Dumbbell-shaped polymeric nanoparticles with one-side anchored Pd-clusters for efficient catalytic hydrogenation at biphasic interfaces
作者：Lei Wang,Badusha Mohamad Ali,Siyang Yu,Sheng Liang,Qingqing Huang, Hao Zhang,Lingyu Zhu, Jianli Wang
關鍵字：Janus polymer, Amphiphilic, Pickering emulsion, Pickering interfacial catalysts, Static hydrogenation
論文來源：期刊
具體來源：Journal of Catalysis
發表時間：2024年
結合兩親性結構的皮克林界面催化劑顯著地擴展了綠色催化系統的可持續性。在這項工作中，我們提出了精確和精心設計的啞鈴形狀的雙面結構聚合物納米粒子，其單側錨定鈀簇(DB-JPP-Pd)作為靜態氫化的Pickering界面催化劑。各葉的潤濕性差異較大，使得啞鈴形的DB-JPP-Pd具有明顯的兩親性。兩親性Janus催化劑表現出優異的界面活性，界面張力從34.06±0.13大幅降低至20.54±0.31 mN/m，促進形成比本體PS-Pd催化劑更穩定的Pickering乳液，可以在反應過程中持續提供較大的界面面積，縮短分子傳質距離。結果表明，在靜態條件下，DB-JPP-Pd催化的硝基芳烴還原反應的歸一化反應速率常數(knor)為3.39 min-1·g-1·L，是本體PS-Pd的56.5倍。所構建的Pickering界面催化(PIC)體系在3分鐘內將硝基苯全部轉化為苯胺，并對不同硝基芳烴的加氫具有良好的選擇性。此外，乳液催化體系可以方便地連續運行10次。因此，這種獨特的兩親啞鈴型催化劑有效地發展了一種高效的靜態雙相催化體系。
Pickering interfacial catalysts incorporated with amphiphilic architecture significantly expand the sustainability of green catalysis systems. In this work, we present precise and well-designed dumbbell-shaped Janus-structured polymeric nanoparticles with one-side anchored palladium clusters (DB-JPP-Pd) as Pickering interfacial catalyst for static hydrogenations. The large wettability difference of each lobe renders the prominent amphiphilicity of the dumbbell-shaped DB-JPP-Pd. The amphiphilic Janus catalyst displays excellent interfacial activity and extensively reduces the interfacial tension from 34.06±0.13 to 20.54±0.31 mN/m, promoting the formation of a more stable Pickering emulsion than that of the bulk PS-Pd catalyst, which can continuously provide a large interfacial area and shorten the molecular mass transfer distance during the reaction process. As a result, the DB-JPP-Pd catalyzed nitroarene reduction reaction exhibits a normalized reaction rate constant (knor) of 3.39 min-1·g-1·L under static conditions, which is 56.5 times higher than that of bulk PS-Pd. The constructed Pickering interfacial catalysis (PIC) system converts all the nitrobenzene into aniline within three minutes and possesses excellent selectivity in hydrogenations of different nitro aromatics. In addition, the emulsion catalytic system was conveniently recycled for ten consecutive runs. Hence, this unique amphiphilic dumbbell-shaped catalyst effectively develops an efficient static biphasic catalysis system.
國家自然科學基金(資助號:22178317、22109138)資助。
https://doi.org/10.1016/j.jcat.2024.115444