贵族金属有机骨架的热缺陷工程：以Ru / Rh-HKUST-1类似物为例。,ACS Applied Materials & Interfaces

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贵族金属有机骨架的热缺陷工程：以Ru / Rh-HKUST-1类似物为例。
ACS Applied Materials & Interfaces ( IF 9.5 ) Pub Date : 2020-08-14 , DOI: 10.1021/acsami.0c10721
Werner R Heinz ₁ , Iker Agirrezabal-Telleria ₂ , Raphael Junk ₁ , Jan Berger ₁ , Junjun Wang , Dmitry I Sharapa , Miryam Gil-Calvo ₂ , Ignacio Luz ₃ , Mustapha Soukri ₃ , Felix Studt , Yuemin Wang , Christof Wöll , Hana Bunzen ₄ , Markus Drees ₁ , Roland A Fischer ₁

Affiliation

引入了一种用于贵金属族有机金属框架（PGM-MOF）的受控后合成热缺陷工程（TDE）的方法。案例研究基于原型结构的[Ru / Rh]类似物[Cu ₃（BTC）₂]（HKUST-1； BTC = 1,3,5-苯三羧酸酯）。使用一组互补的分析和光谱技术对TDE过程进行定量监测和样品的广泛表征，发现组成上非常复杂的TDE-MOF材料是由于辅助配体和/或连接基的消除和/或断裂而产生的。TDE涉及乙酸酯配体的优先分离，这是在合成过程中通过配位调节固有引入的，以及构架接头BTC的连接位点逐渐脱羧。这两个过程都导致修改的Ru / Rh桨轮节点。这些节点表现出较低的平均氧化态和更易接近的开放金属中心，如使用CO作为探针的表面配体IR光谱推论得出的，并得到基于密度泛函理论（DFT）的计算的支持。单金属和混合金属的PGM-MOF在TDE特性，特别是氢化物生成能力（HGA）方面存在系统差异。后一特性是PGM-MOFs催化活性的重要指标，如乙烯与1-丁烯的二聚反应所证明。

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Thermal Defect Engineering of Precious Group Metal-Organic Frameworks: A Case Study on Ru/Rh-HKUST-1 Analogues.

A methodology is introduced for controlled postsynthetic thermal defect engineering (TDE) of precious group metal–organic frameworks (PGM-MOFs). The case study is based on the Ru/Rh analogues of the archetypical structure [Cu₃(BTC)₂] (HKUST-1; BTC = 1,3,5-benzenetricarboxylate). Quantitative monitoring of the TDE process and extensive characterization of the samples employing a complementary set of analytical and spectroscopic techniques reveal that the compositionally very complex TDE-MOF materials result from the elimination and/or fragmentation of ancillary ligands and/or linkers. TDE involves the preferential secession of acetate ligands, intrinsically introduced via coordination modulation during synthesis, and the gradual decarboxylation of ligator sites of the framework linker BTC. Both processes lead to modified Ru/Rh paddlewheel nodes. These nodes exhibit a lowered average oxidation state and more accessible open metal centers, as deduced from surface-ligand IR spectroscopy using CO as a probe and supported by density functional theory (DFT)-based computations. The monometallic and the mixed-metal PGM-MOFs systematically differ in their TDE properties and, in particular in the hydride generation ability (HGA). This latter property is an important indicator for the catalytic activity of PGM-MOFs, as demonstrated by the ethylene dimerization reaction to 1-butene.

更新日期：2020-09-10

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