Electrocatalysis Boosts the Methanol Thermocatalytic Dehydrogenation for High-Purity H₂ and CO Production

Hydrogen production from methanol represents an energy-sustainable way to produce ethanol, but it normally results in heavy CO₂ emissions. The selective conversion of methanol into H₂ and valuable chemical feedstocks offers a promising strategy; however, it is limited by the harsh operating conditions and low conversion efficiency. Herein, we realize efficient high-purity H₂ and CO production from methanol by coupling the thermocatalytic methanol dehydrogenation with electrocatalytic hydrogen oxidation on a bifunctional Ru/C catalyst. Electrocatalysis enables the acceleration of C-H cleavage and reduces the partial pressure of hydrogen at the anode, which drives the chemical equilibrium and significantly enhances methanol dehydrogenation. Furthermore, a bilayer Ru/C + Pd/C electrode is designed to mitigate CO poisoning and facilitate hydrogen oxidation. As a result, a high yield of H₂ (558.54 mmol h^-1 g^-1) with high purity (99.9%) was achieved by integrating an applied cell voltage of 0.4 V at 200 °C, superior to the conventional thermal and electrocatalytic processes, and CO is the main product at the anode. This work presents a new avenue for efficient H₂ production together with valuable chemical synthesis from methanol.