Tuning the performance of Fe-porphyrin aerogel-based PGM-free oxygen reduction reaction catalysts in proton exchange membrane fuel cells.

Fe-N-C catalysts are currently the leading candidates to replace Pt-based catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells. To maximize their activity, it is necessary to optimize their structure to allow high active site density on one hand, and hierarchical porous structure that will allow good mass transport of reactants and products to and from the active sites on the other hand. Hence, the hierarchical structure of the catalyst plays an important role in the balance between the electrochemical active site density and the mass transport resistance. Aerogels were synthesized in this work to study the interplay between these two parameters. Aerogels are covalent organic frameworks with ultra-low density, high porosity, and large surface area. The relative ease of tuning the composition and pore structure of aerogels make them prominent candidates for catalysis. Herein, we report on a tunable Fe-N-C catalyst based on an Fe porphyrin aerogel, which shows high electrocatalytic oxygen reduction reaction activity with tunable hierarchical pore structure and studied the influence of the porous structure on the overall performance in proton exchange membrane fuel cells.

NiFe-mixed metal porphyrin aerogels as oxygen evolution reaction catalysts in alkaline electrolysers.

Aerogels are a very interesting group of materials owing to their unique physical and chemical properties. In the context of electrocatalysis, the focus has been on their physical properties, and they have been used primarily as catalyst supports so far. In this work, we synthesized porphyrin aerogels containing Ni and NiFe mixed metal materials and studied them as catalysts for the oxygen evolution reaction (OER). Different Ni : Fe ratios were synthesized and studied in electrochemical cells, and DFT calculations were conducted in order to gain insight into their behavior. The activity trends were dependent on the metal ratios and differ from known NiFeOOH materials due to the change in the oxidation states of the metals to higher numbers. Herein, we show that Ni and Fe have a synergistic effect on the OER, despite being structurally separated. They are connected electronically, though, through a large organic aromatic system that facilitates electron sharing between them. Among the mixed metal porphyrin aerogels, the best ratio was found to be Ni : Fe = 35 : 65, in contrast to oxide/oxyhydroxide materials in which a ratio of 80 : 20 was found to be ideal.

Application of Molecular Catalysts for the Oxygen Reduction Reaction in Alkaline Fuel Cells.

The development of precious group metal-free (PGM-free) catalysts for the oxygen reduction reaction is considered as the main thrust for the cost reduction of fuel cell technologies and their mass production. Within the PGM-free category, molecular catalysts offer an advantage over other heat-treated PGM-free catalysts owing to their well-defined structure, which enables further design of more active, selective, and durable catalysts. Even though non-heat-treated molecular catalysts with exceptional performance have been reported in the past, they were rarely tested in a fuel cell. Herein, we report on a molecular catalyst under alkaline conditions: fluorinated iron phthalocyanine (FeFPc) supported on cheap and commercially available high-surface area carbon─BP2000 (FeFPc@BP2000). It exhibits the highest activity ever reported for molecular catalysts under alkaline conditions in half-cells and fuel cells.

Bifunctional PGM-free metal organic framework-based electrocatalysts for alkaline electrolyzers: trends in the activity with different metal centers.

In order to solely rely on renewable and efficient energy sources, reliable energy storage and production systems are required. Hydrogen is considered an ideal solution as it can be produced electrochemically by water electrolysis and renewably while no pollutants are released when consumed. The most common catalysts in electrolyzers are composed of rare and expensive precious group metals. Replacing these materials with Earth-abundant materials is important to make these devices economically viable. Metal organic frameworks are one possible solution. Herein we demonstrate the synthesis and characterization studies of metal benzene-tri-carboxylic acid-based metal-organic frameworks embedded in activated carbon. The conductive composite material was found to be electrocatalytically active for both the oxygen evolution reaction and the hydrogen evolution reaction. Furthermore, several metal organic frameworks sharing the same ligand but with different first-row transition metals (M = Co, Cu, Fe, Mn) were compared, and the trend of their activity is discussed. Cobalt was found to have the highest activity among the studied metal centers, and therefore has the best potential to serve as a bifunctional catalyst for alkaline electrolyzers.

Enhancement of the oxygen reduction reaction electrocatalytic activity of metallo-corroles using contracted cobalt(iii) CF3-corrole incorporated in a high surface area carbon support.

Molecular oxygen reduction reaction catalysts based on metallo-corrole with the smallest meso-substituent reported to-date, Co(iii)CF3-corrole, was synthesized and compared to the well-studied Co(iii)tpfcorrole when adsorbed on a high surface area carbon support. This study shows the improved electrocatalytic performance with the new corrole, attributed to its unique compact structure, which enables surface interactions in favor of lowering the reaction overpotential by 70 mV.

Heat-Treated Aerogel as a Catalyst for the Oxygen Reduction Reaction.

Aerogels are fascinating materials that can be used for a wide range of applications, one of which is electrocatalysis of the important oxygen reduction reaction. In their inorganic form, aerogels can have ultrahigh catalytic site density, high surface area, and tunable physical properties and chemical structures-important features in heterogeneous catalysis. Herein, we report on the synthesis and electrocatalytic properties of an iron-porphyrin aerogel. 5,10,15,20-(Tetra-4-aminophenyl)porphyrin (H2 TAPP) and FeII were used as building blocks of the aerogel, which was later heat-treated at 600 °C to enhance electronic conductivity and catalytic activity, while preserving its macrostructure. The resulting material has a very high concentration of atomically dispersed catalytic sites (9.7×1020  sites g-1 ) capable of catalyzing the oxygen reduction reaction in alkaline solution (Eonset =0.92 V vs. RHE, TOF=0.25 e- site-1 s-1 at 0.80 V vs. RHE).

Bioinspired Electrocatalysis of Oxygen Reduction Reaction in Fuel Cells Using Molecular Catalysts.

One of the most important chemical reactions for renewable energy technologies such as fuel cells and metal-air batteries today is oxygen reduction. Due to the relatively sluggish reaction kinetics, catalysts are necessary to generate high power output. The most common catalyst for this reaction is platinum, but its scarcity and derived high price have raised the search for abundant nonprecious metal catalysts. Inspired from enzymatic processes which are known to catalyze oxygen reduction reaction efficiently, employing transition metal complexes as their catalytic centers, many are working on the development of bioinspired and biomimetic catalysts of this class. This research news article gives a glimpse of the recent progress on the development of bioinspired molecular catalyst for oxygen reduction, highlighting the importance of the molecular structure of the catalysts, from advancements in porphyrins and phthalocyanines to the most recent work on corroles, and 3D networks such as metal-organic frameworks and polymeric networks, all with nonpyrolyzed, well-defined molecular catalysts for oxygen reduction reaction.