<p>Catalytic transformation of glucose to 5-hydroxymethylfurfural (HMF), a potential furanic molecule, generally requires a Lewis and Brønsted acid-containing catalyst, which can catalyse glucose isomerisation to fructose and followed by dehydration to HMF. Thus, the present study focuses on synthesising a series of Sn-containing modified ZSM-5 catalysts possessing both Brønsted and Lewis acidic sites. The parent H-ZSM-5 (H-Z) is desilicated using an aqueous solution of 0.5&#xa0;M of LiOH at various times (60, 120 and 180&#xa0;min), enhancing the generation of mesoporous, thus improving the accessibility of active sites in the cavities of the zeolites. Sn incorporated on desilicated H-Z (SnZS) provides enhanced Lewis acidity, favouring the glucose isomerisation step to form fructose. 4 wt% of Sn loading on H-Z desilicated for 120&#xa0;min (Sn<sub>4</sub>ZS<sub>120</sub>) has higher surface area (444 m<sup>2</sup>/g), mesopore volume (0.562 cm<sup>3</sup>/g) and total pore volume (0.674 cm<sup>3</sup>/g) than the parent H-Z (422 m<sup>2</sup>/g, 0.122 cm<sup>3</sup>/g and 0.279 cm<sup>3</sup>/g). XPS spectra of Sn<sub>4</sub>ZS<sub>120</sub> show more than 95.0% of Sn in the tetrahedral form, suggesting the incorporation of Sn in the framework. Sn<sub>4</sub>ZS<sub>120</sub> exhibits 1.2 and 1.7 times higher amounts of weak and medium-strong acidic sites than the parent H-Z catalyst. NH<sub>3</sub>-DRIFT reveals that Sn<sub>4</sub>ZS<sub>120</sub> possesses a large amount of Brønsted and Lewis acidic sites along with stronger Lewis acid strength than the parent H-Z. Sn<sub>4</sub>ZS<sub>120</sub> catalyst yields 1.6 and 1.5 times higher HMF yield than the parent H-Z and Sn<sub>4</sub>H-Z catalysts, indicating the role of modification and Sn species located in the framework, respectively. Sn<sub>4</sub>ZS<sub>120</sub> also shows good catalytic activity for the dehydration of other carbohydrates (mannose, fructose, sucrose, maltose, cellobiose, and inulin) to HMF.</p>

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Bifunctional solid acid catalysed conversion of glucose to 5-hydroxymethylfurfural with Sn-doped desilicated ZSM-5

  • Rahul Gautam,
  • Shunmugavel Saravanamurugan

摘要

Catalytic transformation of glucose to 5-hydroxymethylfurfural (HMF), a potential furanic molecule, generally requires a Lewis and Brønsted acid-containing catalyst, which can catalyse glucose isomerisation to fructose and followed by dehydration to HMF. Thus, the present study focuses on synthesising a series of Sn-containing modified ZSM-5 catalysts possessing both Brønsted and Lewis acidic sites. The parent H-ZSM-5 (H-Z) is desilicated using an aqueous solution of 0.5 M of LiOH at various times (60, 120 and 180 min), enhancing the generation of mesoporous, thus improving the accessibility of active sites in the cavities of the zeolites. Sn incorporated on desilicated H-Z (SnZS) provides enhanced Lewis acidity, favouring the glucose isomerisation step to form fructose. 4 wt% of Sn loading on H-Z desilicated for 120 min (Sn4ZS120) has higher surface area (444 m2/g), mesopore volume (0.562 cm3/g) and total pore volume (0.674 cm3/g) than the parent H-Z (422 m2/g, 0.122 cm3/g and 0.279 cm3/g). XPS spectra of Sn4ZS120 show more than 95.0% of Sn in the tetrahedral form, suggesting the incorporation of Sn in the framework. Sn4ZS120 exhibits 1.2 and 1.7 times higher amounts of weak and medium-strong acidic sites than the parent H-Z catalyst. NH3-DRIFT reveals that Sn4ZS120 possesses a large amount of Brønsted and Lewis acidic sites along with stronger Lewis acid strength than the parent H-Z. Sn4ZS120 catalyst yields 1.6 and 1.5 times higher HMF yield than the parent H-Z and Sn4H-Z catalysts, indicating the role of modification and Sn species located in the framework, respectively. Sn4ZS120 also shows good catalytic activity for the dehydration of other carbohydrates (mannose, fructose, sucrose, maltose, cellobiose, and inulin) to HMF.