Artz Jens, Delidovich Irina, Pilaski Moritz, Niemeier Johannes, Kübber Britta Maria, Rahimi Khosrow, Palkovits Regina
Chair of Heterogeneous Catalysis & Chemical Technology Institut für Technische und Makromolekulare Chemie, RWTH Aachen University Worringerweg 2 52074 Aachen Germany
DWI Leibniz-Institut für Interaktive Materialien Forckenbeckstr. 50 52074 Aachen Germany.
RSC Adv. 2018 Jun 19;8(40):22392-22401. doi: 10.1039/c8ra04254c.
Covalent triazine-based frameworks (CTFs) were synthesized in large scale from various monomers. The materials were post-synthetically modified with acid functionalities gas-phase sulfonation. Acid capacities of up to 0.83 mmol g at sulfonation degrees of up to 10.7 mol% were achieved. Sulfonated CTFs exhibit high specific surface area and porosity as well as excellent thermal stability under aerobic conditions (>300 °C). Successful functionalization was verified investigating catalytic activity in the acid-catalyzed hydrolysis of cellobiose to glucose at 150 °C in HO. Catalytic activity is mostly affected by porosity, indicating that mesoporosity is beneficial for hydrolysis of cellobiose. Like other sulfonated materials, S-CTFs show low stability under hydrothermal reaction conditions. Recycling of the catalyst is challenging and significant amounts of sulfur leached out of the materials. Nevertheless, gas-phase sulfonation opens a path to tailored solid acids for application in various reactions. S-CTFs form the basis for multi-functional catalysts, containing basic coordination sites for metal catalysts, tunable structural parameters and surface acidity within one sole system.
基于共价三嗪的框架材料(CTFs)由各种单体大规模合成。这些材料通过酸官能团进行后合成修饰——气相磺化。在磺化度高达10.7 mol%时,酸容量达到0.83 mmol/g。磺化的CTFs具有高比表面积和孔隙率,以及在有氧条件下(>300°C)优异的热稳定性。通过在150°C的水中研究其在酸催化纤维二糖水解为葡萄糖反应中的催化活性,验证了功能化的成功。催化活性主要受孔隙率影响,表明中孔结构有利于纤维二糖的水解。与其他磺化材料一样,S-CTFs在水热反应条件下稳定性较低。催化剂的循环利用具有挑战性,并且有大量硫从材料中浸出。尽管如此,气相磺化为定制用于各种反应的固体酸开辟了一条途径。S-CTFs构成了多功能催化剂的基础,在单一体系中包含金属催化剂的碱性配位位点、可调节的结构参数和表面酸度。