Heteroatoms ternary-doped porous carbons derived from MOFs as metal-free electrocatalysts for oxygen reduction reaction
TL;DR: The outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media.
Abstract: The nitrogen (N), phosphorus (P) and sulphur (S) ternary-doped metal-free porous carbon materials have been successfully synthesized using MOFs as templates (denoted as NPS-C-MOF-5) for oxygen reduction reaction (ORR) for the first time. The influences of porous carbons from carbonizing different MOFs and carbonization temperature on ORR have been systematically investigated. Due to the synergistic effect of N, P and S ternary-doping, the NPS-C-MOF-5 catalyst shows a higher onset potential as a metal-free electrocatalyst for ORR among the currently reported metal-free electrocatalysts, very close to the commercial Pt-C catalyst. In particular, the kinetic limiting current density of NPS-C-MOF-5 catalyst at −0.6 V is up to approximate −11.6 mA cm−2, which is 1.2 times higher than that of the commercial Pt-C catalyst. Furthermore, the outstanding methanol tolerance and excellent long-term stability of NPS-C-MOF-5 are superior to those of the commercial Pt-C catalyst for ORR in alkaline media.
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TL;DR: In this article, a review of the recent progress in fabricating metal-organic frameworks (MOFs) and MOF-derived nanostructures for electrochemical applications is presented.
Abstract: Metal–organic frameworks (MOFs) have received a lot of attention because of their diverse structures, tunable properties and multiple applications such as gas storage, catalysis and magnetism. Recently, there has been a rapidly growing interest in developing MOF-based materials for electrochemical energy storage. MOFs have proved to be particularly suitable for electrochemical applications because of their tunable chemical composition that can be designed at the molecular level and their highly porous framework in which fast mass transportation of the related species is favorable. In this review, the recent progress in fabricating MOFs and MOF-derived nanostructures for electrochemical applications is presented. The review starts with an introduction of the principles and strategies for designing targeted MOFs followed by a discussion of some novel MOF-derived structures and their potential applications in electrochemical energy storage and conversion. Finally, major challenges in electrochemical energy storage are highlighted and prospective solutions from current progress in MOF-based nanostructure research are given.
1,250 citations
TL;DR: A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the Electrocatalysis of corresponding reactions.
Abstract: Oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are three key reactions for the development of green and sustainable energy systems. Efficient electrocatalysts for these reactions are highly desired to lower their overpotentials and promote practical applications of related energy devices. Metal–organic frameworks (MOFs) have recently emerged as precursors to fabricate carbon-based electrocatalysts with high electrical conductivity and uniformly distributed active sites. In this review, the current progress of MOF-derived carbon-based materials for ORR/OER/HER electrocatalysis is presented. Materials design strategies of MOF-derived carbon-based materials are firstly summarized to show the rich possibilities of the morphology and composition of MOF-derived carbon-based materials. A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the electrocatalysis of corresponding reactions. Finally, perspectives on the development of MOF-derived carbon-based materials for ORR, OER and HER electrocatalysis are provided.
970 citations
TL;DR: There is an immediate need to develop new synthesis methods, which will readily provide stable porous architectures, controlled phase, as well as useful control over dimensions of the metal oxides for improving their performance in supercapacitor applications.
Abstract: Transition metal oxides (TMOs) have attracted significant attention for energy storage applications such as supercapacitors due to their good electrical conductivity, high electrochemical response (by providing Faradaic reactions), low manufacturing costs, and easy processability. Despite exhibiting these attractive characteristics, the practical applications of TMOs for supercapacitors are still relatively limited. This is largely due to their continuous Faradaic reactions, which can lead to major changes or destruction of their structure as well phase changes (in some cases) during cycling, leading to the degradation in their capacitive performance over time. Hence, there is an immediate need to develop new synthesis methods, which will readily provide stable porous architectures, controlled phase, as well as useful control over dimensions (1-D, 2-D, and 3-D) of the metal oxides for improving their performance in supercapacitor applications. Since its discovery in late 1990s, metal–organic frameworks (M...
908 citations
TL;DR: Recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR are highlighted, providing new opportunities for enhancing ORR performance at the molecular level.
Abstract: Replacing the rare and precious platinum (Pt) electrocatalysts with earth-abundant materials for promoting the oxygen reduction reaction (ORR) at the cathode of fuel cells is of great interest in developing high-performance sustainable energy devices. However, the challenging issues associated with non-Pt materials are still their low intrinsic catalytic activity, limited active sites, and the poor mass transport properties. Recent advances in material sciences and nanotechnology enable rational design of new earth-abundant materials with optimized composition and fine nanostructure, providing new opportunities for enhancing ORR performance at the molecular level. This Review highlights recent breakthroughs in engineering nanocatalysts based on the earth-abundant materials for boosting ORR.
881 citations
TL;DR: This tutorial review focuses on the rational design and synthesis of different 3D porous carbon-based nanomaterials, such as heteroatom-doped carbon, metal-nitrogen-carbon nanostructures and a series of carbon/nonprecious metal-based hybrids, whose enhanced ORR performances are demonstrated.
Abstract: Developing a low cost, highly active, durable cathode towards an oxygen reduction reaction (ORR) is one of the high-priority research directions for commercialization of low-temperature polymer electrolyte membrane fuel cells (PEMFCs). However, the electrochemical performance of PEMFCs is still hindered by the high cost and insufficient durability of the traditional Pt-based cathode catalysts. Under these circumstances, the search for efficient alternatives to replace Pt for constructing highly efficient nonprecious metal catalysts (NPMCs) has been growing intensively and has received great interest. Combining with the compositional effects, the accurate design of NPMCs with 3D porous nanostructures plays a significant role in further enhancing ORR performance. These 3D porous architectures are able to provide higher specific surface areas and larger pore volumes, not only maximizing the availability of electron transfer within the nanosized electrocatalyst surface area but also providing better mass transport of reactants to the electrocatalyst. In this Tutorial Review, we focus on the rational design and synthesis of different 3D porous carbon-based nanomaterials, such as heteroatom-doped carbon, metal–nitrogen–carbon nanostructures and a series of carbon/nonprecious metal-based hybrids. More importantly, their enhanced ORR performances are also demonstrated by virtue of their favorably porous morphologies and compositional effects. Finally, the future trends and perspectives for the highly efficient porous NPMCs regarding the material design are discussed, with an emphasis on substantial development of advanced carbon-based NPMCs for ORR in the near future.
744 citations
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5,461 citations
TL;DR: Taking the step towards successful commercialization requires oxygen reduction electrocatalysts that meet exacting performance targets, and these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality.
Abstract: 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.
4,538 citations
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2,103 citations
TL;DR: In this paper, Mesoporous graphene doped with both N and S atoms (N-S-G) was prepared in one step and studied as an electrochemical catalyst for the oxygen reduction reaction (ORR).
Abstract: Doping duo: Mesoporous graphene doped with both N and S atoms (N-S-G) was prepared in one step and studied as an electrochemical catalyst for the oxygen reduction reaction (ORR). The catalyst shows excellent ORR performance comparable to that of commercial Pt/C. The outstanding activity of N-S-G results from both the large number and the synergistic effect of the dopant heteroatoms.
1,936 citations
TL;DR: The experimental results are believed to be significant because they not only give further insight into the ORR mechanism of these metal-free doped carbon materials, but also open a way to fabricate other new low-cost NPMCs with high electrocatalytic activity by a simple, economical, and scalable approach for real FC applications.
Abstract: Tailoring the electronic arrangement of graphene by doping is a practical strategy for producing significantly improved materials for the oxygen-reduction reaction (ORR) in fuel cells (FCs). Recent studies have proven that the carbon materials doped with the elements, which have the larger (N) or smaller (P, B) electronegative atoms than carbon such as N-doped carbon nanotubes (CNTs), P-doped graphite layers and B-doped CNTs, have also shown pronounced catalytic activity. Herein, we find that the graphenes doped with the elements, which have the similar electronegativity with carbon such as sulfur and selenium, can also exhibit better catalytic activity than the commercial Pt/C in alkaline media, indicating that these doped graphenes hold great potential for a substitute for Pt-based catalysts in FCs. The experimental results are believed to be significant because they not only give further insight into the ORR mechanism of these metal-free doped carbon materials, but also open a way to fabricate other ne...
1,884 citations