Department of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China.
Department of Chemistry, Tsinghua University, Beijing, 100084, China.
Small. 2021 Feb;17(8):e2006834. doi: 10.1002/smll.202006834. Epub 2021 Feb 1.
Clear recognition and rational construction of suitable active center for specific reaction is always of great significance in designing highly efficient catalysts. Herein, a dual-active-site copper catalyst (DAS-Cu) containing both CuN and CuN sites is reported. Such catalysts show extremely high catalytic performance (yield: up to 97%) toward oxyphosphorylation of alkenes, while catalysts with single active site (CuN or CuN ) are chemically inert in this reaction. Combined with theoretical and experimental results, the different roles of two different Cu active sites in this reaction are further identified. CuN site captures the oxygen and trigger further oxidizing process, while CuN site provides moderate adsorption sites for the protection of phosphonyl radicals. This work deeply discloses the significant cooperated role with two single-atomic sites in one catalytic active center and brings up a valuable clue for the rational design of better-performing heterogeneous catalyst.
明确识别和合理构建适合特定反应的活性中心，对于设计高效催化剂始终具有重要意义。在此，报道了一种含有 CuN 和 CuN 两种活性位的双活性位铜催化剂（DAS-Cu）。此类催化剂对烯烃的氧膦化反应表现出极高的催化性能（产率高达 97%），而具有单一活性位（CuN 或 CuN ）的催化剂在该反应中则表现出化学惰性。结合理论和实验结果，进一步确定了两种不同 Cu 活性位在该反应中的不同作用。CuN 位捕获氧并引发进一步的氧化过程，而 CuN 位则提供适度的吸附位，以保护膦基自由基。这项工作深入揭示了一个催化活性中心中两个单原子位的显著协同作用，为设计性能更优的多相催化剂提供了有价值的线索。
