Design and Facile Synthesis of Highly Efficient and Durable Bifunctional Oxygen Electrocatalyst Fe-Nx/C Nanocages for Rechargeable Zinc-Air Batteries.
05 Nov 2021-ACS Applied Materials & Interfaces (American Chemical Society (ACS))-Vol. 13, Iss: 45, pp 54032-54042
TL;DR: In this article, a bifunctional electrocatalyst (Fe-Nx/C) based on the zeolite imidazole organic framework-8 (ZIF-8) was used as the template agent, with surface modification coated by ferrocene (Fc) molecules followed by pyrolysis at high temperature under inert atmosphere.
Abstract: Looking for a high-efficiency, durabile, and low-cost dual-functional oxygen electrocatalyst as the air electrode catalyst in rechargeable zinc-air batteries (ZABs) is urgently desirable but faces many challenges. Herein, we propose the preparation strategy of effectively using a bifunctional electrocatalyst (Fe-Nx/C) based on the zeolite imidazole organic framework-8 (ZIF-8) as the template agent, with surface modification coated by ferrocene (Fc) molecules followed by pyrolysis at high temperature under inert atmosphere. Benefiting from the surface modification of ZIF-8 with Fc molecules, more abundant multiple catalytic Fe/Fe-Nx/FeCx sites with high intrinsic activity are derived, the resultant Fe-Nx/C exhibits excellent potential gap (ΔE = 0.63 V) and durability, which is obviously superior to the Pt/C + IrO2 benchmark (ΔE = 0.77 V) and other state-of-the-art electrocatalysts. Furthermore, the assembled rechargeable ZABs employing the Fe-Nx/C as an air-electrode show a reduced charging-discharging potential difference of 0.603 V, high power density of 214.8 mW cm-2, and long-term cycling stability of more than 290 h at 2.0 mA cm-2. Therefore, this work presents a feasible strategy to prepare a high-efficiency and durability ORR/OER bifunctional electrocatalyst toward high performance ZABs and next-generation energy storage devices.
Citations
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TL;DR: In this paper , Fe, Ni-doped ZIF-8 dodecahedron was carbonized at high temperature to obtain bimetallic Fe and Ni modified tension-relaxed carbon (FeNi@trC).
Abstract: Carbon materials derived from metal-organic frameworks have attracted increasing attention as anodes for energy storage. In this study, Fe, Ni-doped ZIF-8 is carbonized at high temperature to obtain bimetallic Fe and Ni modified tension -relaxed carbon (FeNi@trC). Fe and Ni have opposite structural modification effects when the metal ions are doped into the ZIF-8 dodecahedron. The obtained carbon material maintains the regular dodecahedron morphology, which means the relaxation of tension and strong thermal stability during annealing. Moreover, the presence of nickel enhances the carbonization degree and electrochemical stability of FeNi@trC, while the calcination of the tensive ZIF-8 precursor offers more defect sites. The discharge capacities of FeNi@trC materials are stable at 182.9 mAh·g−1 and 567.9 mAh·g−1 for sodium-ion batterie (SIB) and lithium-ion batterie (LIB) at 0.05 A·g−1. Compared with the current density of 0.05 A·g−1, the discharge capacity of SIB and LIB attenuates by 29.4% and 55.9% at 1 A·g−1, respectively, and the FeNi@trC shows good performance stability in the following cycles.
References
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TL;DR: Benefiting from structure functionalities and electronic control of a single-atom iron active center, the catalyst shows a remarkable performance with enhanced kinetics and activity for oxygen reduction in both alkaline and acid media and shows promise for substitution of expensive platinum to drive the cathodic oxygen reduction reaction in zinc-air batteries and hydrogen-air fuel cells.
Abstract: Efficient, durable and inexpensive electrocatalysts that accelerate sluggish oxygen reduction reaction kinetics and achieve high-performance are highly desirable. Here we develop a strategy to fabricate a catalyst comprised of single iron atomic sites supported on a nitrogen, phosphorus and sulfur co-doped hollow carbon polyhedron from a metal-organic framework@polymer composite. The polymer-based coating facilitates the construction of a hollow structure via the Kirkendall effect and electronic modulation of an active metal center by long-range interaction with sulfur and phosphorus. Benefiting from structure functionalities and electronic control of a single-atom iron active center, the catalyst shows a remarkable performance with enhanced kinetics and activity for oxygen reduction in both alkaline and acid media. Moreover, the catalyst shows promise for substitution of expensive platinum to drive the cathodic oxygen reduction reaction in zinc-air batteries and hydrogen-air fuel cells.
596 citations
TL;DR: In this article, a Cu, Co-embedded nitrogen-enriched mesoporous carbon framework (CuCo@NC) is developed using, a facile Cu-confined thermal conversion strategy of zeolitic imidazolate frameworks (ZIF-67) pre-grown on Cu(OH)2 nanowires.
Abstract: Rational synthesis of hybrid, earth-abundant materials with efficient electrocatalytic functionalities are critical for sustainable energy applications. Copper is theoretically proposed to exhibit high reduction capability close to Pt, but its high diffusion behavior at elevated fabrication temperatures limits its homogeneous incorporation with carbon. Here, a Cu, Co-embedded nitrogen-enriched mesoporous carbon framework (CuCo@NC) is developed using, a facile Cu-confined thermal conversion strategy of zeolitic imidazolate frameworks (ZIF-67) pre-grown on Cu(OH)2 nanowires. Cu ions formed below 450 °C are homogeneously confined within the pores of ZIF-67 to avoid self-aggregation, while the existence of CuN bonds further increases the nitrogen content in carbon frameworks derived from ZIF-67 at higher pyrolysis temperatures. This CuCo@NC electrocatalyst provides abundant active sites, high nitrogen doping, strong synergetic coupling, and improved mass transfer, thus significantly boosting electrocatalytic performances in oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). A high half-wave potential (0.884 V vs reversible hydrogen potential, RHE) and a large diffusion-limited current density are achieved for ORR, comparable to or exceeding the best reported earth-abundant ORR electrocatalysts. In addition, a low overpotential (145 mV vs RHE) at 10 mA cm−2 is demonstrated for HER, further suggesting its great potential as an efficient electrocatalyst for sustainable energy applications.
438 citations
TL;DR: In this paper, a pyridinic-N-dominated doped graphene with abundant vacancy defects was constructed and the optimized sample with an ultrahigh pore volume (3.43 cm3 g-1) exhibits unprecedented ORR activity with a half-wave potential of 0.28 V for ORR and 0.85 V in alkaline.
Abstract: Identification of catalytic sites for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in carbon materials remains a great challenge. Here, we construct a pyridinic-N-dominated doped graphene with abundant vacancy defects. The optimized sample with an ultrahigh pore volume (3.43 cm3 g–1) exhibits unprecedented ORR activity with a half-wave potential of 0.85 V in alkaline. For the first time, density functional theory results indicate that the quadri-pyridinic N-doped carbon site synergized with a vacancy defect is the active site, which presents the lowest overpotential of 0.28 V for ORR and 0.28 V for OER. The primary Zn–air batteries display a maximum power density of 115.2 mW cm–2 and an energy density as high as 872.3 Wh kg–1. The rechargeable Zn–air batteries illustrate a low discharge–charge overpotential and high stability (>78 h). This work provides new insight into the correlation between the N configuration synergized with a vacancy defect in electrocatalysis.
427 citations
TL;DR: It is reported that an atomically dispersed Zn-N-C catalyst with an ultrahigh Zn loading of 9.33 wt % could be successfully prepared by simply adopting a very low annealing rate of 1° min-1 and significantly better ORR stability than Fe-n-C catalysts in both acidic and alkaline media.
Abstract: Atomically dispersed Zn-N-C nanomaterials are promising platinum-free catalysts for the oxygen reduction reaction (ORR). However, the fabrication of Zn-N-C catalysts with a high Zn loading remains a formidable challenge owing to the high volatility of the Zn precursor during high-temperature annealing. Herein, we report that an atomically dispersed Zn-N-C catalyst with an ultrahigh Zn loading of 9.33 wt % could be successfully prepared by simply adopting a very low annealing rate of 1° min-1 . The Zn-N-C catalyst exhibited comparable ORR activity to that of Fe-N-C catalysts, and significantly better ORR stability than Fe-N-C catalysts in both acidic and alkaline media. Further experiments and DFT calculations demonstrated that the Zn-N-C catalyst was less susceptible to protonation than the corresponding Fe-N-C catalyst in an acidic medium. DFT calculations revealed that the Zn-N4 structure is more electrochemically stable than the Fe-N4 structure during the ORR process.
406 citations
TL;DR: In this article, a new Fe-N-C catalyst with well-dispersed atomic Fe in a porous carbon matrix was proposed for oxygen reduction reaction (ORR) in acid.
400 citations