The synergistic effect of Ni doping on Cu/Cu2O(111) surface in aqueous phase reforming of methanol for hydrogen production

Aqueous phase reforming of methanol (APRM) is a promising technology for efficiently producing hydrogen (H₂) in a sustainable approach, enabling convenient and safe H₂ storage and transportation. Herein, we develop a Ni/Cu/Cu₂O@CA catalyst with excellent performance by integrating density functional theory (DFT) calculation and experimental investigations. DFT results show that Ni doping greatly reduced the activation energy (E_a) of CH₃OH dehydrogenation and H₂O dissociation, especially the E_a of the rate-limiting step of CH₃O∗ → CH₂O∗ + H∗ from 1.71 eV to 1.28 eV. Additionally, the Cu/Cu₂O(111) surface is found to promote the CO conversion. To verify the synergistic effect between Ni and Cu/Cu₂O(111), a 3D spherical porous Ni/Cu/Cu₂O@CA catalyst is synthesized for APRM experiments, achieving a peak H₂ production rate of 135.93 μmolH₂/g_cat/s at 240 °C, which is 2.0 times higher than that of the Cu/Cu₂O@CA catalyst. Overall, this work presents an implementable strategy for developing non-noble metal catalysts for sustainable H₂ production.