Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry , Fuzhou University , Fuzhou 350116 , People's Republic of China.
Inorg Chem. 2019 Dec 16;58(24):16574-16580. doi: 10.1021/acs.inorgchem.9b02593. Epub 2019 Nov 27.
MOF-253 (Al(OH)(dcbpy), dcbpy = 2,2'-bipyridine-5,5'-dicarboxylic acid) obtained via a microwave-assisted synthesis was used for the construction of a supported Ru complex containing dcbpy (MOF-253-Ru(dcbpy)) by coordinating its open N,N'-chelating sites with Ru(II) in Ru(dcbpy)Cl. The as-obtained MOF-253-Ru(dcbpy) acts as a bifunctional photocatalyst for simultaneous CO reduction to produce formic acid and CO, as well as semidehydrogenation of 1,2,3,4-tetrahydroisoquinoline (THIQ) to obtain 3,4-dihydroisoquinoline (DHIQ). The performance over the surface-supported MOF-253-Ru(dcbpy) is superior to that over Ru-doped MOF-253 (Ru-MOF-253) obtained via a mix-and-match strategy, indicating that the use of open coordination sites in the MOFs for direct construction of a surface-supported complex is a superior strategy to obtain an MOF-supported homogeneous complex. This study shows the possibility of using an MOF as a platform for the construction of multifunctional heterogeneous photocatalytic systems. The coupling of photocatalytic CO reduction with the highly selective dehydrogenation of organics provides an economical and green strategy in photocatalytic CO reduction and production of valuable organics simultaneously.
通过微波辅助合成得到的 MOF-253（Al(OH)(dcbpy)，dcbpy = 2,2'-联吡啶-5,5'-二羧酸），通过其开放的 N,N'-螯合位点与 Ru(dcbpy)Cl 中的 Ru(II)配位，用于构建含有 dcbpy 的负载 Ru 配合物（MOF-253-Ru(dcbpy)）。所得到的 MOF-253-Ru(dcbpy) 作为一种双功能光催化剂，可同时将 CO 还原为甲酸和 CO，并将 1,2,3,4-四氢异喹啉（THIQ）半脱氢为 3,4-二氢异喹啉（DHIQ）。在负载于表面的 MOF-253-Ru(dcbpy) 上的性能优于通过混合匹配策略获得的 Ru 掺杂 MOF-253（Ru-MOF-253），这表明在 MOFs 中使用开放的配位位点直接构建表面负载的配合物是获得 MOF 负载均相配合物的优越策略。该研究展示了将 MOF 用作构建多功能多相光催化系统的平台的可能性。光催化 CO 还原与有机化合物的高选择性脱氢相结合，为光催化 CO 还原和同时生产有价值的有机化合物提供了一种经济和绿色的策略。
