Self-Supported Hierarchical Shell@Core Ni3S2@Ni Foam Composite Electrocatalyst with High Efficiency and Long-Term Stability for Methanol Oxidation

Graphical Ni 3 S 2 acts as a noble catalyst : A 3D porous, defect rich, and self-supported Ni 3 S 2 @Ni foam with core-shell structure is fabricated as electrocatalyst for methanol fuel cells. The electrocatalyst shows Pt-like activity, high poison tolerance, and long-term stability towards methanol oxidation in alkaline media. Direct methanol fuel cells are promising renewable energy devices for automobiles and portable electronic devices. The development of high effciency, poison tolerance, long-term stability, and noble metal-free electrocatalysts for methanol oxidation is still a major challenge. Herein, we develop a noble metal-free, 3D self-supported, defect-rich, hierarchical shell-core structured Ni 3 S 2 composite on Ni foam as electrocatalyst. This electrocatalyst shows a good activity, poison tolerance, and long-term durability towards methanol oxidation in alkaline media. It shows the lowest onset potential (−340 mV vs. Hg/HgO) among all the Ni-based catalysts reported up to date and a Pt-level specific activity. The methanol oxidation peak current of the electrocatalyst retains more than 97.5 % even after 5,000 voltammetry cycles in 0.5 M KOH+1 M CH 3 OH. The morphology and composition of the electrocatalysts before and after stability test were characterized by SEM, TEM, XRD, and XPS. The high activity, poison tolerance, and stability are attributed to the binder-free, directly grown Ni 3 S 2 shell on the Ni foam backbone, the lattice defect sites, and the synergetic effects between the in-situ formed active NiO x core and Ni 3 S 2 shell during methanol oxidation. This work indicates that the self-supported hierarchical shell-core Ni 3 S 2 @Ni foam electrocatalyst is a viable alternative for commercial Pt-based electrocatalyst applied in fuel cells.