The disparity in the transfer of carriers (electrons/mass) during the reaction in zinc-air batteries (ZABs) results in sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), along with elevated overpotentials, thereby imposing additional constraints on its utilization. Therefore, the pre-design and target-development of inexpensive, high-performance, and long-term stable bifunctional catalysts are urgently needed. In this work, an apically guiding dual-functional electrocatalyst (Ag-FeN-N-C) was prepared, in which a hierarchical porous nitrogen-doped carbon with three-dimensional (3D) hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride (FeN) nanoparticles. Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN, of which electron accumulation in the FeN phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration. The effective modulation of local electronic structures felicitously reforms the -band electron-group distribution, and intellectually tunes the mass-transfer reaction energy barriers for both ORR/OER. Additionally, the hollow star-shaped hierarchical porous structure provides an apical region for fast mass transfer. Experimental results show that the half-wave potential for ORR is 0.914 V, and the overpotential for OER is only 327 mV at 10 mA cm. A rechargeable ZAB with Ag-FeN-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles (500 h), with a power density of 180 mW cm. Moreover, when employing Ag-FeN-N-C as the air cathode, flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm. Ag-FeN-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.

中文翻译：

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空心星型反应器内由 Ag/FeNx 莫特肖特基效应诱导的顶部引导电子/质量转移反应走向高性能锌空气电池

锌空气电池（ZAB）反应过程中载流子（电子/质量）转移的差异导致氧还原反应（ORR）和析氧反应（OER）动力学缓慢，同时过电势升高，从而导致对其利用的额外限制。因此，迫切需要预先设计和靶向开发廉价、高性能、长期稳定的双功能催化剂。在这项工作中，制备了一种顶部引导双功能电催化剂（Ag-FeN-NC），其中具有三维（3D）空心星形结构的分级多孔氮掺杂碳作为基底，具有高催化活性。导电性银纳米颗粒与氮化铁 (FeN) 纳米颗粒偶联。理论计算表明，莫特肖特基异质结作为固有电场来自Ag和FeN的两相束缚，其中FeN相区的电子积累和Ag相区的电子耗尽促进了定向引导电荷迁移。局域电子结构的有效调制巧妙地改变了能带电子基团分布，并智能地调整了 ORR/OER 的传质反应能垒。此外，空心星形分层多孔结构为快速传质提供了顶部区域。实验结果表明，在10 mA cm下，ORR的半波电位为0.914 V，OER的过电位仅为327 mV。以 Ag-FeN-NC 作为空气阴极的可充电 ZAB 表现出超过 1500 次循环（500 小时）的长期循环性能，功率密度为 180 mW cm。此外，当采用 Ag-FeN-NC 作为空气阴极时，柔性 ZAB 表现出 1.42 V 的显着开路电压，并实现 65.6 mW cm 的最大功率密度。 Ag-FeN-NC 在 ZAB 的探索前景中显示了电催化剂结构的指导电子/质量传递路线和顶端反应微环境。