A facile one-step strategy for anchoring defective CoN single clusters on partly reduced graphene oxide (RGO) is constructed to significantly improve the catalytic performance of non-noble metal complexes toward oxygen reduction reaction (ORR). Sequent loading with trace amounts of metal-free porphyrin and Co in RGO can dramatically enhance both the half-wave potential and the peak current density. Intriguingly, the RGO/P/2Co single cluster exhibits the best ORR catalytic performance with the half-wave potential of 0.834 V, extremely approaching that of commercial Pt/C (0.836 V). This half-wave potential surpasses most of the reported half-wave potentials of RGO supported non-noble metal ORR catalysts through low-temperature synthesis. Furthermore, the as-prepared RGO/P/2Co delivers a peak current density of 1.3 times higher than that of Pt/C at the same loading, together with a high mass activity of 2.76 A mg. During the durability test, a cathodic current loss less than 10% is recorded after 8000 continuous potential cycles. Insights into this successful example will be conducive to the development of elegant routes for constructing metal nitrogen (MN)-based ORR catalysts with high efficiency, outstanding stability, and excellent selectivity.
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http://dx.doi.org/10.1021/acsami.7b04667 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Henan Provincial Key Laboratory of Nanocomposites and Applications, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou, Henan 450006, China.
Due to the high configuration entropy, unique atomic arrangement, and electronic structures, high-entropy materials are being actively pursued as bifunctional catalysts for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable zinc-air batteries (ZABs). However, a relevant strategy to enhance the catalytic activity of high-entropy materials is still lacking. Herein, a hole doping strategy has been employed to enable the high-entropy perovskite La(CrMnFeCoNi)O to effectively catalyze the ORR and OER.
View Article and Find Full Text PDFSmall
January 2025
Beijing Key Laboratory of Energy Conversion and Storage Materials, College of Chemistry, Beijing Normal University, Beijing, 100875, P. R. China.
Establishing the relationship between catalytic performance and material structure is crucial for developing design principles for highly active catalysts. Herein, a type of perovskite fluoride, NHMnF, which owns strong-field coordination including fluorine and ammonia, is in situ grown on carbon nanotubes (CNTs) and used as a model structure to study and improve the intrinsic catalytic activity through heteroatom doping strategies. This approach optimizes spin-dependent orbital interactions to alter the charge transfer between the catalyst and reactants.
View Article and Find Full Text PDFNat Commun
January 2025
College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, 610065 Chengdu, China.
Dual-atom catalysts featuring synergetic dinuclear active sites, have the potential of breaking the linear scaling relationship of the well-established single-atom catalysts for oxygen reduction reaction; however, the design of dual-atom catalysts with rationalized local microenvironment for high activity and selectivity remains a great challenge. Here we design a bisalphen ladder polymer with well-defined densely populated binuclear cobalt sites on Ketjenblack substrates. The strong electron coupling effect between the fully-conjugated ladder structure and carbon substrates enhances the electron transfer between the cobalt center and oxygen intermediates, inducing the low-to-high spin transition for the 3d electron of Co(II).
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
Department of Aviation Oil and Material, Air Force Logistics Academy, 72 Xi Ge Road, Xuzhou, Jiangsu 221000, China.
Metal-air batteries desire highly active, durable, and low-cost oxygen reduction catalysts to replace expensive platinum (Pt). The Fe-N-C catalyst is recognized as the most promising candidate for Pt; however, its durability is hindered by carbon corrosion, while activity is restricted due to limited oxygen for the reaction. Herein, TiN is creatively designed to be hybridized with Fe-N-C (TiN/Fe-N-C) to relieve carbon corrosion and absorb more oxygen when catalyzing oxygen reduction.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Ulsan National Institute of Science and Technology, Department of Energy and Chemical Engineering/Center for Dimension-Controllable Orga, 50 UNIST, 44919, Ulsan, KOREA, REPUBLIC OF.
Metal-free covalent organic frameworks (COFs) have emerged as promising catalysts for the oxygen reduction reaction (ORR) because of their unique structural properties and notable stability. To enhance both catalytic activity and selectivity, a variety of linkers and linkages have been investigated in efforts to precisely engineer COFs. However, the impact of vertex structures within COFs on ORR catalysis remains largely underexplored.
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