摘要
We report a Pd 1 -MnO 2 that enables efficient bio polyols/sugars electrooxidation under acidic conditions. • The catalyst achieves a fourfold activity that MnO 2 , a 91.1% Faradaic efficiency, and a 288 h stability for formic acid production. • A lattice oxygen assisted deprotonation mechanism is proposed to accelerate C–H/O–H bond activation and C–C bond cleavage in acidic media. Replacing the energy-intensive oxygen evolution reaction (OER) with the oxidation of biomass-derived polyols and sugars has been widely demonstrated in alkaline media, yet it remains fundamentally challenging in acidic environments due to the intrinsic difficulty of activating C–H/O–H bonds. Herein, we report an atomically dispersed palladium doped manganese dioxide (Pd 1 –MnO 2 ) catalyst that effectively overcomes these limitations. This catalyst exhibits over 4-fold enhancement in catalytic activity compared with pristine γ-MnO 2 , achieving a Faradaic efficiency of 91.1% and sustaining a formic acid production rate of 650 μmol cm −2 h −1 over 288 h during glycerol oxidation. Mechanistic investigations reveal a lattice oxygen assisted deprotonation mechanism, wherein single-atom Pd activates adjacent lattice oxygen to accelerate C–H/O–H bonds activation and subsequently promote hydrated C–C bond cleavage, thereby enabling the highly selective oxidation of diverse bio-polyols and sugars to formic acid. Furthermore, by integrating Pd 1 –MnO 2 into a PEM electrolyzer, we demonstrate a practical strategy for upgrading the mixed soluble sugars from hydrolysis of raw biomass to formic acid, and techno-economic analysis corroborates the economic advantages of this approach. Collectively, this work provides molecular-level design principles for developing oxygen-mediated electrocatalysts capable of operating efficiently in acidic environments. Download: Download high-res image (222KB) Download: Download full-size image
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