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      Understanding the mechanism and synergistic interaction of cobalt-based electrocatalysts containing nitrogen-doped carbon for 4 e ORR

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          Abstract

          Considering that the cathodic oxygen reduction reaction (ORR) is sluggish, it is necessary to develop efficient and durable catalysts to accelerate this reaction.

          Abstract

          Considering that the cathodic oxygen reduction reaction (ORR) is sluggish, it is necessary to develop efficient and durable catalysts to accelerate this reaction. Furthermore, the high cost and low abundance of Pt, which is the benchmark catalyst for the cathodic ORR, limit its widespread applications. Among the transition metals, cobalt-based materials have shown significant advancement for the reduction of oxygen molecules, which has been proven by both experimental and theoretical investigations. The high inherent catalytic ability of cobalt among the first row transition metals is the key descriptor for the widespread research in this area. Herein, we review the recent advancements in cobalt-based electrocatalysts supported on nitrogen-doped carbon towards the selective 4 e reduction of oxygen molecules with enhanced operational durability. Furthermore, we highlight the relationship between theory and experiment to investigate the fundamental mechanism of these electrocatalysts. Finally, we present perspectives on suitable approaches for interpreting the mechanism of cobalt-based nitrogen-doped carbon towards the ORR.

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          Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction.

          The large-scale practical application of fuel cells will be difficult to realize if the expensive platinum-based electrocatalysts for oxygen reduction reactions (ORRs) cannot be replaced by other efficient, low-cost, and stable electrodes. Here, we report that vertically aligned nitrogen-containing carbon nanotubes (VA-NCNTs) can act as a metal-free electrode with a much better electrocatalytic activity, long-term operation stability, and tolerance to crossover effect than platinum for oxygen reduction in alkaline fuel cells. In air-saturated 0.1 molar potassium hydroxide, we observed a steady-state output potential of -80 millivolts and a current density of 4.1 milliamps per square centimeter at -0.22 volts, compared with -85 millivolts and 1.1 milliamps per square centimeter at -0.20 volts for a platinum-carbon electrode. The incorporation of electron-accepting nitrogen atoms in the conjugated nanotube carbon plane appears to impart a relatively high positive charge density on adjacent carbon atoms. This effect, coupled with aligning the NCNTs, provides a four-electron pathway for the ORR on VA-NCNTs with a superb performance.
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            Electrocatalyst approaches and challenges for automotive fuel cells.

            Fuel cells powered by hydrogen from secure and renewable sources are the ideal solution for non-polluting vehicles, and extensive research and development on all aspects of this technology over the past fifteen years has delivered prototype cars with impressive performances. But taking the step towards successful commercialization requires oxygen reduction electrocatalysts--crucial components at the heart of fuel cells--that meet exacting performance targets. In addition, these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality. Not all the catalyst approaches currently being pursued will meet those demands.
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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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                Author and article information

                Contributors
                (View ORCID Profile)
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                May 16 2023
                2023
                : 11
                : 19
                : 10095-10124
                Affiliations
                [1 ]Department of Chemistry, Quaid-i-Azam University, Islamabad, 45320, Pakistan
                [2 ]Pakistan Academy of Sciences, 3-Constitution Avenue Sector G-5/2, Islamabad, Pakistan
                Article
                10.1039/D3TA00576C
                eaacad81-7adb-4cf5-873d-74a61bc2bbd7
                © 2023

                http://rsc.li/journals-terms-of-use

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