NiFe and CoFe (MFe) layered double hydroxides (LDHs) are among the most active electrocatalysts for the alkaline oxygen evolution reaction (OER). Herein, we combine electrochemical measurements, ...operando X-ray scattering and absorption spectroscopy, and density functional theory (DFT) calculations to elucidate the catalytically active phase, reaction center and the OER mechanism. We provide the first direct atomic-scale evidence that, under applied anodic potentials, MFe LDHs oxidize from as-prepared α-phases to activated γ-phases. The OER-active γ-phases are characterized by about 8% contraction of the lattice spacing and switching of the intercalated ions. DFT calculations reveal that the OER proceeds via a Mars van Krevelen mechanism. The flexible electronic structure of the surface Fe sites, and their synergy with nearest-neighbor M sites through formation of O-bridged Fe-M reaction centers, stabilize OER intermediates that are unfavorable on pure M-M centers and single Fe sites, fundamentally accounting for the high catalytic activity of MFe LDHs.
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.
The electrical performance of a proton exchange membrane fuel cell is limited by the slow oxygen reduction reaction (ORR) kinetics. Catalytic improvements for the ORR have been obtained on alloyed ...PtM/C or M-rich-core@Pt-rich-shell/C catalysts (where M is an early or late transition metal) in comparison to pure Pt/C, due to a combination of strain and ligand effects. However, the effect of the fine nanostructure of the nanomaterials on the ORR kinetics remains underinvestigated. Here, nanometer-sized PtNi/C electrocatalysts with low Ni content (∼15 atom %) but different nanostructures and different densities of grain boundary were synthesized: solid, hollow, or “sea sponge” PtNi/C nanoalloys, and solid Ni-core@Pt-shell/C nanoparticles. These nanostructures were characterized by transmission and scanning transmission electron microscopy, X-ray energy dispersive spectroscopy, synchrotron wide-angle X-ray scattering (WAXS), atomic absorption spectroscopy, and electrochemical techniques. Their electrocatalytic activities for the ORR were determined and structure–activity relationships established. The results showed the following: (i) The compression of the Pt lattice by ca. 15 atom % Ni provides mild ORR activity enhancement in comparison to pure Pt/C. (ii) Highly defective PtNi/C nanostructures feature up to 9.3-fold enhancement of the ORR specific activity over a commercial Pt/C material with similar crystallite size. (iii) The enhancement of the ORR kinetics can be ascribed to the presence of structural defects, as shown by two independent parameters: the microstrain determined from WAXS and the average COads electrooxidation potential (μ1 CO) determined from COads stripping measurements. This work indicates that, at fixed Ni content, ORR activity can be tuned by nanostructuring and suggests that targeting structural disorder is a promising approach to improve the electrocatalytic properties of mono- or bimetallic nanocatalysts.
NiFe layered double hydroxides (LDHs) are among the most active electrocatalysts for alkaline oxygen evolution reaction (OER) and OER selective seawater oxidation. These promising applications call ...for a fundamental understanding of the catalyst/electrolyte interaction, which is challenging to investigate during operation conditions. This work reports an operando structure–reactivity analysis of NiFe LDH as the electrocatalyst for the OER in alkaline and alkalinized NaCl electrolytes, by combining operando wide-angle X-ray scattering (WAXS) and electrochemical characterization. The operando results showed that higher pH values lead to a higher percentage of the OER active γ-NiFe LDH in the composition of the catalyst layer, larger Ni redox peaks, and higher OER activity. The addition of 0.5 M NaCl to moderate alkaline electrolytes (0.1–0.5 M KOH) also leads to larger Ni redox features and higher activity but appears to limit the percentage of γ-NiFe LDH during the OER in comparison to the corresponding NaCl-free electrolytes. Interestingly, a higher KOH concentration (1.0 M KOH, pH 14) could compensate this structural effect aligning the percentage of OER-active γ-NiFe LDH in both NaCl-free and NaCl-containing electrolytes. Additional scan rate investigations showed a strong correlation of the electrochemical accessibility of NiFe LDH with its history, scan rate, and NaCl addition. In particular, the faster and more effective break-in process induced by NaCl addition is proposed as the origin of the enhanced activity at low pH, despite the lower γ-phase percentage.
Nitrogen-enriched porous carbons have been discussed as supports for Pt nanoparticle catalysts deployed at cathode layers of polymer electrolyte membrane fuel cells (PEMFC). Here, we present an ...analysis of the chemical process of carbon surface modification using ammonolysis of preoxidized carbon blacks, and correlate their chemical structure with their catalytic activity and stability using in situ analytical techniques. Upon ammonolysis, the support materials were characterized with respect to their elemental composition, the physical surface area, and the surface zeta potential. The nature of the introduced N-functionalities was assessed by X-ray photoelectron spectroscopy. At lower ammonolysis temperatures, pyrrolic-N were invariably the most abundant surface species while at elevated treatment temperatures pyridinic-N prevailed. The corrosion stability under electrochemical conditions was assessed by in situ high-temperature differential electrochemical mass spectroscopy in a single gas diffusion layer electrode; this test revealed exceptional improvements in corrosion resistance for a specific type of nitrogen modification. Finally, Pt nanoparticles were deposited on the modified supports. In situ X-ray scattering techniques (X-ray diffraction and small-angle X-ray scattering) revealed the time evolution of the active Pt phase during accelerated electrochemical stress tests in electrode potential ranges where the catalytic oxygen reduction reaction proceeds. Data suggest that abundance of pyrrolic nitrogen moieties lower carbon corrosion and lead to superior catalyst stability compared to state-of-the-art Pt catalysts. Our study suggests with specific materials science strategies how chemically tailored carbon supports improve the performance of electrode layers in PEMFC devices.
Cathode catalyst layers of proton exchange membrane fuel cells (PEMFCs) typically consist of carbon-supported platinum catalysts with varying weight ratios of proton-conducting ionomers. N-Doping of ...carbon support materials is proposed to enhance the performance and durability of the cathode layer under operating conditions in a PEMFC. However, a detailed understanding of the contributing N-moieties is missing. Here, we report the successful synthesis and fuel cell implementation of Pt electrocatalysts supported on N-doped carbons, with a focus on the analysis of the N-induced effect on catalyst performance and durability. A customized fluidized bed reduction reactor was used to synthesize highly monodisperse Pt nanoparticles deposited on N-doped carbons (N–C), the catalytic oxygen reduction reaction activity and stability of which matched those of state-of-the-art PEMFC catalysts. Operando high-energy X-ray diffraction experiments were conducted using a fourth generation storage ring; the light of extreme brilliance and coherence allows investigating the impact of N-doping on the degradation behavior of the Pt/N–C catalysts. Tests in liquid electrolytes were compared with tests in membrane electrode assemblies in single-cell PEMFCs. Our analysis refines earlier views on the subject of N-doped carbon catalyst supports: it provides evidence that heteroatom doping and thus the incorporation of defects into the carbon backbone do not mitigate the carbon corrosion during high-potential cycling (1–1.5 V) and, however, can promote the cell performance under usual PEMFC operating conditions (0.6–0.9 V).
The surface restructuring of Pt(111) electrodes upon electrochemical oxidation/reduction in 0.1 M HClO4 was studied by in situ grazing-incidence small-angle X-ray scattering and complementary ...scanning tunneling microscopy measurements. These methods allow quantitative determination of the formation and structural evolution of nanoscale Pt islands during potential cycles into the oxidation region. A characteristic ripening behavior is observed, where these islands become more prominent and homogeneous in size with increasing number of cycles. Their characteristic lateral dimensions primarily depend on the upper potential limit of the cycle and only slightly increase with cycle number. The structural evolution of the Pt surface morphology strongly resembles that found in studies of Pt(111) homoepitaxial growth and ion erosion in ultrahigh vacuum. It can be fully explained by a microscopic model based on the known surface dynamic behavior under vacuum conditions, indicating that the same dynamics also describe the structural evolution of Pt in the electrochemical environment.
The theoretical design of effective metal electrocatalysts for energy conversion and storage devices relies greatly on supposed unilateral effects of catalysts structure on electrocatalyzed ...reactions. Here, by using high-energy X-ray diffraction from the new Extremely Brilliant Source of the European Synchrotron Radiation Facility (ESRF-EBS) on device-relevant Pd and Pt nanocatalysts during cyclic voltammetry experiments in liquid electrolytes, we reveal the near ubiquitous feedback from various electrochemical processes on nanocatalyst strain. Beyond challenging and extending the current understanding of practical nanocatalysts behavior in electrochemical environment, the reported electrochemical strain provides experimental access to nanocatalysts absorption and adsorption trends (i.e., reactivity and stability descriptors) operando. The ease and power in monitoring such key catalyst properties at new and future beamlines is foreseen to provide a discovery platform toward the study of nanocatalysts encompassing a large variety of applications, from model environments to the device level.
The residual stress through the thickness of a BaTiO3 ceramic film deposited on steel substrate at room temperature with aerosol deposition has been analyzed using synchrotron x-ray microdiffraction. ...A gradient in stress distribution was evident through the film and the maximum biaxial compressive stress of −800 MPa was observed at the film-substrate interface. Heat-treatment was found to relax the internal compressive stress, due to thermal expansion mismatch between the film and substrate. Variation in ferroelectric response was correlated to the change in stress state by thermal treatment. This analysis is crucial for development of micro-and nanoelectronic devices with AD films.
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The catalytic performance of extended and nanometer-sized surfaces strongly depends on the amount and the nature of structural defects that they exhibit. However, whereas the effect of steps or ...adatoms may be unraveled with single crystals (“surface science approach”), implementing reproducibly in a controlled manner structural defects on nanomaterials remains hardly feasible. A case that deserves particular attention is that of bimetallic nanomaterials, which are used to catalyze the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFC). Point defects (vacancies), planar defects (dislocations and grain boundaries), and bulk defects (voids, pores) are likely to be generated in alloy or core@shell nanomaterials based on Pt and a transition metal due to the high lattice mismatch between the two elements. Here, we report the morphological and structural trajectories of hollow PtNi/C nanoparticles during thermal annealing under vacuum, N2, H2, or air atmosphere by in situ transmission electron microscopy and synchrotron X-ray diffraction. We evidence atmosphere-dependent restructuring kinetics, which enabled us to synthesize a set of catalysts with identical chemical compositions and elemental distributions but different morphologies, crystallite sizes, and lattice strain. By combining the results of Rietveld and pair-distribution function analyses and electrochemical measurements, we demonstrate that the structurally disordered areas located at the interface between individual crystallites are highly active for two reactions of interest for PEMFC devices: the electrochemical COads oxidation and the ORR. These results shed fundamental light on the effect of structural defects on the catalytic performance of bimetallic nanomaterials and should aid in the rational design of more efficient ORR electrocatalysts.
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