Selectively Electrocatalytic Reductive Dehydroxylation of 2‐butene‐1,4‐diol to 3‐buten‐1‐ol over Cu Nanowire Arrays at Industrial Current Densities

Abstract Electrocatalytic reductive dehydroxylation is a promising strategy for sustainable synthesis of commodity and high‐value‐added chemicals but remains a formidable challenge due to the high dissociation energy of C─OH bond. Here, we report a selectively electrocatalytic reductive dehydroxylation of 1,4‐butenediol (BED) to produce 3‐buten‐1‐ol (BTO) over Cu nanowire arrays (Cu NWAs) under ambient conditions. A high BED conversion of ∼90.5% and a BTO selectivity of ∼80.2% are achieved at –0.9 V versus RHE. Even in a large‐scale two‐electrode H‐type elecrolyser (1 L), the Cu NWAs stably exhibit a BED conversion of ≥ 92.3%, a BTO selectivity of ≥ 82.7%, and a BTO production rate of 190.8 mmol · g cat −1 · h −1 at an industrial current density of 200 mA cm −2 . Experimental and theoretical investigations reveal that the Cu surface facilitates the dissociation of C─OH bond in BED and the desorption of BTO, which thus promotes the selective dehydroxylation of BED to BTO. This work highlights a sustainable and efficient strategy for producing high‐value‐added chemicals.