原位电化学重构硼掺杂金属有机框架作为用于稳定阴离子交换膜水电解的高效析氧反应电催化剂
In Situ Electrochemical Restructuring B-Doped Metal-Organic Frameworks as Efficient OER Electrocatalysts for Stable Anion Exchange Membrane Water Electrolysis.
作者信息
Lin Xuanni, Li Xue, Shi Lei, Ye Fenghui, Liu Feng, Liu Dong
机构信息
State Key Laboratory of Organic-Inorganic Composites, College of Chemical Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing, 100190, China.
出版信息
Small. 2024 May;20(22):e2308517. doi: 10.1002/smll.202308517. Epub 2023 Dec 28.
Metal organic frameworks (MOFs) are promising as effective electrocatalysts toward oxygen evolution reaction (OER). However, the origin of OER activity for MOF-based electrocatalysts is still unclear because of their structure reconstruction during electrocatalysis process. Here, a novel MOF (B-MOF-Zn-Co) with spherical superstructure is developed by hydrothermal treatment of zeolitic imidazolate framework-Zn, Co (ZIF-Zn-Co) using boric acid. The resultant B-MOF-Zn-Co shows high OER activity with a low overpotential of 362 mV at 100 mA cm. Remarkably, B-MOF-Zn-Co displays excellent stability with only 3.6% voltage delay over 300 h at 100 mA cm in alkaline electrolyte. Surprisingly, B-MOF-Zn-Co thoroughly transforms into B-doped CoOOH (B-CoOOH) during electrolysis process, which is served as actual active material for high OER electrocatalytic performance. The newly-formed B-CoOOH possesses lower energy barrier of potential-determining step (PDS) for OOH formation compared with CoOOH, benefiting for high OER activity. More importantly, B-MOF-Zn-Co based anion exchange membrane water electrolytic cell (AEMWE) demonstrates continuously durable operation with stable current density of 200 mA cm over 300 h, illustrating its potential application in practice water electrolysis. This work offers an in situ electrochemical reconstruction strategy for the development of stable and effective OER electrocatalysts toward practice AEMWE.
金属有机框架材料(MOFs)有望成为析氧反应(OER)的有效电催化剂。然而,基于MOF的电催化剂的OER活性起源仍不明确,因为它们在电催化过程中会发生结构重构。在此,通过使用硼酸对沸石咪唑酯框架-Zn, Co(ZIF-Zn-Co)进行水热处理,开发出一种具有球形超结构的新型MOF(B-MOF-Zn-Co)。所得的B-MOF-Zn-Co表现出高OER活性,在100 mA cm²时过电位低至362 mV。值得注意的是,B-MOF-Zn-Co在碱性电解液中于100 mA cm²下经过300小时仅出现3.6%的电压延迟,显示出优异的稳定性。令人惊讶的是,B-MOF-Zn-Co在电解过程中完全转变为B掺杂的CoOOH(B-CoOOH),其作为具有高OER电催化性能的实际活性材料。与CoOOH相比,新形成的B-CoOOH在OOH形成的电位决定步骤(PDS)中具有更低的能垒,这有利于高OER活性。更重要的是,基于B-MOF-Zn-Co的阴离子交换膜水电解槽(AEMWE)在300小时内以200 mA cm²的稳定电流密度持续稳定运行,表明其在实际水电解中的潜在应用。这项工作为开发用于实际AEMWE的稳定且有效的OER电催化剂提供了一种原位电化学重构策略。