Biomass in situ conversion to Fe single atomic sites coupled with Fe 2O 3 clusters embedded in porous carbons for the oxygen reduction reaction

Author(s): Ying Lei ¹ ^, ² ^, ³ ^, ⁴ , Fuwen Yang ¹ ^, ² ^, ³ ^, ⁴ , Huaming Xie ¹ ^, ² ^, ³ ^, ⁴ , Yongpeng Lei ⁵ ^, ⁶ ^, ⁷ ^, ⁸ ^, ⁹ , Xingyong Liu ¹ ^, ² ^, ³ ^, ⁴ , Yujun Si ¹ ^, ² ^, ³ ^, ⁴ , Honghui Wang ¹ ^, ² ^, ³ ^, ⁴

Publication date (Electronic): 2020

Journal: Journal of Materials Chemistry A

Publisher: Royal Society of Chemistry (RSC)

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Abstract

Small metal clusters have received increasing attention due to their attractive and superior performance in electrocatalytic energy conversion.

Abstract

Small metal clusters have received increasing attention due to their attractive and superior performance in electrocatalytic energy conversion. However, the design and synthesis of well-dispersed metal clusters is a great challenge owing to their ease of aggregation. Here, we develop a biomass in situ conversion strategy to synthesize Fe single atomic sites (Fe–N ₄) combined with ultra-small Fe ₂O ₃ nanoclusters embedded in N, S codoped porous carbons (Fe _SA/FeO _NC/NSC) for the oxygen reduction reaction (ORR). The resultant Fe _SA/FeO _NC/NSC exhibits a high half-wave potential ( E _1/2 = 0.86 V vs. RHE) and an outstanding kinetic current density at 0.80 V ( J _k = 32.15 mA cm ⁻²), which even surpasses those of commercial Pt/C ( E _1/2 = 0.85 V, J _k = 16.5 mA cm ⁻²). Atomic level dispersed Fe–N ₄ sites integrated with Fe ₂O ₃ clusters embedded in N, S-mediated carbon are mainly responsible for the excellent ORR activity. More importantly, the assembled Zn–air battery can output a prominent power density of 179.0 mW cm ⁻² and energy density of 837.4 W h kg ⁻¹ along with robust stability, outperforming the commercial Pt/C and most non-platinum catalysts. This work opens up an avenue for biomass in situ conversion into non-precious metal electrocatalysts for energy conversion and storage technologies.

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Structural absorption by barbule microstructures of super black bird of paradise feathers

Dakota E. McCoy, Teresa J. Feo, Todd Alan Harvey … (2018)

Many studies have shown how pigments and internal nanostructures generate color in nature. External surface structures can also influence appearance, such as by causing multiple scattering of light (structural absorption) to produce a velvety, super black appearance. Here we show that feathers from five species of birds of paradise (Aves: Paradisaeidae) structurally absorb incident light to produce extremely low-reflectance, super black plumages. Directional reflectance of these feathers (0.05–0.31%) approaches that of man-made ultra-absorbent materials. SEM, nano-CT, and ray-tracing simulations show that super black feathers have titled arrays of highly modified barbules, which cause more multiple scattering, resulting in more structural absorption, than normal black feathers. Super black feathers have an extreme directional reflectance bias and appear darkest when viewed from the distal direction. We hypothesize that structurally absorbing, super black plumage evolved through sensory bias to enhance the perceived brilliance of adjacent color patches during courtship display.

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A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions.

Jintao Zhang, Zhenghang Zhao, Zhenhai Xia … (2015)

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO₂ and MnO₂) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of ∼1,663 m(2) g(-1) and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn-air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn(-1) (corresponding to an energy density of 835 Wh kgZn(-1)), a peak power density of 55 mW cm(-2), and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm(-2). We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn-air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.