Iron-nitrogen-carbon (Fe-N-C) catalysts are a promising class of non-precious electrocatalysts for the oxygen reduction reaction (ORR), with strong potential for integration into emerging energy technologies. Here, an oxygen-bridged axial coordination strategy is employed to anchor iron phthalocyanine (FePc) onto manganese oxide decorated carbon nanotubes (Mn3O4-CNTs). The resulting synergy between asymmetric Fe-N4-O sites and heterojunction interfaces finely tailors the local coordination of Fe centers, which induces electron transfer from the Fe center to the axial O atom and downshifts the Fe d-band center, thereby weakening the adsorption strength of oxygen-containing intermediates and substantially boosting ORR activity. In alkaline media, the optimized FePc-Mn3O4-CNTs catalyst exhibits a high half-wave potential (E1/2) of 0.89 V vs. reversible hydrogen electrode (RHE), a low Tafel slope of 41.51 mV·dec–1, and follows an efficient four-electron pathway. This catalytic performance translates directly into a zinc-air battery that delivers a peak power density of 171.81 mW·cm–2, a specific capacity of 754.12 mAh·g–1, and stable operation for 160 h. This work demonstrates a coordinated strategy combining axial coordination engineering with heterojunction design to synergistically optimize the catalytic properties of Fe-N-C molecular catalysts.
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Open Access
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Direct ethanol fuel cells (DEFCs) are a promising alternative to conventional energy sources, offering high energy density, environmental sustainability, and operational safety. Compared to methanol fuel cells, DEFCs exhibit lower toxicity and a more mature preparation process. Unlike hydrogen fuel cells, DEFCs provide superior storage and transport feasibility, as well as cost-effectiveness, significantly enhancing their commercial viability. However, the stable C–C bond in ethanol creates a high activation energy barrier, often resulting in incomplete electrooxidation. Current commercial platinum (Pt)- and palladium (Pd)-based catalysts demonstrate low C–C bond cleavage efficiency (<7.5%), severely limiting DEFC energy output and power density. Furthermore, high catalyst costs and insufficient activity impede large-scale commercialization. Recent advances in DEFC anode catalyst design have focused on optimizing material composition and elucidating catalytic mechanisms. This review systematically examines developments in ethanol electrooxidation catalysts over the past five years, highlighting strategies to improve C1 pathway selectivity and C–C bond activation. Key approaches, such as alloying, nanostructure engineering, and interfacial synergy effects, are discussed alongside their mechanistic implications. Finally, we outline current challenges and future prospects for DEFC commercialization.
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Research Article
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The development of electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is crucial for sustainable energy and environmental initiatives. This work establishes an atomically-dispersed Ru-based model to investigate the promoting mechanism by the Ru-Integration effect in RuCo bimetallic nanoparticles supported on nitrogen-doped carbon (RuCo@NC). Specially, the Ru content in RuCo@NC plays a vital role for both HER and OER. The optimized catalyst shows an outstanding performance, requiring only 217 and 97 mV overpotential to reach a current density of 10 mA·cm−2 for OER and HER respectively in alkaline conditions. Combined with advanced characterizations such as spherical aberration-corrected scanning transmission electron microscopy, X-ray absorption spectroscopy, in-situ Raman spectroscopy, and density functional theory calculations, it is found that Ru plays multiple crucial roles: (1) Ru restricts the growth of large Co NPs, while the small-sized Co NPs facilitate the formation of carbon nanotubes, which significantly enhances the mass/electron transfer; (2) Ru not only tunes the surface properties of Co but also acts as an active site for HER. As a result, when using RuCo@NC as an overall water splitting catalyst, it only needs a potential of 1.62 V to reach a current density of 100 mA·cm−2. This work offers valuable insights into designing Ru-based electrocatalysts for water splitting.
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Research Article
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Zinc-air batteries hold great promise as a next-generation efficient and environmentally friendly energy technology. However, the sluggish kinetics of the oxygen reduction reaction (ORR) process pose a significant challenge to their development. To address this issue, atom dispersion catalysts are developed to maximize the utilization of metal active centers. Metal-organic frameworks (MOFs) are a series of molecular materials with high atomic-level dispersion metal utilization, but they often lack sufficient electrical conductivity. Their application in MOF electrocatalysis remains limited unless the MOF material is transferred to a carbon-based material through heat treatment. To overcome this limitation, we employed coordination engineering to incorporate hexaaminotriphenylene (HATP) molecules with strong conjugation into Co-MOF-74. The resulting Co-MOF-74-HATP catalyst represents high activity, achieving an ORR half-wave potential (E1/2) of 0.84 V and demonstrating good stability (ΔE1/2 = 20 mV after 10,000 cycles). Additionally, the Co-MOF-74-HATP also performs a 320 mV overpotential (10 mA·cm−2) for the oxygen evolution reaction. Meanwhile, Co-MOF-74-HATP displays a peak power density of 96.6 mW·cm−2 in zinc-air batteries, surpassing the commercially available Pt/C + RuO2. This work presents a new pathway to design MOF-based ORR catalysts and provides a new direction for the preparation of key materials for zinc-air battery (ZAB).
Polyoxometalate-based nanocomposites with electrocatalytic activity have been applied in hydrogen evolution reactions (HER). Seawater as the main water resource on the earth should be developed as the water electrolysis to prepare high-purity hydrogen. In this paper, we used two synthesis strategies to prepare the nanocomposite Co4-POM@Co-PGDY (Co4-POM: the Kegging-type microcrystals of K10[Co4(PW9O34)2] and Co-PGDY: cobalt-porphyrin linked graphdiyne) with excellent activity for HER. Co-PGDY as the porous material is applied not only as the protection of microcrystals towards the metal ion in seawater but also as the co-electrocatalyst of Co4-POM. Co4-POM@Co-PGDY exhibits excellent HER performance in seawater electrolytes with low overpotential and high stability at high density. Moreover, we have observed a key H3O+ intermediate emergence on the surface of nanocomposite during hydrogen evolution process in seawater by Raman synchrotron radiation-based Fourier transform infrared (SR-FTIR). The results in this paper provide an effective strategy for preparing polyoxometalate-based electrocatalysts with high-performance toward hydrogen evolution reaction.
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