Synthesis of Porous Organic Polymer-Based Solid-Acid Catalysts for 5-Hydroxymethylfurfural Production from Fructose

Abstract

Herein, we report the synthesis of nanoporous polytriphenylamine polymers (PPTPA) by a simple one-step oxidative polymerization pathway and the materials were sulfonated with chlorosulfonic acid to introduce acidic sulfonic groups to the polymers to form solid acid catalysts (SPPTPA). Magnetic properties were added to SPPTPA catalysts by depositing Fe3O4 nanoparticles to develop (FeSPPTPA) solid acid catalysts, for performing dehydration of fructose to 5-hydroxymethylfurfural (HMF), which is regarded as a sustainable source for liquid fuels and commodity chemicals. XRD, FTIR spectroscopy, SEM, TGA, and N2 sorption techniques were used to characterize synthesized materials. The FeSPPTPA80 nanocatalyst showed superior catalytic activities in comparison to other catalysts due to the nanorods that formed after sulfonation of the PPTPA polymeric material which gave the catalyst enough catalytic centers for dehydration reaction of fructose. The recyclability tests revealed that the magnetic solid acid catalysts could be reused for four consecutive catalytic runs, which made FeSPPTPA a potential nanocatalyst for production of HMF.

Probing the effects of fructose concentration on the evolution of humins during fructose dehydration

“…16,17 High HMF yields (>90%) were normally achieved when the concentration of fructose was extremely low (1-5 wt%). 15,18,19 Several studies have been attempted to improve the HMF yield in the conversion of high-concentration fructose. For example, the use of a macroporous sulfonated styrenedivinylbenzene resin (DR-2030) catalyst in DMSO 20 or betainebased solid acid catalyst in biphasic solvent with a deep eutectic solvent as an additive 21 led to higher HMF yields (>85%) from fructose (30 wt%), wherein DMSO or ChCl played important roles in promoting fructose dehydration and stabilizing HMF, although the high boiling point solvents were hard to recycle.…”

Cross-Linked Porous Polymers as Heterogeneous Organocatalysts for Task-Specific Applications in Biomass Transformations, CO2 Fixation, and Asymmetric Reactions

“…Fe 3 O 4 and sulfonic acid functionalized POP synthesized via the polymerization of triphenylamine. [Reproduced with permission from ref . Copyright 2019, MDPI.…”

“…For the facile recovery of the solid catalysts after the reactions, Sebatiet al 31 developed a magnetic nanocatalyst by incorporating Fe 3 O 4 in the POP framework (Figure 3). The nanorodshaped POP was prepared by FeCl 3 -catalyzed oxidative polymerization of triphenylamine in dichloroethane solvent at the temperature ranges of 80−200 °C.…”

Promoting the production of 5-hydroxymethylfurfural from high-concentration fructose by creating micro-reactors in a mixed solvent

“…Until now, satisfactory HMF yields have always been achieved at low fructose concentrations (<10.0 wt%). 15,16 Therefore, the suppression of humin formation from high loading of fructose is by far the most challenging issue for furture HMF biorefineries.…”