Zinc Vaporization Induced Formation of Desired Ni Nanoparticles Coated with Ultrathin Carbon Shells for Efficient Electrocatalytic H2 Production Coupling with Methanol Upgrading

The integration of the hydrogen evolution reaction (HER) with the methanol oxidation reaction (MOR) has been demonstrated to be a viable strategy for the energy-saving generation of H₂ and value-added formate, which relies primarily on highly active and cost-effective bifunctional electrocatalysts. Herein, an efficient electrocatalyst consisting of controllable Ni nanoparticles (NPs) coated with ultrathin graphitic carbon shells was obtained by the pyrolysis of a Ni–Zn metal–organic framework. Intriguingly, we found that zinc vaporization not only resulted in the relatively small Ni NPs but also ultrathin carbon shells (≤3 layers). The density functional theory simulations confirmed that these ultrathin carbon shells significantly influenced electrocatalytic activity by facilitating electron transfer from the Ni core to the carbon shell. The optimized Ni₁(Zn)@C demonstrated high catalytic activity for both HER and MOR, and only a low potential of 97 mV at 10 mA cm^–2 was required for HER and 1.48 V at 30 mA cm^–2 for MOR. In a two-electrode electrocatalytic cell measurement, a cell voltage of 1.63 V was observed at 10 mA cm^–2 in the presence of methanol, 240 mV lower than that without methanol.