具有原位接枝开放金属和碱性位点的波状 Ni(II) 框架用于高性能电化学水氧化和柔性复合材料驱动的尺寸排他自串联催化,ACS Sustainable Chemistry & Engineering

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具有原位接枝开放金属和碱性位点的波状 Ni(II) 框架用于高性能电化学水氧化和柔性复合材料驱动的尺寸排他自串联催化
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2022-12-22 , DOI: 10.1021/acssuschemeng.2c05673
Nilanjan Seal _{1,

2} , Arun Karmakar _{1,

3} , Subrata Kundu _{1,

3} , Subhadip Neogi _{1,

2}

Affiliation

金属有机框架 (MOF) 中目的驱动的孔功能工程体现了将电化学水氧化作为可再生能源的最具吸引力的方法，而 MOF 复合材料驱动的原子经济反应在现代环境中赋予了生态友好的属性科学时代。我们报告了多个活性位点的空前整合，包括路易斯酸中心、游离吡啶和胺部分，位于热化学稳定且起伏的混合配体 Ni(II) 框架的孔壁内。^{通过准可逆 Ni +2} /Ni ⁺³，含有活化 MOF 的大量可接近和发散的开放金属节点在碱性介质中表现出优异的析氧反应（OER）扭矩并显示电催化参数范围在最佳报告值之间。除了低过电势外，显着的塔菲尔斜率 (35.4 mV/dec) 优于基准电催化剂，如 RuO ₂、IrO ₂和商用 Co ₃ O ₄。值得注意的是，周转频率增加了三倍 (0.696 s ^–1) 与商用 NiO 相比，98% 的法拉第效率和多次 OER 循环后足够的耐久性验证了材料的高性能。三官能化 MOF 进一步证明了在醇氧化-Knoevenagel 缩合中的温和条件自串联催化具有广泛的底物耐受性和多环性能。精心设计的对照实验证实，在微孔容器内发生高度协同的酸碱串联偶联，其中考虑到空间阻碍的醇，实现了最稀有的分子尺寸介导的尺寸选择性。三聚氰胺泡沫 (MF) 内部原位接枝的 MOF 产生了 MOF@MF 作为可重构的智能复合材料，它促进了这种单锅级联反应，具有与单一 MOF 相当的活性和可重用性，

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Undulated Ni(II)-Framework with In Situ-Grafted Open-Metal and Basic Sites for High-Performance Electrochemical Water Oxidation and Flexible Composite-Driven Size-Exclusive Autotandem Catalysis

Purpose-driven pore functionality engineering in metal–organic frameworks (MOFs) manifests the most attractive approach to pursue electrochemical water oxidation as a renewable energy source, whereas the MOF-composite-driven atom-economic reaction confers an eco-friendly attribute in the modern scientific era. We report an unprecedented integration of multiple active sites, including Lewis acid centers, free pyridine, and amine moiety, inside the pore wall of a thermochemically stable and undulated mixed-ligand Ni(II) framework. The plentiful accessible and divergent open-metal nodes containing activated MOFs display excellent oxygen evolution reaction (OER) in alkaline medium through the quasi-reversible Ni⁺²/Ni⁺³ couple and show electrocatalytic parameters ranging among the best-reported values. Apart from the low overpotential, the remarkable Tafel slope (35.4 mV/dec) outperforms those of benchmark electrocatalysts like RuO₂, IrO₂, and commercial Co₃O₄. Importantly, the threefold increased turnover frequency (0.696 s^–1) compared to commercial NiO, 98% Faradaic efficiency, and sufficient durability after multiple OER cycles validate the high performance of the material. The trifunctionalized MOF further demonstrates mild-condition autotandem catalysis in alcohol oxidation-Knoevenagel condensation with broad substrate tolerance and multicyclic performance. The astutely designed control experiments confirm that highly synergistic acid–base tandem coupling transpires inside the microporous vessel, wherein the rarest molecular-dimension-mediated size selectivity is realized considering sterically encumbered alcohols. The in situ-grafted MOF inside melamine foam (MF) yielded MOF@MF as a reconfigurable smart composite that promotes this one-pot cascade reaction with comparable activity and reusability to that of the sole MOF, and demonstrates a paradigm shift toward futuristic sustainable catalysis over a real-life platform.

更新日期：2022-12-22

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