Bifunctional Acid‐Base Zirconium Phosphonate for Catalytic Transfer Hydrogenation of Levulinic Acid and Cascade Transformation of Furfural to Biofuel Molecules

Abstract

The production of biofuels, such as furfural ether and γvalerolactone (GVL) from biomass platform chemicals furfural (FFA) and Levulinic acid (LA) is of significant interest. In this study, a nanoporous inorganic-organic ZrÀ phosphonate catalyst (ZrNPO 3 ) was synthesized and employed in the selective production of GVL (98.2 %) via catalytic transfer hydrogenation of LA. The catalyst containing acid-base sites was further used to produce biofuel molecules like GVL and furfuryl ether under a mild reaction condition via cascade furfural transformation. The GVL selectivity was further improved using phosphotungs-tic acid@ZrNPO 3 . The catalytic optimization studies were combined with poisoning studies and the detailed physicochemical characterization to acquire insight into the structureactivity correlation and reaction mechanism. The synergistic presence of the Lewis acidity and basicity on the catalyst was responsible for its remarkable activity. Designing a single catalyst for the one-pot tandem transformation of FFA to GVL would be highly motivating for catalysis researchers and industrialists.

Influence of Additives and Growth Inhibitors in Improving the Physicochemical Properties of Silicoaluminophosphate Molecular Sieve, SAPO‐11

“…The effect of the synthetic methodologies on the acidity of the SAPO‐11 molecular sieves was studied by pyridine‐adsorbed FTIR for these materials (Figure 5b). Every SAPO‐11 sample showed two bands at 1540 cm −1 and 1450 cm −1 , attributed to the Brønsted and Lewis acid sites of the molecular sieves, respectively [16] . The peak at 1490 cm −1 arises from the Lewis and Brønsted acid sites [17] .…”

“…Every SAPO-11 sample showed two bands at 1540 cm À 1 and 1450 cm À 1 , attributed to the Brønsted and Lewis acid sites of the molecular sieves, respectively. [16] The peak at 1490 cm À 1 arises from the Lewis and Brønsted acid sites. [17] Although pyridine-adsorbed FTIR provides data on the acidity of these materials, it cannot be employed to quantify different types of acid sites.…”

Identifying Metal–Halogen Bonding for Hydrogen-Induced Acid Generation in Bifunctional Catalysis

“…As depicted in Figure 2, in the presence of isopropyl alcohol as a solvent, the reductive transformation of furfural yields multiple products (Figure S1, SI). There are generally three types of reactions: (1) conversion of furfural to furfuryl alcohol (FA) and tetrahydrofurfuryl alcohol (THFA) by hydrogenation over metal sites, 31 (2) reaction of furfural with isopropanol to form an ether through an intermediate acetal over medium-strength acid sites, 32 and (3) deoxygenation of furfuryl alcohol to methylfuran (MF) and methyl tetrahydrofuran (THMF), which requires strong acid sites. 33 All of the metal catalysts were tested in the furfural hydrogenation reaction in a high-throughput reactor.…”

Fine-Tuning of Ni/NiO over H-NbOx for Enhanced Eugenol Hydrogenation through Enhanced Oxygen Vacancies and Synergistic Participation of Active Sites

“…In recent years, extensive research has been conducted on the hydrogenation of biomass-derived monomers with hydrogen or other hydrogen donors via the catalytic transfer hydrogenation route. − Various catalysts containing noble metals such as palladium, platinum, and ruthenium or transition metals have been investigated for the hydrogenation of guaiacol, eugenol, vanillin, and other lignin-based phenolics. − Eugenol, which possesses key functional groups commonly found in lignin structures, has emerged as the most extensively studied model compound for lignin. Notably, eugenol is obtained from various sources, such as clove and cinnamon, contributing to approximately 45–90% of its composition.…”