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铱和钌掺杂的层状双氢氧化物作为用于电化学水氧化的经济适用的多相催化剂。

Ir- and Ru-doped layered double hydroxides as affordable heterogeneous catalysts for electrochemical water oxidation.

作者信息

Fagiolari Lucia, Zaccaria Francesco, Costantino Ferdinando, Vivani Riccardo, Mavrokefalos Christos K, Patzke Greta R, Macchioni Alceo

机构信息

Department of Chemistry, Biology and Biotechnology, Università di Perugia and CIRCC-Via Elce di Sotto 8, I-06123 Perugia, Italy.

Department of Pharmaceutical Sciences, Università di Perugia - Via del Liceo 1, I-06123 Perugia, Italy.

出版信息

Dalton Trans. 2020 Feb 25;49(8):2468-2476. doi: 10.1039/c9dt04306c.

DOI:10.1039/c9dt04306c
PMID:31993601
Abstract

Three M-doped LDHs (M = noble metal active site, LDH = layered double hydroxides; Ir-1, Ir-ZnAl; Ru, Ru-ZnAl; Ir-2, Ir-MgAl), containing small amounts of M (ca. 2 mol% and even <1 mol% for Ru and Ir, respectively), were prepared by following simple and established synthetic procedures. Their characterization indicates that M atoms are effectively incorporated into the brucite-like layers of LDH, without phase segregation. The resulting materials catalyse electrochemical water oxidation (WO), when immobilized in carbon paste electrodes, with performances that exceed those of the benchmark system IrO2, as probed by linear sweep voltammetry (LSV). Some of these catalysts undergo continuous activation upon chronoamperometric and chronopotentiometric treatments over several hours. The crystalline structure of all of them is preserved during electrocatalytic experiments, and no significant leaching of noble metal in solution is detected. The results herein reported highlight the remarkable potential of these doped M-LDHs and confirm that dispersing Ir and Ru centers in layered and cheap inorganic materials results in easily accessible metal centers, providing highly active catalysts, while minimizing the utilization of noble metals.

摘要

通过遵循简单且成熟的合成程序制备了三种M掺杂的层状双氢氧化物(M = 贵金属活性位点,LDH = 层状双氢氧化物;Ir-1,Ir-ZnAl;Ru,Ru-ZnAl;Ir-2,Ir-MgAl),它们含有少量的M(Ru和Ir分别约为2 mol%,甚至<1 mol%)。其表征表明,M原子有效地掺入到LDH的水镁石状层中,没有相分离。当固定在碳糊电极中时,所得材料催化电化学水氧化(WO),通过线性扫描伏安法(LSV)探测,其性能超过基准体系IrO₂。其中一些催化剂在恒电流和恒电位处理数小时后会持续活化。在电催化实验过程中,它们所有的晶体结构都得以保留,并且未检测到溶液中有明显的贵金属浸出。本文报道的结果突出了这些掺杂M-LDHs的显著潜力,并证实将Ir和Ru中心分散在层状且廉价的无机材料中会产生易于接近的金属中心,提供高活性催化剂,同时最大限度地减少贵金属的使用。

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