Single-Atomic Dispersion of Fe and Co Supported on Reduced Graphene Oxide for High-Performance Lithium-Sulfur Batteries.

High theoretical energy density and low cost make lithium-sulfur (LSB) batteries a promising system for next-generation energy storage. LSB performance largely depends on efficient reversible conversion of elemental sulfur to Li2S. Here, well-designed sulfur host materials including Fe or Co single atoms embedded on N-doped reduced graphene oxide (MNC/G with M = Fe or Co) are proposed to tackle the LSB challenges and enhance the electrochemical performance. Using a combination of Mössbauer spectroscopy and high-resolution scanning electron microscopy, the atomic dispersion of Co and Fe was revealed up to relatively high mass loadings. After optimization of the electrolyte/sulfur (E/S) ratio, FeNC/G shows the most promising cycle performance combining a constant high discharge capacity at low E/S values with the lowest polarization. In particular, the material FeNC/G@S with a high sulfur loading (9.4 mg cm-2) delivers a high area capacity of 7.7 mAh cm-2 under lean electrolyte conditions (6 mL g-1).

Review on the Degradation Mechanisms of Metal-N-C Catalysts for the Oxygen Reduction Reaction in Acid Electrolyte: Current Understanding and Mitigation Approaches.

One bottleneck hampering the widespread use of fuel cell vehicles, in particular of proton exchange membrane fuel cells (PEMFCs), is the high cost of the cathode where the oxygen reduction reaction (ORR) occurs, due to the current need of precious metals to catalyze this reaction. Electrochemists tackle this issue in the short/medium term by developing catalysts with improved utilization or efficiency of platinum, and in the longer term, by developing catalysts based on Earth-abundant elements. Considerable progress has been achieved in the initial performance of Metal-nitrogen-carbon (Metal-N-C) catalysts for the ORR, especially with Fe-N-C materials. However, until now, this high performance cannot be maintained for a sufficiently long time in an operating PEMFC. The identification and mitigation of the degradation mechanisms of Metal-N-C electrocatalysts in the acidic environment of PEMFCs has therefore become an important research topic. Here, we review recent advances in the understanding of the degradation mechanisms of Metal-N-C electrocatalysts, including the recently identified importance of combined oxygen and electrochemical potential. Results obtained in a liquid electrolyte and a PEMFC device are discussed, as well as insights gained from in situ and operando techniques. We also review the mitigation approaches that the scientific community has hitherto investigated to overcome the durability issues of Metal-N-C electrocatalysts.

On the Influence of Oxygen on the Degradation of Fe-N-C Catalysts.

Fe-N-C catalysts containing atomic FeNx sites are promising candidates as precious-metal-free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The durability of Fe-N-C catalysts in fuel cells has been extensively studied using accelerated stress tests (AST). Herein we reveal stronger degradation of the Fe-N-C structure and four-times higher ORR activity loss when performing load cycling AST in O2 - vs. Ar-saturated pH 1 electrolyte. Raman spectroscopy results show carbon corrosion after AST in O2 , even when cycling at low potentials, while no corrosion occurred after any load cycling AST in Ar. The load-cycling AST in O2 leads to loss of a significant fraction of FeNx sites, as shown by energy dispersive X-ray spectroscopy analyses, and to the formation of Fe oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O2 is due to reactive oxygen species produced between H2 O2 and Fe sites via Fenton reactions.

Carbon Corrosion in Proton-Exchange Membrane Fuel Cells: Spectrometric Evidence for Pt-Catalysed Decarboxylation at Anode-Relevant Potentials.

The carbon oxidation reaction (COR) is a critical issue in proton-exchange membrane fuel cells (PEMFCs), as carbon in various forms is the most used electrocatalyst support material. The COR is thermodynamically possible above the C/CO2 standard potential, but its rate becomes significantly important only at high overpotential (e. g. PEMFC cathode potential). Herein, using on-line differential electrochemical mass spectrometry, we show that oxygen-containing carbon surface groups present on high-surface aera carbon, Vulcan XC72 or reinforced graphite are oxidized at PEMFC anode-relevant potential (E=0.1 V vs. the reversible hydrogen electrode, RHE), but not at E=0.4 V vs. RHE. We rationalized our findings by considering a Pt-catalysed decarboxylation mechanism in which Pt nanoparticles provide adsorbed hydrogen species to the oxygen-containing carbon surface groups, eventually leading to evolution of carbon dioxide and carbon monoxide. These results shed fundamental light on an unexpected degradation mechanism and facilitate the understanding of the long-term stability of PEMFC anode nanocatalysts.

Top-Down Synthesis of Nanostructured Platinum-Lanthanide Alloy Oxygen Reduction Reaction Catalysts: Pt xPr/C as an Example.

The oxygen reduction reaction (ORR) is of great interest for future sustainable energy conversion and storage, especially concerning fuel cell applications. The preparation of active, affordable, and scalable electrocatalysts and their application in fuel cell engines of hydrogen cars is a prominent step toward the reduction of air pollution, especially in urban areas. Alloying nanostructured Pt with lanthanides is a promising approach to enhance its catalytic ORR activity, whereby the development of a simple synthetic route turned out to be a nontrivial endeavor. Herein, for the first time, we present a successful single-step, scalable top-down synthetic route for Pt-lanthanide alloy nanoparticles, as witnessed by the example of Pr-alloyed Pt nanoparticles. The catalyst was characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and photoelectron spectroscopy, and its electrocatalytic oxygen reduction activity was investigated using a rotating disk electrode technique. Pt xPr/C showed ∼3.5 times higher [1.96 mA/cm2Pt, 0.9 V vs reversible hydrogen electrode (RHE)] specific activity and ∼1.7 times higher (0.7 A/mgPt, 0.9 V vs RHE) mass activity compared to commercial Pt/C catalysts. On the basis of previous findings and characterization of the Pt xPr/C catalyst, the activity improvement over commercial Pt/C originates from a lattice strain introduced by the alloying process.

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

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

A Review on Recent Developments and Prospects for the Oxygen Reduction Reaction on Hollow Pt-alloy Nanoparticles.

Due to their interesting electrocatalytic properties for the oxygen reduction reaction (ORR), hollow Pt-alloy nanoparticles (NPs) supported on high-surface-area carbon attract growing interest. However, the suitable synthesis methods and associated mechanisms of formation, the reasons for their enhanced specific activity for the ORR, and the nature of adequate alloying elements and carbon supports for this type of nanocatalysts remain open questions. This Review aims at shedding light on these topics with a special emphasis on hollow PtNi NPs supported onto Vulcan C (PtNi/C). We first show how hollow Pt-alloy/C NPs can be synthesized by a mechanism involving galvanic replacement and the nanoscale Kirkendall effect. Nickel, cobalt, copper, zinc, and iron (Ni, Co, Cu, Zn, and Fe, respectively) were tested for the formation of Pt-alloy/C hollow nanostructures. Our results indicate that metals with standard potential -0.4

Elucidating the Mechanisms Driving the Aging of Porous Hollow PtNi/C Nanoparticles by Means of COads Stripping.

The oxygen reduction reaction (ORR) activity of Pt-alloy electrocatalysts depends on (i) the strain/ligand effects induced by the non-noble metal (3d-transition metal or a rare-earth element) alloyed to Pt, (ii) the orientation of the catalytic surfaces, and (iii) the density of structural defects (SDs) (e.g., vacancies, voids, interconnections). These SDs influence the "generalized" coordination number of Pt atoms, the Pt-alloy lattice parameter, and thus the adsorption strength of the ORR intermediates (O*, OH*, OOH*). Here, we discuss a set of parameters derived from COads stripping measurements and the Rietveld refinement of X-ray diffraction (XRD) patterns, aiming to show how the leaching of the non-noble metal and the density of SDs influence the ORR activity of porous hollow PtNi/C nanoparticles (PH-PtNi/C NPs). PH-PtNi/C NPs were aged at T = 353 K in an Ar-saturated 0.1 M HClO4 electrolyte during 20 000 potential cycles between E = 0.6 and 1.0 V versus the reversible hydrogen electrode, with an intermediate characterization after 5000 cycles. The losses in the ORR specific activity were attributed to the dissolution of Ni atoms (modifying strain/ligand effects) and to the increase of the crystallite size (dXRD), resulting in a diminution of the density of grain boundaries. In agreement with the Gibbs-Thompson equation, the electrocatalysts that presented larger crystallites (dXRD > 3 nm) were far more stable than the ones with the smallest crystallites (dXRD < 2 nm). We also observed that performing intermediate characterizations (in an O2-saturated electrolyte) results in activity losses for the ORR.

Atomic-Scale Snapshots of the Formation and Growth of Hollow PtNi/C Nanocatalysts.

Determining the formation and growth mechanism of bimetallic nanoparticles (NPs) with atomic detail is fundamental to synthesize efficient "catalysts by design". However, an understanding of the elementary steps which take place during their synthesis remains elusive. Herein, we have exploited scanning transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy, operando wide angle and small-angle X-ray scattering, and electrochemistry to unveil the formation and growth mechanism of hollow PtNi/C NPs. Such NPs, composed of a PtNi shell surrounding a nanoscale void, catalyze efficiently and sustainably the oxygen reduction reaction (ORR) in an acidic electrolyte. Our step-by-step study reveals that (i) Ni-rich/C NPs form first, before being embedded in a NixByOz shell, (ii) the combined action of galvanic displacement and the nanoscale Kirkendall effect then results in the sequential formation of Ni-rich core@Pt-rich/C shell and ultimately hollow PtNi/C NPs. The electrocatalytic properties for the ORR and the stability of the different synthesis intermediates were tested and structure-activity-stability relationships established both in acidic and alkaline electrolytes. Beyond its interest for the ORR electrocatalysis, this study also presents a methodology that is capable to unravel the formation and growth mechanism of various nanomaterials including preferentially shaped metal NPs, core@shell NPs, onion-like NPs, Janus NPs, or a combination of several of these structures.

Reversibility of Pt-Skin and Pt-Skeleton Nanostructures in Acidic Media.

Following a well-defined series of acid and heat treatments on a benchmark Pt3Co/C sample, three different nanostructures of interest for the electrocatalysis of the oxygen reduction reaction were tailored. These nanostructures could be sorted into the "Pt-skin" structure, made of one pure Pt overlayer, and the "Pt-skeleton" structure, made of 2-3 Pt overlayers surrounding the Pt-Co alloy core. Using a unique combination of high-resolution aberration-corrected STEM-EELS, XRD, EXAFS, and XANES measurements, we provide atomically resolved pictures of these different nanostructures, including measurement of the Pt-shell thickness forming in acidic media and the resulting changes of the bulk and core chemical composition. It is shown that the Pt-skin is reverted toward the Pt-skeleton upon contact with acid electrolyte. This change in structure causes strong variations of the chemical composition.