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源自钴钼金属有机框架的纳米片组装过渡金属硫化物纳米花用于高效析氧反应

Nanosheet-assembled transition metal sulfides nanoflowers derived from CoMo-MOF for efficient oxygen evolution reaction.

作者信息

Yu Shudi, Liu Dongmei, Wang Cheng, Li Jie, Yu Rui, Wang Yong, Yin Jiongting, Wang Xiaomei, Du Yukou

机构信息

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Renai Road, Suzhou 215123, PR China.

College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Renai Road, Suzhou 215123, PR China.

出版信息

J Colloid Interface Sci. 2024 Jan;653(Pt B):1464-1477. doi: 10.1016/j.jcis.2023.10.006. Epub 2023 Oct 2.

Abstract

Oxygen evolution reaction (OER) is a multi-electron transfer process, whose intrinsic sluggish dynamic restricts the whole process of overall water splitting (OWS). To address this issue, a porous transition metal sulfide (TMS) catalyst with rich heterojunctions was prepared by vulcanization and trace Fe doping of CoMo-based metal-organic framework (MOF). In this work, the nanoflower composed of ultrathin 2D nanosheets anchored on a nickel foam presents a layered interface that contributes to the exposure of active regions. The resulting electrode denoted as Fe@CoMoS/NiS/NF required a low overpotential (η = 167 mV @ 10 mA cm, η = 260 mV @ 50 mA cm) in 1.0 M KOH for OER and a small cell voltage (E = 1.513 V @ 10 mA cm) to power OWS when coupled with commercial Pt/C. It also exhibited splendid morphological and chemical stability with virtually invariant polarization curve and flower-like appearance after 1000 CV cycles, as well as long-term durability over 100 h with a constant current density of 10 mA cm. This work revealed the multi-anionic regulation mechanism in the surface reconstruction of sulfide electrocatalysts, and verified that Co/Mo/Ni-based oxysulfide was the true active substance of OER, which inspired the understanding and design of multi-anionic regulated electrocatalysts.

摘要

析氧反应(OER)是一个多电子转移过程,其固有的缓慢动力学限制了全水解(OWS)的整个过程。为了解决这个问题,通过对CoMo基金属有机框架(MOF)进行硫化和微量Fe掺杂,制备了一种具有丰富异质结的多孔过渡金属硫化物(TMS)催化剂。在这项工作中,由锚定在泡沫镍上的超薄二维纳米片组成的纳米花呈现出分层界面,这有助于活性区域的暴露。所得电极标记为Fe@CoMoS/NiS/NF,在1.0 M KOH中进行OER时需要较低的过电位(在10 mA cm时η = 167 mV,在50 mA cm时η = 260 mV),与商业Pt/C耦合时为OWS供电所需的电池电压较小(在10 mA cm时E = 1.513 V)。在1000次循环伏安循环后,它还表现出出色的形态和化学稳定性,极化曲线和花状外观几乎不变,以及在10 mA cm的恒定电流密度下超过100 h的长期耐久性。这项工作揭示了硫化物电催化剂表面重构中的多阴离子调控机制,并验证了Co/Mo/Ni基氧硫化物是OER的真正活性物质,这激发了对多阴离子调控电催化剂的理解和设计。

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