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      Nanostructured Iron Sulfide/N, S Dual-Doped Carbon Nanotube-Graphene Composites as Efficient Electrocatalysts for Oxygen Reduction Reaction

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          Abstract

          Nanostructured FeS dispersed onto N, S dual-doped carbon nanotube–graphene composite support (FeS/N,S:CNT–GR) was prepared by a simple synthetic method. Annealing an ethanol slurry of Fe precursor, thiourea, carbon nanotube, and graphene oxide at 973 K under N 2 atmosphere and subsequent acid treatment produced FeS nanoparticles distributed onto the N, S-doped carbon nanotube–graphene support. The synthesized FeS/N,S:CNT–GR catalyst exhibited significantly enhanced electrochemical performance in the oxygen reduction reaction (ORR) compared with bare FeS, FeS/N,S:GR, and FeS/N,S:CNT with a small half-wave potential (0.827 V) in an alkaline electrolyte. The improved ORR performance, comparable to that of commercial Pt/C, could be attributed to synergy between the small FeS nanoparticles with a high activity and the N, S-doped carbon nanotube–graphene composite support providing high electrical conductivity, large surface area, and additional active sites.

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          Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts.

          Nitrogen (N)-doped carbon materials exhibit high electrocatalytic activity for the oxygen reduction reaction (ORR), which is essential for several renewable energy systems. However, the ORR active site (or sites) is unclear, which retards further developments of high-performance catalysts. Here, we characterized the ORR active site by using newly designed graphite (highly oriented pyrolitic graphite) model catalysts with well-defined π conjugation and well-controlled doping of N species. The ORR active site is created by pyridinic N. Carbon dioxide adsorption experiments indicated that pyridinic N also creates Lewis basic sites. The specific activities per pyridinic N in the HOPG model catalysts are comparable with those of N-doped graphene powder catalysts. Thus, the ORR active sites in N-doped carbon materials are carbon atoms with Lewis basicity next to pyridinic N.
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            Reduced graphene oxide by chemical graphitization.

            Reduced graphene oxides (RG-Os) have attracted considerable interest, given their potential applications in electronic and optoelectronic devices and circuits. However, very little is known regarding the chemically induced reduction method of graphene oxide (G-O) in both solution and gas phases, with the exception of the hydrazine-reducing agent, even though it is essential to use the vapour phase for the patterning of hydrophilic G-Os on prepatterned substrates and in situ reduction to hydrophobic RG-Os. In this paper, we report a novel reducing agent system (hydriodic acid with acetic acid (HI-AcOH)) that allows for an efficient, one-pot reduction of a solution-phased RG-O powder and vapour-phased RG-O (VRG-O) paper and thin film. The reducing agent system provided highly qualified RG-Os by mass production, resulting in highly conducting RG-O(HI-AcOH). Moreover, VRG-O(HI-AcOH) paper and thin films were prepared at low temperatures (40 °C) and were found to be applicable to flexible devices. This one-pot method is expected to advance research on highly conducting graphene platelets.
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              Metal-free catalysts for oxygen reduction reaction.

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                Author and article information

                Contributors
                Role: Academic Editor
                Journal
                Materials (Basel)
                Materials (Basel)
                materials
                Materials
                MDPI
                1996-1944
                23 April 2021
                May 2021
                : 14
                : 9
                : 2146
                Affiliations
                [1 ]Division of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea; she213@ 123456postech.ac.kr
                [2 ]Interdisciplinary Program in Advanced Functional Materials and Devices Development, Department of Chemical Engineering, Kangwon National University, Chuncheon, Gangwon-do 24341, Korea
                [3 ]School of Energy & Chemical Engineering, Ulsan National University of Science and Technology (UNIST), Ulsan 44919, Korea
                Author notes
                [* ]Correspondence: youndh@ 123456kangwon.ac.kr (D.H.Y.); jlee1234@ 123456unist.ac.kr (J.S.L.)
                Author information
                https://orcid.org/0000-0001-7338-6715
                Article
                materials-14-02146
                10.3390/ma14092146
                8122905
                33922588
                feeaa946-0d55-4356-b85b-7a80f3c6a9e0
                © 2021 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 11 April 2021
                : 20 April 2021
                Categories
                Article

                fuel cells,oxygen reduction reaction,iron sulfide,carbon nanotube–graphene composites,n, s dual doping

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