Nitrogen-Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells.
TL;DR: A high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation and achieves respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media.
Abstract: Due to the Fenton reaction, the presence of Fe and peroxide in electrodes generates free radicals causing serious degradation of the organic ionomer and the membrane. Pt-free and Fe-free cathode catalysts therefore are urgently needed for durable and inexpensive proton exchange membrane fuel cells (PEMFCs). Herein, a high-performance nitrogen-coordinated single Co atom catalyst is derived from Co-doped metal-organic frameworks (MOFs) through a one-step thermal activation. Aberration-corrected electron microscopy combined with X-ray absorption spectroscopy virtually verifies the CoN4 coordination at an atomic level in the catalysts. Through investigating effects of Co doping contents and thermal activation temperature, an atomically Co site dispersed catalyst with optimal chemical and structural properties has achieved respectable activity and stability for the oxygen reduction reaction (ORR) in challenging acidic media (e.g., half-wave potential of 0.80 V vs reversible hydrogen electrode (RHE). The performance is comparable to Fe-based catalysts and 60 mV lower than Pt/C -60 μg Pt cm-2 ). Fuel cell tests confirm that catalyst activity and stability can translate to high-performance cathodes in PEMFCs. The remarkably enhanced ORR performance is attributed to the presence of well-dispersed CoN4 active sites embedded in 3D porous MOF-derived carbon particles, omitting any inactive Co aggregates.
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TL;DR: In this article, the authors highlight and summarize recent advances in wet-chemistry synthetic methods for single-atom catalysts with special emphasis on how to achieve the stabilization of single metal atoms against migration and agglomeration.
1,383 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
29 Oct 2018
TL;DR: In this article, Wu et al. reported an efficient oxygen reduction reaction (ORR) catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C).
Abstract: Platinum group metal (PGM)-free catalysts that are also iron free are highly desirable for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells, as they avoid possible Fenton reactions. Here we report an efficient ORR catalyst that consists of atomically dispersed nitrogen-coordinated single Mn sites on partially graphitic carbon (Mn-N-C). Evidence for the embedding of the atomically dispersed MnN4 moieties within the carbon surface-exposed basal planes was established by X-ray absorption spectroscopy and their dispersion was confirmed by aberration-corrected electron microscopy with atomic resolution. The Mn-N-C catalyst exhibited a half-wave potential of 0.80 V versus the reversible hydrogen electrode, approaching that of Fe-N-C catalysts, along with significantly enhanced stability in acidic media. The encouraging performance of the Mn-N-C catalyst as a PGM-free cathode was demonstrated in fuel cell tests. First-principles calculations further support the MnN4 sites as the origin of the ORR activity via a 4e− pathway in acidic media. Platinum group metal- and iron-free catalysts are highly desirable for the oxygen reduction reaction in proton-exchange membrane fuel cells. Now, Wu and co-workers show a carbon catalyst with atomically dispersed single Mn sites as an efficient catalyst with enhanced stability in acidic media.
920 citations
01 Mar 2019
TL;DR: Shui et al. as mentioned in this paper reported a class of concave Fe-N-C single-atom catalysts possessing an enhanced external surface area and mesoporosity that meets the 2018 PGM-free catalyst activity target.
Abstract: To achieve the US Department of Energy 2018 target set for platinum-group metal-free catalysts (PGM-free catalysts) in proton exchange membrane fuel cells, the low density of active sites must be overcome. Here, we report a class of concave Fe–N–C single-atom catalysts possessing an enhanced external surface area and mesoporosity that meets the 2018 PGM-free catalyst activity target, and a current density of 0.047 A cm–2 at 0.88 ViR-free under 1.0 bar H2–O2. This performance stems from the high density of active sites, which is realized through exposing inaccessible Fe–N4 moieties (that is, increasing their utilization) and enhancing the mass transport of the catalyst layer. Further, we establish structure–property correlations that provide a route for designing highly efficient PGM-free catalysts for practical application, achieving a power density of 1.18 W cm−2 under 2.5 bar H2–O2, and an activity of 129 mA cm−2 at 0.8 ViR-free under 1.0 bar H2–air. Iron single-atom catalysts are among the most promising fuel cell cathode materials in acid electrolyte solution. Now, Shui, Xu and co-workers report concave-shaped Fe–N–C nanoparticles with increased availability of active sites and improved mass transport, meeting the US Department of Energy 2018 target for platinum-group metal-free fuel cell catalysts.
803 citations
TL;DR: In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed and the personal view on future research directions is wrapped up.
Abstract: More than 95% (in volume) of all of today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic rese...
772 citations
References
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TL;DR: Metal-organic frameworks are porous materials that have potential for applications such as gas storage and separation, as well as catalysis, and methods are being developed for making nanocrystals and supercrystals of MOFs for their incorporation into devices.
Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
10,934 citations
TL;DR: A family of non–precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power.
Abstract: The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).
3,464 citations
Journal Article•
TL;DR: In this article, a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power.
Abstract: Fuel cell catalysts synthesized from abundant metals approach the performance and durability of platinum at lower cost. The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non–precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non–precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).
2,974 citations
TL;DR: In this paper, a microporous carbon-supported iron-based catalysts with active sites believed to contain iron cations coordinated by pyridinic nitrogen functionalities in the interstices of graphitic sheets within the micropores was produced.
Abstract: Iron-based catalysts for the oxygen-reduction reaction in polymer electrolyte membrane fuel cells have been poorly competitive with platinum catalysts, in part because they have a comparatively low number of active sites per unit volume. We produced microporous carbon-supported iron-based catalysts with active sites believed to contain iron cations coordinated by pyridinic nitrogen functionalities in the interstices of graphitic sheets within the micropores. We found that the greatest increase in site density was obtained when a mixture of carbon support, phenanthroline, and ferrous acetate was ball-milled and then pyrolyzed twice, first in argon, then in ammonia. The current density of a cathode made with the best iron-based electrocatalyst reported here can equal that of a platinum-based cathode with a loading of 0.4 milligram of platinum per square centimeter at a cell voltage of >/=0.9 volt.
2,762 citations
2,720 citations