The ZnO/ZrO2–SiO2 catalyst prepared by using zinc oxide nanoparticles and ZrO2–SiO2 provides a BD yield of ∼52.4% in the conversion of 80% ethanol–20% H2O mixture (673 K, 1.3 gEtOH gcat−1 h−1); a BD productivity of 0.4 gBD gcat−1 h−1 can be achieved.

Ceria represents a technologically indispensable reducible catalyst support. Besides the general impact on the surface chemistry, the oxygen content of the ceria surface directly influences the dispersion of ceria-supported metal nanoparticles, and the properties of ceria-supported metal catalysts. We investigate the role of oxygen atoms on a CeO2(111) surface in supporting Pt as smallest metallic Pt clusters or, concurrently, as monodispersed Pt2+ ions. We demonstrate that the necessary condition for the formation of Pt2+ ions is the availability of lattice O or excess O atoms at surface step edges. Although Pt2+ ions can exist on partially reduced surfaces, excess O atoms are required to maximize the capacity of the surface to accommodate Pt2+ and to trigger the redispersion of metallic Pt clusters. Our study provides atomic-level understanding and control of the highest dispersions of Pt on the ceria surface for advancing the state-of-the-art Pt/ceria catalysts that are presently identified at the verge of single-atom Pt dispersion.

International audience; Pt-based materials are widely used as heterogeneous catalysts, in particular for pollutant removal applications. The nature of the active Pt phase responsible for CO oxidation has long been investigated with a view at designing more efficient formulations. The state of Pt has often been proposed to differ depending on experimental conditions, e.g. metallic Pt poisoned with CO being present at lower temperature before light-off, while an oxidized Pt surface prevails above light-off temperature. In stark contrast with all previous reports, we show here that both metallic and oxidized Pt are present in similar proportions under reaction conditions at the surface of ca. 1 nm nanoparticles showing high activity at 30 °C. The simultaneous presence of metallic and oxidized Pt enables a synergy between these phases. The main role of metallic Pt phase is to provide strong adsorption sites for CO, while that of oxidized Pt supposedly supplies reactive oxygen. Our results emphasize the complex dual oxidic-metallic nature of supported Pt catalysts and its evolving nature under reaction conditions, warranting a whole rethink of the mechanism of other reaction and metals, particularly redox and electrochemical reactions.

By means of electrocatalytic tests, surface-science techniques and density functional theory, we unveil the physicochemical mechanisms ruling the electrocatalytic activity of recently discovered mitrofanovite (Pt3Te4) mineral. Mitrofanovite represents a very promising electrocatalyst candidate for energy-related applications, with a reduction of costs by 47% compared to pure Pt and superior robustness to CO poisoning. We show that Pt3Te4 is a weak topological metal with the Z2 invariant, exhibiting electrical conductivity (∼4 × 106 S/m) comparable with pure Pt. In hydrogen evolution reaction (HER), the electrode based on bulk Pt3Te4 shows a very small overpotential of 46 mV at 10 mA cm-2 and a Tafel slope of 36-49 mV dec-1 associated with the Volmer-Heyrovsky mechanism. The outstanding ambient stability of Pt3Te4 also provides durability of the electrode and long-term stability of its efficient catalytic performances. © 2021 American Chemical Society. Deutsche Forschungsgemeinschaft, DFG: SFB 1083; National Natural Science Foundation of China, NSFC: 21775078, 22075159, tsqn202103058; Ministry of Education and Science of the Russian Federation, Minobrnauka: FEUZ-2020-0060 L.Z. acknowledges funding by the National Natural Science Foundation of China (Nos. 21775078 and 22075159) and Taishan Scholar Program (No. tsqn202103058). F.C.B. acknowledges funding by the DFG through the SFB 1083 Structure and Dynamics of Internal Interfaces (Project A 12). D.W.B. acknowledged support Ministry of Science and Higher Education of the Russian Federation (through the basic part of the government mandate, Project No. FEUZ-2020-0060) and Jiangsu Innovative and Entrepreneurial Talents Project. I.V. and J.F. thank NFFA-Trieste.

Catalysis science & technology 11, 250 - 263 (2020). doi:10.1039/D0CY01533D, The improvement of the low-temperature activity of the supported platinum catalysts in selective ammonia oxidation to nitrogen is still a challenging task. The recent developments in in situ/operando characterization techniques allows to bring new insight into the properties of the systems in correlation with their catalytic activity. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando X-ray absorption spectroscopy (XAS) techniques were applied to study Pt/TiO$_{2}$ catalysts in ammonia oxidation (NH$_{3}$ + O$_{2}$ reaction). Several synthesis methods were used to obtain samples with different size of Pt particles, oxidation state of Pt, and morphology of the support. Metal platinum particles on titania prepared by pulsed laser ablation in liquids exhibited the highest activity at lower temperatures with the temperature of 50% conversion of NH$_{3}$ being 150 ��C. The low-temperature activity of the catalysts synthesized by impregnation can be improved by the reductive pretreatment. NAP-XPS and operando XANES data do not show formation of PtO$_{x}$ surface layers or PtO/PtO$_{2}$ oxides during NH$_{3}$ + O$_{2}$ reaction. Despite the differences in the oxidation state of platinum in the as-prepared catalysts, their treatment in the reaction mixture results in the formation of metallic platinum particles, which can serve as centers for stabilization of the adsorbed oxygen species. Stabilization of the bulk platinum oxide structures in the Pt/TiO$_{2}$ catalysts seems to be less favorable due to the metal���support interaction., Published by RSC Publ., London

Gallium selenide (GaSe) is a van der Waals semiconductor widely used for optoelectronic devices, whose performances are dictated by bulk properties, including band-gap energy. However, recent experimental observations that the exfoliation of GaSe into atomically thin layers enhances performances in electrochemistry and photocatalysis have opened new avenues for its applications in the fields of energy and catalysis. Here, it is demonstrated by surface-science experiments and density functional theory (DFT) that the oxidation of GaSe into Ga2O3, driven by Se vacancies and edge sites created in the exfoliation process, plays a pivotal role in catalytic processes. Specifically, both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are energetically unfavorable in pristine GaSe, due to energy barriers of 1.9 and 5.7-7.4 eV, respectively. On the contrary, energy barriers are reduced concurrently with surface oxidation. Especially, the Heyrovsky step (Hads + H+ + e- -> H2) of HER becomes energetically favorable only in sub-stoichiometric Ga2O2.97 (-0.3 eV/H+). It is also discovered that the same mechanisms occur for the case of the parental compound indium selenide (InSe), thus ensuring the validity of the model for the broad class of III-VI layered semiconductors

Advanced electronic materials 1900808 (2019). doi:10.1002/aelm.201900808, Published by Wiley, Chichester

Platinum is the most widely used and best performing sole element for catalyzing the oxygen reduction reaction (ORR) in low-temperature fuel cells. Although recyclable, there is a need to reduce the amount used in current fuel cells for their extensive uptake in society. Alloying platinum with rare-earth elements such as yttrium can provide an increase in activity of more than seven times, reducing the amount of platinum and the total amount of catalyst material required for the ORR. As yttrium is easily oxidized, exposure of the Pt-Y catalyst layer to air causes the formation of an oxide layer that can be removed during acid treatment, leaving behind a highly active pure platinum overlayer. This paper presents an investigation of the overlayer composition and quality of Pt

PtCu bimetallic alloys are known to provide better activity than pure platinum in proton exchange membrane fuel cells. However, such catalysts undergo complex degradation processes during fuel cell operation, resulting in deterioration of their activity. By using in situ electrochemical (EC) atomic force microscopy combined with in situ EC infrared reflection absorption spectroscopy, we provide a comprehensive investigation of morphological and structural transformations of PtCu model thin film catalysts during accelerated degradation tests (ADTs). The ADTs consist of potentiodynamic cycling to three different upper potentials relevant for different modes of fuel cell operation. The results show that, depending on the upper potential limit, PtCu alloy electrocatalysts are subject to drastic changes in the surface composition, morphology, and structure.

Electrocatalysis is at the heart of our future transition to a renewable energy system. Most energy storage and conversion technologies for renewables rely on electrocatalytic processes and, with increasing availability of cheap electrical energy from renewables, chemical production will witness electrification in the near future1-3. However, our fundamental understanding of electrocatalysis lags behind the field of classical heterogeneous catalysis that has been the dominating chemical technology for a long time. Here, we describe a new strategy to advance fundamental studies on electrocatalytic materials. We propose to 'electrify' complex oxide-based model catalysts made by surface science methods to explore electrocatalytic reactions in liquid electrolytes. We demonstrate the feasibility of this concept by transferring an atomically defined platinum/cobalt oxide model catalyst into the electrochemical environment while preserving its atomic surface structure. Using this approach, we explore particle size effects and identify hitherto unknown metal-support interactions that stabilize oxidized platinum at the nanoparticle interface. The metal-support interactions open a new synergistic reaction pathway that involves both metallic and oxidized platinum. Our results illustrate the potential of the concept, which makes available a systematic approach to build atomically defined model electrodes for fundamental electrocatalytic studies.

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH4 → CH3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy and density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. These findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels. Fil: Lustemberg, Pablo German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Física de Rosario. Universidad Nacional de Rosario. Instituto de Física de Rosario; Argentina Fil: Palomino, Robert M.. Brookhaven National Laboratory; Estados Unidos Fil: Gutiérrez, Ramón A.. Universidad Central de Venezuela; Venezuela Fil: Grinter, David C.. Harwell Science and Innovation Campus; Reino Unido Fil: Vorokhta, Mykhailo. Charles University; República Checa Fil: Liu, Zongyuan. Brookhaven National Laboratory; Estados Unidos Fil: Ramírez, Pedro J.. Universidad Central de Venezuela; Venezuela Fil: Matolín, Vladimír. Charles University; República Checa Fil: Ganduglia Pirovano, Maria Veronica. Consejo Superior de Investigaciones Científicas. Instituto de Catálisis y Petroleoquímica; España Fil: Senanayake, Sanjaya D.. Brookhaven National Laboratory; Estados Unidos Fil: Rodriguez, José A.. Brookhaven National Laboratory; Estados Unidos

Reactions of reduced cerium oxide CeOx with water are fundamental processes omnipresent in ceria-based catalysis. Using thin epitaxial films of ordered CeOx, we investigate the influence of oxygen vacancy concentration and coordination on the oxidation of CeOx by water. Upon changing the CeOx stoichiometry from CeO2 to Ce2O3, we observe a transition from a slow surface reaction to a productive H2-evolving CeOx oxidation with reaction yields exceeding the surface capacity and indicating the participation of bulk OH species. Both the experiments and the ab initio calculations associate the effective oxidation of highly reduced CeOx by water to the next-nearest-neighbor oxygen vacancies present in the bixbyite c-Ce2O3 phase. Next-nearest-neighbor oxygen vacancies allow for the effective incorporation of water in the bulk via formation of OH- groups. Our study illustrates that the coordination of oxygen vacancies in CeOx represents an important parameter to be considered in understanding and improving the reactivity of ceria-based catalysts.

The interplay between the metal-support interaction and stability with respect to sintering has been investigated for Pt nanoparticles supported on well-ordered Co3O4(111)/Ir(100) films in UHV and under oxidizing conditions by means of synchrotron radiation photoelectron spectroscopy (SRPES) and near ambient pressure X-ray photoelectron spectroscopy (NAP XPS). The electronic metal-support interaction between Pt and Co3O4(111) associated with charge transfer results in partial reduction of Co3O4(111) yielding partially oxidized Ptδ+ species at the interface. The stability of the supported Pt particles is coupled with the oxidation state of Ptδ+ species, which can be reduced or oxidized depending on the Pt coverage and reactive environment. Annealing of Pt/Co3O4(111)/Ir(100) in UHV triggers the reduction of Ptδ+ species. At higher temperature, reverse spillover of oxygen to the Pt nanoparticles is accompanied by reduction of Co3O4(111). Under these conditions, the oxidation state of Ptδ+ species depends strongly on Pt coverage. Thus, at low Pt coverage (0.3 ML Pt), Ptδ+ is converted to Pt4+, at intermediate coverage (1.3 ML Pt), Ptδ+ remains stable, and at high Pt coverage (1.93 ML), Ptδ+ is reduced to Pt0. Sintering of Pt particles is associated with the reduction of the Ptδ+ species. This process is prevented under oxidizing conditions due to the formation of an interfacial oxide PtOx. The formation of an interfacial PtOx is observed at 300 K under exposure to 1 × 10−6 mbar O2 at Pt coverages below 1.3 ML. Using NAP XPS, we observe the formation of an interfacial PtOx at high Pt coverage (2.0 ML) in an oxygen atmosphere (1 mbar) at 300 K while the formation of surface PtOx is kinetically hindered and occurs above 550 K only.

The emergence of Dirac semimetals has stimulated growing attention, owing to the considerable technological potential arising from their peculiar exotic quantum transport related to their nontrivial topological states. Especially, materials showing type-II Dirac fermions afford novel device functionalities enabled by anisotropic optical and magnetotransport properties. Nevertheless, real technological implementation has remained elusive so far. Definitely, in most Dirac semimetals, the Dirac point lies deep below the Fermi level, limiting technological exploitation. Here, it is shown that kitkaite (NiTeSe) represents an ideal platform for type-II Dirac fermiology based on spin-resolved angle-resolved photoemission spectroscopy and density functional theory. Precisely, the existence of type-II bulk Dirac fermions is discovered in NiTeSe around the Fermi level and the presence of topological surface states with strong (≈50%) spin polarization. By means of surface-science experiments in near-ambient pressure conditions, chemical inertness towards ambient gases (oxygen and water) is also demonstrated. Correspondingly, NiTeSe-based devices without encapsulation afford long-term efficiency, as demonstrated by the direct implementation of a NiTeSe-based microwave receiver with a room-temperature photocurrent of 2.8 µA at 28 GHz and more than two orders of magnitude linear dynamic range. The findings are essential to bringing to fruition type-II Dirac fermions in photonics, spintronics, and optoelectronics. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH. I.V., A.B.S., and L.Z. contributed equally to this work. L.W. acknowledged support from the State Key Program for Basic Research of China (No. 2017YFA0305500, 2018YFA0306204), Shanghai Municipal Science and Technology Major Project (Grant No. 2019SHZDZX01), and the Science and Technology Commission of Shanghai Municipality (21ZR1473800). A.P. thanks CERIC‐ERIC for the access to the NAP‐XPS facility. D.W.B. acknowledged support from the Ministry of Science and Higher Education of the Russian Federation (through the basic part of the government mandate, Project No. FEUZ‐2020‐0060) and Jiangsu Innovative and Entrepreneurial Talents Project. This work has been partly performed in the framework of the nanoscience foundry and fine analysis (NFFA‐MUR Italy Progetti Internazionali) facility. A.B, B.G, and A.A. acknowledge funding from Science and Engineering Research Board (SERB) and Department of Science and Technology (DST), government of India. A.A. thanks the HPC facility at IIT Kanpur for computational resources.

The adsorption of adenine, one of the structural units of DNA and RNA, on nanostructured cerium oxide was studied using synchrotron radiation based techniques: photoelectron and X-ray absorption spectroscopies. Using a systematic approach, we studied this biomolecule’s bonding to the inorganic surface and examined the effects of different stoichiometry, morphology and composition of cerium oxide films, as well as two methods of molecular deposition (evaporation in vacuum and deposition from aqueous solution). The adenine molecule chemisorbs on the stoichiometric (IV) cerium oxide intact via nitrogen atoms, independent of the oxide morphology and deposition technique. Annealing of the adenine adlayer at 250 °C causes CeO2 surface partial reduction, along with the partial deprotonation of the nitrogen. The reaction of adenine with ex situ prepared CeO2 films (nanostructured compact and porous) activates Ce4+ cation reduction not only on the surface but also in the subsurface layers accompanied by water deso...

Samples of a palladium catalyst for direct formic acid fuel cell (DFAFC) applications were prepared on the Elat ® carbon cloth by magnetron sputtering. The quantity of Pd was equal to 3.6, 120 and 720 μg/cm 2 . The samples were tested in a fuel cell for electro-oxidation of formic acid, and were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The XPS measurements revealed a high contribution of PdC x phase formed at the Pd/Elat ® surface interface, with carbon concentration in PdC x from x = 9.9–14.6 at.%, resulting from the C substrate and CO residual gases. Oxygen groups, e.g. hydroxyl (–OH), carbonyl (C O) and carboxyl (COOH), resulted from the synthesis conditions due to the presence of residual gases, electro-oxidation during the reaction and oxidation in the atmosphere. Because of the formation of CO and CO 2 on the catalysts during the reaction, or because of poisoning by impurities containing the –CH 3 group, together with the risk of Pd losses due to dissolution in formic acid, there was a negative effect of catalyst degradation on the active area surface. The effect of different loadings of Pd layers led to increasing catalyst efficiency. Current–voltage curves showed that different amounts of catalyst did not increase the DFAFC power to a great extent. One reason for this was the catalyst structure formed on the carbon cloth. AFM and SEM measurements showed a layer-by-layer growth with no significant variations in morphology. The results for electric power recalculated for the Pd loading per 1 mg of catalyst layers in comparison to carbon substrates decorated by Pd nanoparticles showed that there is potential for applying anodes for formic acid fuel cells prepared by magnetron sputtering.

As-deposited Pt-Ni and annealed Pt-Ni alloy catalyst films prepared by magnetron co-sputtering were investigated in order to quantify their ageing during accelerated durability test. The parameters of the durability test were chosen to simulate severe potential conditions that may occur at start-up/shut-down cycles of a fuel cell. Using in situ electrochemical atomic force microscopy complemented with ex situ energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, synchrotron radiation photoelectron spectroscopy and X-ray diffraction provided step-by-step correlation of chemical and morphology changes induced by catalyst’s aging processes. We show that the as-deposited Pt-Ni films face severe chemical stability problem which leads to almost complete destruction of the alloy during the durability test. On the other hand Pt-Ni films annealed in vacuum are more resistive to morphological and chemical changes. It was confirmed that upon annealing due to redistribution of Pt and Ni atoms Pt-skin is formed on catalyst surface, which is responsible for a better stability during the aging test.

The interfacial interaction and charge transfer dynamics between a F16CuPc molecular thin film and rutile TiO2(110) (1×1) surface have been studied by photoelectron spectroscopy (PES), near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, and resonant photoemission spectroscopy (RPES). The evolution of PES spectra as a function of F16CuPc film thickness shows strong coupling between the molecules and the TiO2 surface. Adsorbed molecules experience substrate mediated charge transfer. Electrons being pulled away from nitrogen atoms toward to carbon ring results in an opposite direction binding energy shift for C 1s and N 1s. Moreover, the molecule gets deformed due to their strong interaction with the TiO2 surface. Ultrafast charge transfer from F16CuPc molecules to the TiO2 substrate takes place on the time scale of 10 fs due to their strong electronic coupling. The results pave the way for the design and realization of F16CuPc based electronic devices.

A new method based on transformation of magnetron sputtered platinum thin films into platinum nanostructures enclosed by high-index facets, using electrochemical potential cycling in a twin working electrode system is reported. The controllable formation of various Pt nanostructures, described in this paper, indicates that this method can be used to control a selective growth of high purity Pt nanostructures with specific shapes (facets or edges). The method opens up new possibilities for electrochemical preparation of nanostructured Pt catalysts at high yield.