Platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) with atomically dispersed FeN 4 sites have emerged as a potential replacement for low-PGM catalysts in acidic polymer electrolyte fuel cells (PEFCs). In this work, we carefully tuned the doped Fe content in zeolitic imidazolate framework (ZIF)-8 precursors and achieved complete atomic dispersion of FeN 4 sites, the sole Fe species in the catalyst based on Mößbauer spectroscopy data. The Fe–N–C catalyst with the highest density of active sites achieved respectable ORR activity in rotating disk electrode (RDE) testing with a half-wave potential ( E 1/2 ) of 0.88 ± 0.01 V vs. the reversible hydrogen electrode (RHE) in 0.5 M H 2 SO 4 electrolyte. The activity degradation was found to be more significant when holding the potential at 0.85 V relative to standard potential cycling (0.6–1.0 V) in O 2 saturated acid electrolyte. The post-mortem electron microscopy analysis provides insights into possible catalyst degradation mechanisms associated with Fe–N coordination cleavage and carbon corrosion. High ORR activity was confirmed in fuel cell testing, which also divulged the promising performance of the catalysts at practical PEFC voltages. We conclude that the key factor behind the high ORR activity of the Fe–N–C catalyst is the optimum Fe content in the ZIF-8 precursor. While too little Fe in the precursors results in an insufficient density of FeN 4 sites, too much Fe leads to the formation of clusters and an ensuing significant loss in catalytic activity due to the loss of atomically dispersed Fe to inactive clusters or even nanoparticles. Advanced electron microscopy was used to obtain insights into the clustering of Fe atoms as a function of the doped Fe content. The Fe content in the precursor also affects other key catalyst properties such as the particle size, porosity, nitrogen-doping level, and carbon microstructure. Thanks to using model catalysts exclusively containing FeN 4 sites, it was possible to directly correlate the ORR activity with the density of FeN 4 species in the catalyst.
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Thermal Stability and Potential Cycling Durability of Nitrogen-Doped Graphene Modified by Metal-Organic Framework for Oxygen Reduction Reactions
Here we report a nitrogen-doped graphene modified metal-organic framework (N-G/MOF) catalyst, a promising metal-free electrocatalyst exhibiting the potential to replace the noble metal catalyst from the electrochemical systems; such as fuel cells and metal-air batteries. The catalyst was synthesized with a planetary ball milling method, in which the precursors nitrogen-functionalized graphene (N-G) and ZIF-8 are ground at an optimized grinding speed and time. The N-G/MOF catalyst not only inherited large surface area from the ZIF-8 structure, but also had chemical interactions, resulting in an improved Oxygen Reduction Reaction (ORR) electrocatalyst. Thermogravimetric Analysis (TGA) curves revealed that the N-G/MOF catalyst still had some unreacted ZIF-8 particles, and the high catalytic activity of N-G particles decreased the decomposition temperature of ZIF-8 in the N-G/MOF catalyst. Also, we present the durability study of the N-G/MOF catalyst under a saturated nitrogen and oxygen environment in alkaline medium. Remarkably, the catalyst showed no change in the performance after 2000 cycles in the N2 environment, exhibiting strong resistance to the corrosion. In the O2 saturated electrolyte, the performance loss at lower overpotentials was as low compared to higher overpotentials. It is expected that the catalyst degradation mechanism during the potential cycling is due to the oxidative attack of the ORR intermediates.
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- Award ID(s):
- 1838369
- NSF-PAR ID:
- 10099736
- Date Published:
- Journal Name:
- Catalysts
- Volume:
- 8
- Issue:
- 12
- ISSN:
- 2073-4344
- Page Range / eLocation ID:
- 607
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Electrocatalysts are required for clean energy technologies (for example, water‐splitting and metal‐air batteries). The development of a multifunctional electrocatalyst composed of nitrogen, phosphorus, and fluorine tri‐doped graphene is reported, which was obtained by thermal activation of a mixture of polyaniline‐coated graphene oxide and ammonium hexafluorophosphate (AHF). It was found that thermal decomposition of AHF provides nitrogen, phosphorus, and fluorine sources for tri‐doping with N, P, and F, and simultaneously facilitates template‐free formation of porous structures as a result of thermal gas evolution. The resultant N, P, and F tri‐doped graphene exhibited excellent electrocatalytic activities for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The trifunctional metal‐free catalyst was further used as an OER–HER bifunctional catalyst for oxygen and hydrogen gas production in an electrochemical water‐splitting unit, which was powered by an integrated Zn–air battery based on an air electrode made from the same electrocatalyst for ORR. The integrated unit, fabricated from the newly developed N, P, and F tri‐doped graphene multifunctional metal‐free catalyst, can operate in ambient air with a high gas production rate of 0.496 and 0.254 μL s−1for hydrogen and oxygen gas, respectively, showing great potential for practical applications.
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Abstract Developing high performance nonprecious metal‐based electrocatalysts has become a critical first step towards commercial applications of metal‐air batteries. Herein, nanocomposites based on Co/Co2P nanoparticles encapsulated within hierarchically porous N, P, S co‐doped carbon are prepared by controlled pyrolysis of zeolitic imidazolate frameworks (ZIF‐67) and poly(cyclotriphosphazene‐co‐4,4’‐sulfonyldiphenol) (PZS). The resulting Co/Co2P@NPSC nanocomposites exhibit apparent oxygen reduction reaction (ORR) and evolution reaction (OER) catalytic performance, and are used as the reversible oxygen catalyst for zinc‐air batteries (ZABs). Density functional theory (DFT) calculations exhibit that Co2P could provide active sites for the ORR and promote the conversion between the adsorbed intermediates, and porous N,P,S co‐doped carbon with Co2P nanoparticles also improves the exposure of actives sites and endows charge transport. Liquid‐state ZABs with Co/Co2P@NPSC as the cathode catalysts demonstrate the greater power density of 198.1 mW cm−2and a long cycling life of 50 h at 10 mA cm−2, likely due to the encapsulation of Co/Co2P nanoparticles by the carbon shell. Solid‐state ZABs also display a remarkable performance with a high peak power density of 74.3 mW cm−2. Therefore, this study indicates the meaning of the design and engineering of hierarchical porous carbon nanomaterial as electrocatalyst for rechargeable metal‐air batteries.
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Metal-free carbon materials have emerged as cost-effective and high-performance catalysts for the production of hydrogen peroxide (H 2 O 2 ) through the two-electron oxygen reduction reaction (ORR). Here, we show that 3D crumpled graphene with controlled oxygen and defect configurations significantly improves the electrocatalytic production of H 2 O 2 . The crumpled graphene electrocatalyst with optimal defect structures and oxygen functional groups exhibits outstanding H 2 O 2 selectivity of 92–100% in a wide potential window of 0.05–0.7 V vs. reversible hydrogen electrode (RHE) and a high mass activity of 158 A g −1 at 0.65 V vs. RHE in alkaline media. In addition, the crumpled graphene catalyst showed an excellent H 2 O 2 production rate of 473.9 mmol gcat −1 h −1 and stability over 46 h at 0.4 V vs. RHE. Moreover, density functional theory calculations revealed the role of the functional groups and defect sites in the two-electron ORR pathway through the scaling relation between OOH and O adsorption strengths. These results establish a structure-mechanism-performance relationship of functionalized carbon catalysts for the effective production of H 2 O 2 .more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/catal8120607
