It remains a grand challenge to replace platinum group metal (PGM) catalysts with earth-abundant materials for the oxygen reduction reaction (ORR) in acidic media, which is crucial for large-scale deployment of proton exchange membrane fuel cells (PEMFCs). Here, we report a high-performance atomic Fe catalyst derived from chemically Fe-doped zeolitic imidazolate frameworks (ZIFs) by directly bonding Fe ions to imidazolate ligands within 3D frameworks. Although the ZIF was identified as a promising precursor, the new synthetic chemistry enables the creation of well-dispersed atomic Fe sites embedded into porous carbon without the formation of aggregates. The size of catalyst particles is tunable through synthesizing Fe-doped ZIF nanocrystal precursors in a wide range from 20 to 1000 nm followed by one-step thermal activation. Similar to Pt nanoparticles, the unique size control without altering chemical properties afforded by this approach is able to increase the number of PGM-free active sites. The best ORR activity is measured with the catalyst at a size of 50 nm. Further size reduction to 20 nm leads to significant particle agglomeration, thus decreasing the activity. Using the homogeneous atomic Fe model catalysts, we elucidated the active site formation process through correlating measured ORR activity with the change of chemical bonds in precursors during thermal activation up to 1100 °C. The critical temperature to form active sites is 800 °C, which is associated with a new Fe species with a reduced oxidation number (from Fe to Fe) likely bonded with pyridinic N (FeN) embedded into the carbon planes. Further increasing the temperature leads to continuously enhanced activity, linked to the rise of graphitic N and Fe-N species. The new atomic Fe catalyst has achieved respectable ORR activity in challenging acidic media (0.5 M HSO), showing a half-wave potential of 0.85 V vs RHE and leaving only a 30 mV gap with Pt/C (60 μg/cm). Enhanced stability is attained with the same catalyst, which loses only 20 mV after 10 000 potential cycles (0.6-1.0 V) in O saturated acid. The high-performance atomic Fe PGM-free catalyst holds great promise as a replacement for Pt in future PEMFCs.
High dispersion Pt nanoparticles supported on 2D Ti3C2X2 (X = OH, F) nanosheets are presented and electro-chemical measurements confirm that the Pt/Ti3C2X2 catalyst shows enhanced durability and improved ORR activity compared with the commercial Pt/C catalyst.
Oxygen reduction reaction (ORR) is one of the essential electrochemical reactions for the energy conversion and storage devices such as fuel cells and metal-air batteries. However, a large amount of Pt is required for catalyzing the kinetically sluggish ORR at the air cathode, therefore greatly limiting their large scale implementation. Development of high-performance platinum group-metal (PGM)-free ORR catalysts has been a long-term goal for such clean energy technologies. However, current PGM-free catalysts are still significantly suffering from insufficient activity and limited durability especially in more challenging acidic media, such as proton exchange membranes (PEM) fuel cells. Recently, metal-organic frameworks (MOFs), constructed from bridging metal ions and ligands, have emerged as a new type of attractive precursors for the synthesis of PGM-free catalysts, which has led to encouraging performance improvement. Compared to other catalyst precursors, MOFs have well-defined crystal structure with tunable chemistry and contain all required elements (e.g., carbon, nitrogen, and metal). Here, we provide an account of recent innovative PGM-free catalyst design and synthesis derived from the unique MOF precursors with special emphasis on engineering nanostructure and morphology of catalysts. We aim to provide new insights into the design and synthesis of advanced PGM-free
Fuel cells as an attractive clean energy technology have recently regained popularity in academia, government, and industry. In a mainstream proton exchange membrane (PEM) fuel cell, platinum‐group‐metal (PGM)‐based catalysts account for ≈50% of the projected total cost for large‐scale production. To lower the cost, two materials‐based strategies have been pursued: 1) to decrease PGM catalyst usage (so‐called low‐PGM catalysts), and 2) to develop alternative PGM‐free catalysts. Grand stability challenges exist when PGM catalyst loading is decreased in a membrane electrode assembly (MEA)—the power generation unit of a PEM fuel cell—or when PGM‐free catalysts are integrated into an MEA. More importantly, there is a significant knowledge gap between materials innovation and device integration. For example, high‐performance electrocatalysts usually demonstrate undesired quick degradation in MEAs. This issue significantly limits the development of PEM fuel cells. Herein, recent progress in understanding the degradation of low‐PGM and PGM‐free catalysts in fuel cell MEAs and materials‐based solutions to address these issues are reviewed. The key factors that degrade the MEA performance are highlighted. Innovative, emerging material concepts and development of low‐PGM and PGM‐free catalysts are discussed.
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