Key points are not available for this paper at this time.
Methanol oxidation-assisted water electrolysis offers the dual benefit of producing hydrogen fuel at the cathode and valuable formate at the anode. However, the methanol oxidation reaction (MOR) often suffers from slow kinetics, which are largely governed by the catalyst’s redox characteristics. Therefore, designing highly active MOR electrocatalysts requires careful tuning of their redox properties. Herein, we develop a nitrogen-modified Ni0/Ni(OH)2 denoted as N@Ni heterojunction as an efficient MOR electrocatalyst. The N@Ni demonstrated an MOR current density of 10 mA cm–2 at a potential of 1.38 V vs RHE, smaller than the 1.47 V vs RHE required by pristine Ni prepared without N-modification. Nitrogen modification induced surface distortion and altered electronic features of the catalyst, thereby facilitating the adsorption and desorption of reactive intermediates. Experimental results demonstrated that N-doping not only altered the Ni2+/Ni3+ redox behavior and reaction pathway but also lowered the activation energy for both OER and MOR. In situ electrochemical impedance spectroscopy confirmed enhanced charge transfer and faster reaction kinetics upon nitrogen incorporation, while in situ Raman analysis highlighted the active participation of electro-generated Ni3+ species during MOR.
Verma et al. (Mon,) studied this question.