Theoretical insight into highly durable iron phthalocyanine derived non-precious catalysts for oxygen reduction reactions

Seo, Min Ho; Higgins, Drew; Jiang, Gaopeng; Choi, Sung Mook; Han, Byungchan; Chen, Zhongwei

doi:10.1039/c4ta04690k

Cited by 55 publications

(47 citation statements)

References 74 publications

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“…The result reveals that the Fe–N X complexes are the most active functionalities for boosting the ORR in low‐pH media. This is similar to other reported results, stating that the Fe–N X species are pivotal for the adsorption and reduction of oxygen and intermediates in acidic solution . The pyridine‐like and pyrrole‐like N groups with high negative charge densities are susceptible to protonation in acidic conditions, which may make these two configurations inert toward the ORR .…”

Section: Resultsmentioning

confidence: 99%

High‐Performance Fe–N‐Doped Graphene Electrocatalysts with pH‐Dependent Active Sites for the Oxygen Reduction Reaction

et al. 2015

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Advanced Fe–N‐doped graphene (FeNG) electrocatalysts are developed for the oxygen reduction reaction (ORR) by annealing a mixture of sustainable and low‐cost corn starch, urea, and FeCl3. The Fe–N coordinations and Fe/Fe3C nanoparticles can be controllably achieved through space confinement and pyrolysis temperature‐induced effects, respectively. Electrochemical tests show that, compared to the commercial Pt/C catalyst, the ORR half‐wave potential of FeNG is 99 mV more positive in KOH and 34 mV more negative in H2SO4, with higher stabilities in both media. More importantly, the ORR mechanisms of FeNG are demonstrated to be diverse in both KOH and H2SO4, owing to the various catalytic centers. The obtained results indicate that the enhanced ORR activity in basic media can mainly be ascribed to quaternary N and Fe/Fe3C sites, whereas the ORR performance in acidic media originates primarily from Fe–NX complexes. The electrocatalytic origin of these species is governed, primarily, by their unique electronic structures and specific environments in different pH solutions.

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Section: Resultsmentioning

confidence: 99%

High‐Performance Fe–N‐Doped Graphene Electrocatalysts with pH‐Dependent Active Sites for the Oxygen Reduction Reaction

et al. 2015

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“…Seo et al, utilized DFT to calculate cohesive energy of Fe in phthalocyanine structures and found a strong effect of oxygen acting to stabilize Fe against demetalation. [96] Such a strong dependence, confirmed experimentally, suggests that even small atomic-scale perturbations of active sites can have dramatic effects on their durability. This also implies that other local perturbations of active-site atomic-scale structure may dramatically affect activity and any mechanism leading to such perturbation could aid in activity loss.…”

Section: Atomic-scale Degradation Of Active Sitesmentioning

confidence: 93%

Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction

et al. 2019

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Development of alternative energy sources is crucial to tackle challenges encountered by the growing global energy demand. Hydrogen-fuel, a promising way to store energy produced from renewable power sources, can be converted into electrical energy at high efficiency via direct electrochemical conversion in fuel cells, releasing water as the sole byproduct. One important drawback to current fuel-cell technology is the high content of platinum-group-metal (PGM) electrocatalysts required to perform the sluggish oxygen reduction reaction (ORR). Addressing this challenge, remarkable progress has been made in the development of low-cost PGM-free electrocatalysts synthesized from inexpensive, earth-abundant, and easily sourced materials such as iron, nitrogen, and carbon (Fe-N-This article is protected by copyright. All rights reserved. C). PGM-free Fe-N-C electrocatalysts now exhibit ORR activities approaching that of PGM electrocatalysts but at a fraction of the cost, promising to significantly reduce overall fuel-cell technology costs. Herein, recent developments in PGM-free electrocatalysis, demonstrating increased fuel-cell performance, as well as efforts aimed at understanding the key limiting factor, i.e., the nature of the PGM-free active site, are summarized. Further improvements will be accomplished through the controlled and/or rationally designed synthesis of materials with higher active-site densities, while at the same time establishing methods to mitigate catalyst degradation.

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“…By calculating the oxygen adsorption energy and d‐band center in a metal, a successful prediction of the catalysis was achieved using pure metals and Pt‐alloys as examples (Figure a,b) [21a]. Based on these approaches, nonprecious catalysts such as heteroatom‐doped carbons,[8c] metal‐N4 macrocycle metal complexes, and metal oxides have also been explored. For example, in the spinel oxide structured nano‐crystals, the first‐principles DFT analysis of the catalysts revealed an activity trend, observed in the order of (Mn,Co) 3 O 4 < Co 3 O 4 < (Ni,Co) 3 O 4 for ORR and (Mn,Co) 3 O 4 < (Ni,Co) 3 O 4 < Co 3 O 4 for the oxygen evolution reaction (OER) based on the Gibbs free energy obtained at the potential for which all the intermediate reactions occur spontaneously .…”

Section: Trends In Quantum Mechanics Computation Approach For Highly mentioning

confidence: 99%

A Review on Recent Progress in the Aspect of Stability of Oxygen Reduction Electrocatalysts for Proton‐Exchange Membrane Fuel Cell: Quantum Mechanics and Experimental Approaches

et al. 2019

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Proton‐exchange membrane fuel cells (PEMFCs) have been intensively developed. Their advantages include low working temperature, high power density, and fast reaction rate. PEMFCs are considered the most promising candidates for the reliable and efficient large‐scale conversion system of hydrogen in automotive engines, distributed power generation, and portable electronic applications. In time, the current use of significant amounts of precious metals as catalysts, especially for the oxygen reduction reaction (ORR) at the cathode, can limit the sustainable utilization of PEMFCs. The significant findings in studies, which combine experiments with theories, markedly improved the understanding of catalytic activity based on the interpretation of electronic configuration. For the commercialization of PEMFCs, ensuring the reliable durability of the system is an important prerequisite. However, voluminous studies on the durability of crucial materials are still insufficient. In particular, studies on improving the durability using quantum mechanics are comparatively rare relative to the studies on the nature of the activity. Therefore, the aim of this Review is to summarize the recent trends in the research on catalysts in terms of durability by combining quantum mechanics simulations with experiments to provide some insights and potential directions for the future design of stable ORR catalysts for PEMFCs.

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Theoretical insight into highly durable iron phthalocyanine derived non-precious catalysts for oxygen reduction reactions

Abstract: N4-chelate macrocycles comprise the foundation for non-precious metal oxygen reduction reaction (ORR) catalyst research, where the main electrochemical process occurs in polymer electrolyte membrane (PEM) fuel cells.

Cited by 55 publications

References 74 publications

High‐Performance Fe–N‐Doped Graphene Electrocatalysts with pH‐Dependent Active Sites for the Oxygen Reduction Reaction

High‐Performance Fe–N‐Doped Graphene Electrocatalysts with pH‐Dependent Active Sites for the Oxygen Reduction Reaction

Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction

A Review on Recent Progress in the Aspect of Stability of Oxygen Reduction Electrocatalysts for Proton‐Exchange Membrane Fuel Cell: Quantum Mechanics and Experimental Approaches

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