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掺镍二氧化锰纳米片阵列用于高效尿素氧化。

Ni-Doped MnO Nanosheet Arrays for Efficient Urea Oxidation.

机构信息

School of Chemistry and Materials Science, Institute of Advanced Materials and Flexible Electronics (IAMFE), Nanjing University of Information Science and Technology, Nanjing, Jiangsu 210044, China.

College of Science, Nanjing Forestry University, Nanjing, Jiangsu 210037, China.

出版信息

Inorg Chem. 2023 Mar 27;62(12):5023-5031. doi: 10.1021/acs.inorgchem.3c00234. Epub 2023 Mar 10.

Abstract

Urea oxidation reaction (UOR), with a low thermodynamic potential, offers great promise for replacing anodic oxygen evolution reaction of electrolysis systems such as water splitting, carbon dioxide reduction, etc., thus reducing the overall energy consumption. To promote the sluggish kinetics of UOR, highly efficient electrocatalysts are required, and Ni-based materials have been widely investigated. However, most of these reported Ni-based catalysts suffer from large overpotentials, as they generally undergo self-oxidation to form NiOOH species at high potentials, which act as catalytically active sites for UOR. Herein, Ni-doped MnO (Ni-MnO) nanosheet arrays were successfully prepared on nickel foam. The as-fabricated Ni-MnO shows distinct UOR behavior with most of the previously reported Ni-based catalysts, as urea oxidation on Ni-MnO proceeds before the formation of NiOOH. Notably, a low potential of 1.388 V vs reversible hydrogen electrode was required to achieve a high current density of 100 mA cm on Ni-MnO. It is suggested that both Ni doping and nanosheet array configuration are responsible for the high UOR activities on Ni-MnO. The introduction of Ni modifies the electronic structure of Mn atoms, and more Mn species are generated in Ni-MnO, contributing to its outstanding UOR performance.

摘要

尿素氧化反应 (UOR) 的热力学势较低,有望替代水分解、二氧化碳还原等电解系统的阳极析氧反应,从而降低整体能耗。为了促进 UOR 的缓慢动力学,需要高效的电催化剂,而镍基材料已被广泛研究。然而,这些报道的大多数镍基催化剂都存在较大的过电势,因为它们通常在高电势下经历自氧化形成 NiOOH 物种,这些物种作为 UOR 的催化活性位点。在此,成功地在泡沫镍上制备了掺镍的 MnO(Ni-MnO)纳米片阵列。所制备的 Ni-MnO 表现出明显的 UOR 行为,与大多数先前报道的 Ni 基催化剂相比,尿素在 Ni-MnO 上的氧化发生在 NiOOH 形成之前。值得注意的是,在 Ni-MnO 上实现 100 mA cm 的高电流密度需要 1.388 V 相对于可逆氢电极的低电位。这表明 Ni 掺杂和纳米片阵列结构都对 Ni-MnO 的高 UOR 活性负责。Ni 的引入改变了 Mn 原子的电子结构,并且在 Ni-MnO 中生成了更多的 Mn 物种,这有助于其出色的 UOR 性能。

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