TEMPO-Appended Metal–Organic Frameworks as Highly Active, Selective, and Reusable Catalysts for Mild Aerobic Oxidation of Alcohols,ACS Applied Materials & Interfaces

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TEMPO-Appended Metal–Organic Frameworks as Highly Active, Selective, and Reusable Catalysts for Mild Aerobic Oxidation of Alcohols
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2017-09-20 00:00:00 , DOI: 10.1021/acsami.7b09914
Krzysztof M. Zwoliński ₁ , Michał J. Chmielewski ₁

Affiliation

Metal–organic frameworks (MOFs) decorated with stable organic radicals are highly promising materials for redox catalysis. Unfortunately however, the synthesis of chemically robust MOFs typically requires harsh solvothermal conditions, which are not compatible with organic radicals. Here, we describe the synthesis of two isoreticular families of stable, mixed component, zirconium MOFs with UiO-66 and UiO-67 structures and controlled amounts of covalently attached TEMPO radicals. The materials were obtained using a relatively low-temperature, HCl-modulated de novo method developed by Hupp and Farha and shown to contain large amounts of missing cluster defects, forming nanodomains of the reo phase with 8-connected clusters. In the extreme case of homoleptic UiO-67-TEMPO(100%), the material exists as an almost pure reo phase. Large voids due to missing clusters and linkers allowed these materials to accommodate up to 2 times more of bulky TEMPO substituents than theoretically predicted for the idealized structures and proved to be beneficial for catalytic activity. The TEMPO-appended MOFs were shown to be highly active and recyclable catalysts for selective aerobic oxidation of a broad range of primary and secondary alcohols under exceptionally mild conditions (room temperature, atmospheric pressure of air). The influence of various parameters, including the pore size and TEMPO content, on the catalytic activity was also comprehensively investigated.

中文翻译：

TEMPO认证的金属有机骨架，对酒精的轻度需氧氧化具有高活性，选择性和可重复使用的催化剂

装饰有稳定有机自由基的金属有机骨架（MOF）是用于氧化还原催化的极有前途的材料。然而不幸的是，化学上稳定的MOF的合成通常需要苛刻的溶剂热条件，该条件与有机基团不相容。在这里，我们描述了两个等网状家族的稳定，混合成分，具有UiO-66和UiO-67结构以及可控量的共价连接的TEMPO自由基的锆MOF的合成。这些材料是使用由Hupp和Farha开发的相对较低温度的HCl调节的从头方法获得的，表明含有大量缺失的团簇缺陷，形成了具有8个连接团簇的reo相的纳米域。在均质UiO-67-TEMPO（100％）的极端情况下，该材料以几乎纯的reo相存在。由于缺少簇和连接基而导致的大空隙使这些材料可容纳的最大TEMPO取代基比理论上理想结构的理论预测多2倍，并被证明对催化活性有益。TEMPO附加的MOF被证明是高活性和可循环使用的催化剂，可在异常温和的条件下（室温，空气大气压）对各种伯醇和仲醇进行选择性好氧氧化。还全面研究了包括孔径和TEMPO含量在内的各种参数对催化活性的影响。TEMPO附加的MOF被证明是高活性和可循环使用的催化剂，可在异常温和的条件下（室温，空气大气压）对各种伯醇和仲醇进行选择性好氧氧化。还全面研究了包括孔径和TEMPO含量在内的各种参数对催化活性的影响。TEMPO附加的MOF被证明是高活性和可循环使用的催化剂，可在异常温和的条件下（室温，空气大气压）对各种伯醇和仲醇进行选择性好氧氧化。还全面研究了包括孔径和TEMPO含量在内的各种参数对催化活性的影响。

更新日期：2017-09-20

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