The stability, activity and selectivity of various Sn-Beta catalysts are investigated to identify how the composition of the catalyst, in addition to its method of preparation, impact its ability to continuously isomerise glucose to fructose. Increasing the Sn loading in post-synthetically prepared catalysts leads to a decrease of both activity and stability. Accordingly, materials containing dilute amounts of Sn appear to be most suitable for continuous operation. Furthermore, the method of preparation has a profound impact on the overall performance of the catalyst. In fact, preparation of Sn-Beta by hydrothermal synthesis results in improvements of both activity and stability, with respect to the post-synthetic preparation of an otherwise-analogous material. The improved resistance of hydrothermal Sn-Beta is attributed, through a combination of operando UV-Vis, TPD-MS and vapour adsorption isotherms, to its greater resistance to deactivation by methanol (the reaction solvent). Complementary 119 Sn CPMG MAS NMR experiments also indicate the presence of different Sn sites in the hydrothermal material, which, alongside the presence of a less adsorptive siliceous matrix, may be intrinsically less prone to solvent interaction than those present in post-synthetic Sn-Beta.
Sn-Beta has emerged as a state-of-the-art catalyst for a range of sustainable chemical transformations. Conventionally prepared by bottom-up hydrothermal synthesis methods, recent research has demonstrated the efficiency of several top-down...
Minimizing catalyst deactivation and developing regeneration protocols are critical challenges in the area of biomass upgrading. Herein, we investigate the regeneration of Sn-containing zeolites for the continuous conversion of glucose. In doing so, we reveal that permanent changes to the properties of the catalyst occur following continuous operation and regeneration, resulting in surprising improvements to performance during subsequent operational cycles. Through a combination of characterization (119Sn CPMG MAS NMR, DRIFTS, and vapor sorption) and kinetic methodologies, we reveal that improved performance arises from restructuring of the catalyst, which causes the active-site environment to become more accessible, more hydrophobic, more reactive, and more stable. Based on these findings, we demonstrate how these positive changes can be emulated without resorting to extended operation, by optimizing pretreatment of the catalyst prior to reaction. This process, termed preactivation, involves treatment of the fresh catalyst in a flow of methanol at 110 °C for 0.5 h, prior to its heat treatment at 550 °C in air for 3 h. This relatively rapid procedure allows substantial improvements to catalyst activity and stability to be achieved in a permanent fashion prior to the first operational cycle.
The isomerisation of glucose to fructose is a critical step towards manufacturing petroleum-free chemicals from lignocellulosic biomass. Herein we show that Hf-containing zeolites are unique catalysts for this reaction, enabling true thermodynamic equilibrium to be achieved in a single step during intensified continuous operation, which no chemical or biological catalyst has yet been able to achieve. Unprecedented single-pass yields of 58 % are observed at a fructose selectivity of 94 %, and continuous operation for over 100 hours is demonstrated. The unexpected performance of the catalyst is realised following a period of activation within the reactor, during which time interaction with the solvent generates a state of activity that is absent in the synthesised catalyst. Mechanistic studies by X-ray absorption spectroscopy, chemisorption FTIR, operando UV/Vis and 1 H-13 C HSQC NMR spectroscopy indicate that activity arises from isolated Hf IV atoms with monofunctional acidic properties.
The retro-aldol fragmentation of glucose is a complex reaction of industrial relevance, which provides a potentially sustainable route for the production of α-hydroxyester compounds of relevance to the green polymer industry, such as methyl lactate and methyl vinyl glycolate. Although the zeolite catalyst, Sn-Beta, has shown itself to be a promising catalyst for this process, important information concerning the stability of the catalyst during continuous operation is not yet known, and improvements to its yield of retro-aldol products are also essential. Here, we perform detailed spectroscopic studies of a selection of Sn-Beta catalysts and evaluate their performances for the retro-aldol fragmentation of glucose under continuous processing conditions, with the dual aims of developing new structure–activity–lifetime relationships for the reaction and maximizing the productivity and selectivity of the process. Kinetic studies are performed under both established reaction conditions and in the presence of additional promoters, including water and alkali salts. Generally, this study demonstrates that the reaction conditions and choice of catalyst cannot be optimized in isolation, since each catalyst explored in this study responds differently to each particular process perturbation. However, by evaluating each type of the Sn-Beta catalyst under each set of reaction conditions, we reveal that postsynthetic Sn-Beta catalysts exhibit the best levels of performance when activity, selectivity, and stability are taken into account. Specifically, the best levels of performance are obtained with a postsynthetic Sn-Beta catalyst that is preactivated in a flow of methanol prior to reaction, which provides α-hydroxyester yields over 90% at the early stages of continuous operation and operates at high yield and selectivity for over 60 h on stream. Space–time-yields over two orders of magnitude higher than any previously reported for this reaction are achieved, setting a new benchmark in terms of the retro-aldol fragmentation of glucose.
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