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    Sulfonated covalent triazine-based frameworks as catalysts for the hydrolysis of cellobiose to glucose
    (London : RSC Publishing, 2018) Artz, Jens; Delidovich, Irina; Pilaski, Moritz; Niemeier, Johannes; Kübber, Britta Maria; Rahimi, Khosrow; Palkovits, Regina
    Covalent triazine-based frameworks (CTFs) were synthesized in large scale from various monomers. The materials were post-synthetically modified with acid functionalities via gas-phase sulfonation. Acid capacities of up to 0.83 mmol g−1 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 H2O. 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.
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    Comparison of transition metal (Fe, Co, Ni, Cu, and Zn) containing tri-metal layered double hydroxides (LDHs) prepared by urea hydrolysis
    (Cambridge : RSC, 2019) Naseem, Sajid; Gevers, Bianca; Boldt, Regine; Labuschagné, Frederick J. W. J.; Leuteritz, Andreas
    This paper details a successful synthesis and comparison of a range of tri-metal hydrotalcite-like layered double hydroxides (LDHs) using urea hydrolysis. Transition-metal-substituted MgMAl-LDHs were synthesized with M = Fe, Co, Ni, Cu or Zn. 5 mol% and 10 mol% substitutions were performed, where Mg was substituted with Co, Ni, Cu and Zn, and Al with Fe. The successful synthesis of crystalline MgMAl-LDHs was confirmed using X-ray powder diffraction (XRD) analysis. Energy-dispersive X-ray (EDX) spectroscopy was used to identify substituted metals and determine changes in composition. Changes in morphology were studied using scanning electron microscopy (SEM). Thermogravimetric analysis was used to determine the effect of Fe-, Co-, Ni-, Cu- or Zn-substitution on the thermal degradation of the MgMAl-LDH phase. The structure, morphology and thermal behavior of the LDHs were shown to be influenced by the substituted transition metals. The observed thermal stability took the order MgNiAl- > MgFeAl- = MgAl- ≥ MgCoAl- > MgCuAl- > MgZnAl-LDH. The urea hydrolysis method was shown to be a simple preparation method for well-defined crystallite structures with large hexagonal platelets and good distribution of transition metal atoms in the substituted LDHs. © 2019 The Royal Society of Chemistry.