Oxidative Conversion of Glucose to Formic Acid as a Renewable Hydrogen Source Using an Abundant Solid Base Catalyst

Abstract

Formic acid is one of the most desirable liquid hydrogen carriers. The selective production of formic acid from monosaccharides in water under mild reaction conditions using solid catalysts was investigated. Calcium oxide, an abundant solid base catalyst available from seashell or limestone by thermal decomposition, was found to be the most active of the simple oxides tested, with formic acid yields of 50 % and 66 % from glucose and xylose, respectively, in 1.4 % H 2 O 2 aqueous solution at 343 K for 30 min. The main reaction pathway is a sequential formation of formic acid from glucose by C−C bond cleavage involving aldehyde groups in the acyclic form. The reaction also involves base‐catalyzed aldose‐ketose isomerization and retroaldol reaction, resulting in the formation of fructose and trioses including glyceraldehyde and dihydroxyacetone. These intermediates were further decomposed into formic acid or glycolic acid. The catalytic activity remained unchanged for further reuse by a simple post‐calcination.

Green hydrogen generation assisted by electroreforming of raw sugarcane bagasse waste

“…The production of some O 2 as the oxidant could be beneficial for achieving high formic acid selectivity, as demonstrated in another study with H 2 O 2 as the oxidant. 72 Overall, the H 2 faradaic efficiency of the above electrooxidation reactions was well above 95% as illustrated in Fig. 3f.…”

“…71 Additionally, the side reaction of trioses could also produce glycolic acid and formic acid. 72 We further investigated glucose electrooxidation at different working potentials (1.30, 1.48, 1.58 and 2.00 V vs. RHE) to study their corresponding products. The HPLC plots revealed different product ratios over the electrooxidation time, as shown in Fig.…”

Facile Synthesis of Microporous Carbons from Biomass Waste as High Performance Supports for Dehydrogenation of Formic Acid

“…Among them, hydrogen mass density and volume capacity of formic acid (FA) are as high as 4.4 wt% and 53.4 g•L −1 , respectively. It is a nontoxic, harmless and cheap chemical hydrogen storage material that can effectively avoid the problem of hydrogen storage and transportation [8,9]. Through a cycle constituted of dehydrogenation of FA and CO 2 hydrogenation, C1 resources can be effectively recycled, and zero carbon dioxide emission can be realized in theory, which is of great significance in the field of energy and environment [10,11].…”

Lignocellulosic biomass reform for co-producing green chemicals and green hydrogen

“…The production of some reactive oxygen species / O2 near the OER potential could be beneficial to achieving high formic acid selectivity, as demonstrated in another study with H2O2 as the oxidant. 399 Overall, the H2 Faradaic efficiencies of the above electrooxidation reactions is well above 95% as illustrated in Fig. 42c.…”

“…398 A further side reaction on the trioses could produce glycolic acid and formic acid. 399 Like glucose, xylose is another aldose sugar type, and it can also undergo the same isomerization reaction to form xylulose. The HPLC results of xylose conversion (Fig.…”