One
of the questions not yet elucidated in the electrocatalytic
oxidation of glucose is whether the first step of dehydrogenating
proton-coupled electron transfer (PCET) concerns the hydrogen directly
bound to an anomeric carbon (β-anomer) or that bound to oxygen
of the anomeric carbon (α-anomer). The knowledge is necessary
for renewable-energy-powered electrosynthesis of chemicals/fuels.
To decipher that, we have used α-d-, β-d-, and d-glucose models to interrogate the electrocatalysis
of the glucose anomers in neutral and alkaline pHs. We have also optimized
a pulse methodology to directly grow surfactant- and binder-free gold
particles onto the gas diffusion electrode (GDE) as free-standing
electrocatalysts to bridge the scales between fundamental and applied
research in fuel cells and electrolysis. Cyclic voltammetry measurements
show that the electrooxidation of all of the glucose anomers starts
at a potential region, where the gold surface is not yet fully oxidized
and is dominated by the dehydrogenating adsorption of glucose, which
rules out the hypothesis that glucose first adsorbs on the hydroxylated
gold surface. The results in neutral pHs highlight the better electrocatalytic
reactivity of the α-anomer over the β-anomer and the opposite
in alkaline pHs, which invalidates the traditional thoughts that the
β-anomer would always be the most reactive. Potential-dependent
energy profiles computed by density functional theory (DFT) mainly
confirm the promoted approach by the OH of the anomeric carbon (α-anomer).
The deciphering of the electrocatalytic reactivity of glucose anomers
at GDE-Au electrocatalysts, where gluconate is the main oxidation
product at high selectivity and faradaic efficiency (>80%), opens
opportunities to stimulate the electrosynthesis of renewable platform
chemicals from the cellulosic biomass. The high selectivity and faradaic
efficiency toward gluconate, a commodity renewable chemical, open
opportunities to stimulate the biomass-fueled electrosynthesis.