Régis Chenitz

Bio: Régis Chenitz is an academic researcher from Institut national de la recherche scientifique. The author has contributed to research in topics: Catalysis & Proton exchange membrane fuel cell. The author has an hindex of 14, co-authored 20 publications receiving 4675 citations. Previous affiliations of Régis Chenitz include Mines ParisTech.

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction

Abstract: The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.

Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells

Abstract: Hydrogen produced from water and renewable energy could fuel a large fleet of proton-exchange-fuel-cell vehicles in the future. However, the dependence on expensive Pt-based electrocatalysts in such fuel cells remains a major obstacle for a widespread deployment of this technology. One solution to overcome this predicament is to reduce the Pt content by a factor of ten by replacing the Pt-based catalysts with non-precious metal catalysts at the oxygen-reducing cathode. Fe- and Co-based electrocatalysts for this reaction have been studied for over 50 years, but they were insufficiently active for the high efficiency and power density needed for transportation fuel cells. Recently, several breakthroughs occurred that have increased the activity and durability of non-precious metal catalysts (NPMCs), which can now be regarded as potential competitors to Pt-based catalysts. This review focuses on the new synthesis methods that have led to these breakthroughs. A modeling analysis is also conducted to analyze the improvements required from NPMC-based cathodes to match the performance of Pt-based cathodes, even at high current density. While no further breakthrough in volume-specific activity of NPMCs is required, incremental improvements of the volume-specific activity and effective protonic conductivity within the fuel-cell cathode are necessary. Regarding durability, NPMCs with the best combination of durability and activity result in ca. 3 times lower fuel cell performance than the most active NPMCs at 0.80 V. Thus, major tasks will be to combine durability with higher activity, and also improve durability at cell voltages greater than 0.60 V.

A specific demetalation of Fe–N4 catalytic sites in the micropores of NC_Ar + NH3 is at the origin of the initial activity loss of the highly active Fe/N/C catalyst used for the reduction of oxygen in PEM fuel cells

Abstract: In this study, we explored the behavior of NC_Ar + NH3, an initially highly active catalyst for oxygen electroreduction, in H2/air fuel cells from 0.8 to 0.2 V at 80 °C and 25 °C, in order to find the causes of its instability. We discovered that the decay of the current density always involves the superposition of fast and slow first order kinetics, for which half-lives were obtained. The half-life of the fast decay was practically the same at all potentials and temperatures with a value of around 138 ± 55 min, while the half-life of the slow decay greatly varied from a minimum of ≈2400 min (40 h) to infinity. From the adsorption–desorption isotherm of NC_Ar + NH3, it was deduced that the Fe/N/C carbonaceous catalyst is characterized by interconnected open-end slit-shaped micropores, in which water (with dissolved H+ and O2) quickly flows in the fuel cells if their width is ≥0.7 nm as it has no interaction with the hydrophobic walls of the micropores. The driving force of this quick water flow is the humidified air streaming through the working cathode. Fe–N4-like active sites are thermodynamically stable in stagnant acidic conditions, but according to the Le Chatelier principle, they demetalate in the flux of water running into the micropores. This specific demetalation is the cause of the initial loss of ORR activity of NC_Ar + NH3 catalysts assigned to the fast current decay in fuel cells.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

Abstract: A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt

Abstract: The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt

Abstract: Fuel cell catalysts synthesized from abundant metals approach the performance and durability of platinum at lower cost. The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non–precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non–precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction

Abstract: The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts

Abstract: Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).