Wang Li, Zhao Jiahua, Zhang Pengfei, Yang Shize, Zhan Wangcheng, Dai Sheng
Institute of Industrial Catalysis, East China University of, Science and Technology, Shanghai, 200237, P. R. China.
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, P. R. China.
Chemistry. 2019 Jun 26;25(36):8494-8498. doi: 10.1002/chem.201901714. Epub 2019 May 24.
Ruthenium (Ru)@Ordered mesoporous carbon (OMC) is a key catalyst in fine-chemical production. In general, the OMC support is prepared by a wet self-assembly requiring excessive solvent, toxic phenol-aldehyde precursors and a long reaction time, followed by post-immobilization to load Ru species. Herein, we wish to report a solid-state, rapid, and green strategy for the synthesis of Ru@OMC with biomass tannin as the precursor. The chemistry essence of this strategy lies in the mechanical-force-driven assembly, during which tannin-metal (Zn and Ru ) coordination polymerization and hydrogen-bonding interactions between tannin-block copolymer (PEO-PPO-PEO, F127) simultaneously occur. After thermal treatment, Ru@OMC catalysts with mesoporous channels, narrow pore-size distribution (≈7 nm), and high surface area (up to 779 m g ) were directed by F127 micelles. Meanwhile, the Zn ions dilute Ru and avoid the sintering of Ru species, resulting in Ru clusters around 1.4-1.7 nm during carbonization (800 °C). Moreover, the Ru@OMC catalyst afforded a good activity (TOF: up to 4170 h ) in the selective oxidation of benzyl alcohol to benzaldehyde by molecular oxygen.
钌（Ru）@有序介孔碳（OMC）是精细化学品生产中的关键催化剂。一般来说，OMC载体是通过湿自组装制备的，这种方法需要大量溶剂、有毒的酚醛前驱体以及较长的反应时间，随后还要进行后固定以负载Ru物种。在此，我们希望报道一种以生物质单宁为前驱体合成Ru@OMC的固态、快速且绿色的策略。该策略的化学本质在于机械力驱动的组装，在此过程中，单宁与金属（锌和钌）的配位聚合以及单宁与嵌段共聚物（聚环氧乙烷-聚环氧丙烷-聚环氧乙烷，F127）之间的氢键相互作用同时发生。经过热处理后，由F127胶束引导形成了具有介孔通道、窄孔径分布（约7 nm）和高比表面积（高达779 m² g）的Ru@OMC催化剂。同时，锌离子稀释了钌，避免了Ru物种的烧结，在碳化（800 °C）过程中形成了约1.4 - 1.7 nm的Ru簇。此外，Ru@OMC催化剂在以分子氧将苯甲醇选择性氧化为苯甲醛的反应中表现出良好的活性（TOF：高达4170 h⁻¹）。
