Facile Strategy of Directing Metal–Organic Frameworks into Hollow Nanostructures by Halide Ions
Facile Strategy of Directing Metal–Organic Frameworks into Hollow Nanostructures by Halide Ions
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DOI：
10.1021/acs.jpcc.3c00083
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发表时间：
2023-03
期刊：
影响因子：
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通讯作者：
Chuangwei Jiao;Zetan Cao;Jia He;Zhiwen Liu;Linfeng Xu;Cheng Zheng;Simin Peng;Guliziba Haldun-Guliziba-Hal
中科院分区：
文献类型：
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作者：
Chuangwei Jiao;Zetan Cao;Jia He;Zhiwen Liu;Linfeng Xu;Cheng Zheng;Simin Peng;Guliziba Haldun-Guliziba-Hal
金属有机框架（MOFs）的快速发展使其在催化、吸附、分离/纯化和能量储存方面具有广泛的潜力，但具有增强功能的新的再工程选择提供了令人兴奋的机会。然而，在基于溶液的方案中，向MOF衍生物的转化策略主要涉及湿化学反应，其中阳离子蚀刻/交换通常起着至关重要的作用。在这里，我们报告了一个简单而有效的策略，通过使用卤素阴离子将MOFs调谐成各种中空纳米结构。通过控制溶剂、离子和反应时间，可以将ZIF-67 MOFs调制成核-壳或完全中空的纳米结构。与阳离子蚀刻策略相反，衍生物的外壳是层状氢氧化钴，没有来自添加的盐的任何额外的金属元素。与纯ZIF-67相比，空心Co（OH）2具有更好的析氢反应活性，在10 mA cm-2电流密度下的过电位为216 mV，并且具有长期的电化学稳定性。讨论了卤阴离子的转化机理。这一发现为设计和控制不含外来金属杂质的复杂MOF衍生中空纳米结构提供了重要见解，保留了原始框架，但具有多种先进功能。
The rapid development of metal–organic frameworks (MOFs) enables the widespread potentials in catalysis, adsorption, separation/purification, and energy storage, but new re-engineering options with enhanced functions offer exciting opportunities. However, the conversion strategies to MOF derivatives in the solution-based scheme mainly involve the wet chemical reactions, for which the cation etching/exchange normally plays the vital role. Here, we report a facile and effective strategy of tuning MOFs into various hollow nanostructures by using the halide anions. The ZIF-67 MOFs would be modulated into the core–shell or completely hollow nanostructures through controlling the solvents, ions, and reaction times. The outer shell of the derivatives was the layered cobalt hydroxides without any additional metal elements from the added salts, in contrast to the cation etching strategy. Upon comparison with the pristine ZIF-67, the hollow Co(OH)2exhibits better hydrogen evolution reaction activity with a low overpotential of 216 mV at a current density of 10 mA cm–2and also long-term electrochemical stability. The underlying conversion mechanism by the halide anions was discussed. The finding provides a critical insight into the design and control of complex MOF-derived hollow nanostructures without foreign metal impurities, retaining the original frameworks but possessing multiple advanced functions.