RESUMO
It is challenging yet promising to design highly accessible N-doped carbon skeletons to fully expose the active sites inside single-atom catalysts. Herein, mesoporous N-doped carbon hollow spheres with regulatable through-pore size can be formulated by a simple sequential synthesis procedure, in which the condensed SiO2 is acted as removable dual-templates to produce both hollow interiors and through-pores, meanwhile, the co-condensed polydopamine shell is served as N-doped carbon precursor. After that, FeâNâC hollow spheres (HSs) with highly accessible active sites can be obtained after rationally implanting Fe single-atoms. Microstructural analysis and X-ray absorption fine structure analysis reveal that high-density FeâN4 active sites together with tiny Fe clusters are uniformly distributed on the mesoporous carbon skeleton with abundant through-pores. Benefitted from the highly accessible FeâN4 active sites arising from the unique through-pore architecture, the FeâNâC HSs demonstrate excellent oxygen reduction reaction (ORR) performance in alkaline media with a half-wave potential up to 0.90 V versus RHE and remarkable stability, both exceeding the commercial Pt/C. When employing FeâNâC HSs as the air-cathode catalysts, the assembled Zn-air batteries deliver a high peak power density of 204 mW cm-2 and stable discharging voltage plateau over 140 h.
RESUMO
The low energy efficiency and limited cycling life of rechargeable Zn-air batteries (ZABs) arising from the sluggish oxygen reduction/evolution reactions (ORR/OERs) severely hinder their commercial deployment. Herein, a zeolitic imidazolate framework (ZIF)-derived strategy associated with subsequent thermal fixing treatment is proposed to fabricate dual-atom CoFeâNâC nanorods (Co1 Fe1 âNâC NRs) containing atomically dispersed bimetallic Co/Fe sites, which can promote the energy efficiency and cyclability of ZABs simultaneously by introducing the low-potential oxidation redox reactions. Compared to the mono-metallic nanorods, Co1 Fe1 âNâC NRs exhibit remarkable ORR performance including a positive half-wave potential of 0.933 V versus reversible hydrogen electrode (RHE) in alkaline electrolyte. Surprisingly, after introducing the potassium iodide (KI) additive, the oxidation overpotential of Co1 Fe1 âNâC NRs to reach 10 mA cm-2 can be significantly reduced by 395 mV compared to the conventional destructive OER. Theoretical calculations show that the markedly decreased overpotential of iodide oxidation can be ascribed to the synergistic effects of neighboring CoâFe diatomic sites as the unique adsorption sites. Overall, aqueous ZABs assembled with Co1 Fe1 âNâC NRs and KI as the air-cathode catalyst and electrolyte additive, respectively, can deliver a low charging voltage of 1.76 V and ultralong cycling stability of over 230 h with a high energy efficiency of ≈68%.
RESUMO
Single-atom Fe-N-C (Fe1 -N-C) materials represent the benchmarked electrocatalysts for oxygen reduction reaction (ORR). However, single Fe atoms in the carbon skeletons cannot be fully utilized due to the mass transfer limitation, severely restricting their intrinsic ORR properties. Herein, a self-sacrificing template strategy is developed to fabricate ultrathin nanosheets assembled Fe1 -N-C hollow microspheres (denoted as Fe1 /N-HCMs) by rational carbonization of Fe3+ chelating polydopamine coated melamine cyanuric acid complex. The shell of Fe1 /N-HCMs is constructed by ultrathin nanosheets with thickness of only 2 nm, which is supposed to be an ideal platform to isolate and fully expose single metal atoms. Benefiting from unique hierarchical hollow architecture with highly open porous structure, 2 nm-thick ultrathin nanosheet subunits and abundant Fe-N4 O1 active sites revealed by X-ray absorption fine structure analysis, the Fe1 /N-HCMs exhibit high ORR performance with a positive half-wave potential of 0.88 V versus the reversible hydrogen electrode and robust stability. When served as air-cathode catalysts with ultralow loading mass of 0.25 mg cm-2 , Fe1 /N-HCMs based Zn-air batteries present a maximum power density of 187 mW cm-2 and discharge specific capacity of 806 mA h gZn -1 in primary Zn-air batteries, all exceeding those of commercial Pt/C.
