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Platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) with atomically dispersed FeN 4 sites have emerged as a potential replacement for low-PGM catalysts in acidic polymer electrolyte fuel cells (PEFCs). In this work, we carefully tuned the doped Fe content in zeolitic imidazolate framework (ZIF)-8 precursors and achieved complete atomic dispersion of FeN 4 sites, the sole Fe species in the catalyst based on Mößbauer spectroscopy data. The Fe–N–C catalyst with the highest density of active sites achieved respectable ORR activity in rotating disk electrode (RDE) testing with a half-wave potential ( E 1/2 ) of 0.88 ± 0.01 V vs. the reversible hydrogen electrode (RHE) in 0.5 M H 2 SO 4 electrolyte. The activity degradation was found to be more significant when holding the potential at 0.85 V relative to standard potential cycling (0.6–1.0 V) in O 2 saturated acid electrolyte. The post-mortem electron microscopy analysis provides insights into possible catalyst degradation mechanisms associated with Fe–N coordination cleavage and carbon corrosion. High ORR activity was confirmed in fuel cell testing, which also divulged the promising performance of the catalysts at practical PEFC voltages. We conclude that the key factor behind the high ORR activity of the Fe–N–C catalyst is the optimum Fe content in the ZIF-8 precursor. While too little Fe in the precursors results in an insufficient density of FeN 4 sites, too much Fe leads to the formation of clusters and an ensuing significant loss in catalytic activity due to the loss of atomically dispersed Fe to inactive clusters or even nanoparticles. Advanced electron microscopy was used to obtain insights into the clustering of Fe atoms as a function of the doped Fe content. The Fe content in the precursor also affects other key catalyst properties such as the particle size, porosity, nitrogen-doping level, and carbon microstructure. Thanks to using model catalysts exclusively containing FeN 4 sites, it was possible to directly correlate the ORR activity with the density of FeN 4 species in the catalyst.
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This content will become publicly available on December 1, 2026
Electrodeposited palladium and tin bimetallic catalysts for efficient ethanol oxidation to acetate in alkaline electrolyte
Acetic acid (AA), an important commodity chemical, is produced via methanol carbonylation, emitting one ton of CO₂ per ton of product. As a sustainable alternative, we report the electrochemical oxidation of bioethanol to selectively produce AA using a novel Pdsingle bondSn alloy catalyst with nanodendritic morphology supported on nickel foam (PdSn@NF). The catalyst was synthesized via electrodeposition, and the presence of ammonium chloride in the deposition bath was found to critically affect the Pd-to-Sn ratio and, consequently, the catalyst performance. The vital role of catalyst structure, surface composition, and morphology on the activity and selectivity of PdSn@NF towards the EOR was revealed by X-ray diffractometry, emission spectroscopy, and electron microscopy. Specifically, the nanodendritic morphology of the PdSn@NF resulted in the formation of highly active undercoordinated sites, while in situ Raman spectroscopy suggested that Sn helps mitigate CO poisoning – likely a result of a lowered d-band center. Due to the strong synergy between the structural and electronic properties of PdSn@NF, ~100 % faradaic efficiency (FE) to AA at 400 mA cm−2 was achieved with lab-grade ethanol (LGE) in an H-type cell. In continuous flow operation, the FE declined due to product accumulation on active sites; however, this was mitigated by employing current pulses to remove surface-bound products. An optimized pulsing protocol restored ~100 % FE of AA for LGE and achieved ~94 % FE with bioethanol at 400 mA cm−2 despite the presence of fermentation impurities. This study underscores the promise of PdSn@NF as a highly selective and industrially relevant electrocatalyst for sustainable AA production.
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- PAR ID:
- 10654663
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Chemical Engineering Journal
- Volume:
- 527
- ISSN:
- 1385-8947
- Page Range / eLocation ID:
- 171698
- Subject(s) / Keyword(s):
- Pulsed electrolysis, Electrocatalysis, Bimetallic alloyed catalyst, Bio upgrading, Nanodendrite morphology
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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