Low-Temperature Production of Glyceric Acid from Biomass-Based Sugar via the Cooperative Roles of MgO and NaBF₄

Abstract

Seeking new chemo-catalytic routes to produce glyceric acid using renewable biomass-based sugar as feedstock is of significance but remains a big challenge due to a quite low yield (<5%). Herein, we prepare an MgO catalyst with an oxygen vacancy and explore a simple but robust MgO–NaBF4 system, achieving the selective production of glyceric acid from fructose with a high yield of 78.8% in an O2 atmosphere via chemo-catalysis at mild conditions (373 K), eliminating the use of strong inorganic alkalis and severe reaction conditions. As far as we know, this has the highest value among the state-of-the-art chemo-catalytic strategies. Evidenced by the isotope-probe experiment and theoretical calculation, it was revealed that MgO and NaBF4 exhibited pronounced cooperative effects. The hydroxyl group exposed on the MgO surface first facilitated the adsorption of fructose. With the assistance of MgO, B­(OH)4 – from NaBF4 hydrolysis preferentially combined with β-d-fructofuranose, as evidenced by 11B and 13C NMR spectroscopy, due to its strong electron-withdrawing ability, producing a complex which could easily undergo ring-opening reaction with an attack of OH– derived from the alkaline MgO. More importantly, the oxygen vacancies on the MgO surface subsequently assisted the C3–C4 cleavage in fructose by MgO species to produce a glyceraldehyde intermediate and activated O2 to oxidize glyceraldehyde, yielding glyceric acid. The conjunction of B­(OH)4 – with a glyceraldehyde intermediate or glyceric acid could also hinder its over-oxidation. The insights in this work might provide new chemo-catalytic approaches for glyceric acid production from renewable biomass.

Selective Stereoretention of Carbohydrates upon C−C Cleavage Enabling D‐Glyceric Acid Production with High Optical Purity over a Ag/γ‐Al2O3 Catalyst

“…O 2 ‐temperature programmed desorption (TPD) analysis (Figure S13 and Table S16) showed that Ag/γ‐Al 2 O 3 ‐H 2 gave much higher content of chemisorbed oxygen species/active surface oxygen species [30] when compared to Ag/γ‐Al 2 O 3 , while Ag/γ‐Al 2 O 3 ‐O 2 showed a lower content. Given the fact that Ag/γ‐Al 2 O 3 ‐H 2 had the highest Ag 0 /Ag + ratio, it was proposed that Ag 0 species in Ag/γ‐Al 2 O 3 catalyst contributed to adsorb and activate O 2 .…”

BF4– Tailoring Solvation Chemistry of Ether-Based Electrolytes to Construct Stable Electrode/Electrolyte Interfaces for Sodium-Ion Full Batteries

“…Therefore, constructing stable cathode electrolyte interface (CEI) films on cathodes and SEI layers on anodes is the key to promoting the application of etherbased electrolytes in full cells with high-potential cathodes. NaBF 4 is another commonly used sodium salt, which is also widely used in the fields of chemistry, 24,25 biotechnology, 26 pharmaceutical industry, 27 and so forth. Compared with NaPF 6 , NaBF 4 has a lower cost and shows outstanding performance when applied to ether-based electrolytes.…”

“…NaBF 4 is another commonly used sodium salt, which is also widely used in the fields of chemistry, , biotechnology, pharmaceutical industry, and so forth. Compared with NaPF 6 , NaBF 4 has a lower cost and shows outstanding performance when applied to ether-based electrolytes.…”

Coproduction of Glyceric Acid and Glycolic Acid from Biomass-Based Sugars over a Ru/Co3O4 Catalyst

“…With the help of substantial NaOH (6 times), 23.5 and 25.0% yields of glyceric acid were obtained from glucose and fructose feedstock, respectively . Our group recently developed a MgO–NaBF 4 catalytic system, affording 39.4% yield (based on the total carbon in fructose) of glyceric acid from fructose feedstock . With respect to glycolic acid production from biomass, two advanced studies were reported by Han and Guan, and a <50% yield was obtained with the necessity of heteropolyacid with strong acidity.…”