Matching the Activity of Homogeneous Sulfonic Acids: The Fructose-to-HMF Conversion Catalyzed by Hierarchically Porous Sulfonic-Acid-Functionalized Porous Organic Polymer (POP) Catalysts

Abstract

Three HO3S-functionalized porous organic polymers (HO3S-POPs) with high surface areas (500–700 m2/g) and a broad range of porosity profiles were synthesized and tested against homogeneous-acid analogs and commercially available acid resins to evaluate their relative catalytic activities in the acid-catalyzed conversion of fructose to HMF. Comparison of fructose conversions and HMF yields demonstrates that the sulfonated POPs with hierarchical porosity can achieve catalytic activities that rival those of their homogeneous counterparts. The associated HMF selectivities represent optimized values that increase with higher temperature and faster heating, both of which can reduce the reaction time and limit product decomposition. Due to their intrinsically high mesoporosity and number of accessible acid sites, these HO3S-POPs also outperform the commercially available Amberlyst 15 resin catalyst and its crushed variant.

Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

“…Of the 94 productso btained from these sugars, 25 were selected as involving feasible technologiest hat are suitablef or large-scale prototype testing in ap ilot plant. [11][12][13] Other research has focused on optimizingh eterogeneous catalysts for dehydration reactions involving both metal catalysts [14][15][16][17][18][19][20] and supported ionic liquids. [3] The main route to form HMF is by the dehydration of sugars, [4] and important resultsh ave been achieved for HMF production using ionic liquids.…”

“…[10] Deep eutectic solvents andw ater have also been investigated for the dehydration of fructose into HMF but improvedy ields are still needed. [11][12][13] Other research has focused on optimizingh eterogeneous catalysts for dehydration reactions involving both metal catalysts [14][15][16][17][18][19][20] and supported ionic liquids. [21,22] In particular, ionic liquidsw ith halide counteranions have provenv ery efficient for the production of HMF from fructose, glucose,a nd cellulose with both Brønsted and Lewis acid catalysts.…”

Sulfonated Hyper‐cross‐linked Porous Polyacetylene Networks as Versatile Heterogeneous Acid Catalysts

“…[29] Du et al studied the influence of pore size distribution of SO 3 H-containing PPCs on their activity in the fructose conversion to 5-hydroxymethylfurfural. [30] The authors revealed the PPCs with a hierarchical texture containing both micro-and mesopores to be more efficient than PPCs containing only micropores. Most probably the mesopores of PPCs facilitated the accessibility of catalytic centres for the substrate molecules.…”

Sulfonic Acids Supported on UiO-66 as Heterogeneous Catalysts for the Esterification of Fatty Acids for Biodiesel Production

“…The solid acid catalysts not only have high catalytic activity, but also can be readily recycled [6,14,15]. For instance, sulfonic acid functionalization of porous materials is considered as one of the most efficient strategies to produce solid acid catalysts, such as sulfonic acid-functionalized metal-organic frameworks (e.g., UiO-66) [16], sulfonic acid-functionalized porous organic polymers (HO3S-POP) [17], sulfonic acidfunctionalized mesoporous silica (SBA-15-SO3H) [18], sulfonic acid-functionalized mesoporous zeolites (e.g., ZSM-5) [19] and so on.…”