Two major challenges that impede fuel cell technology breakthrough are the insufficient activity of the electrocatalysts for the oxygen reduction reaction and their degradation during operation, caused by the potential-induced corrosion of their carbon-support upon fuel cell operation. Unsupported electrocatalysts derived from tailored noble-metal nanostructures are superior to the conventional carbon-supported Pt nanoparticle catalysts and address these barriers by fine-tuning the surface composition and eliminating the support. Herein, recent efforts and achievements in the design, synthesis and characterization of unsupported electrocatalysts are reviewed, paying special attention to noble-metal aerogels, nano/meso-structured thin films and template-derived metal nanoarchitectures. Their electrocatalytic performances for oxygen reduction are compared and discussed, and examples of successful catalyst transfer to polymer electrolyte fuel cells are highlighted. This report aims to demonstrate the potential and challenges of implementing unsupported catalysts in fuel cells, thereby providing a perspective on the further development of these materials.

The development of core-shell structures remains a fundamental challenge for pure metallic aerogels. Here we report the synthesis of PdxAu-Pt core-shell aerogels comprised of an ultrathin Pt shell and a composition-tunable PdxAu alloy core. The universality of this strategy ensures the extension of core compositions to Pd-transition metal alloys. The core-shell aerogels exhibited largely improved Pt utilization efficiency for oxygen reduction reaction and their activities show a volcano-type relationship as a function of the lattice parameter of the core substrate. The maximum mass and specific activities are 5.25 A mg-1Pt and 2.53 mA cm-2, which are 18.7 and 4.1 times higher than those of Pt/C, respectively, demonstrating the superiority of the core-shell metallic aerogels. The proposed core-based activity descriptor provides a new possible strategy for the design of future core-shell electrocatalysts.

Single-atom catalysts (SACs), as promising alternatives to Pt-based catalysts, suffer from the limited choice of center metals and low single-atom loading. Here, we report a pentacoordinated Zr-based SAC with nontrivial axial O ligands (denoted O−Zr−N−C) for oxygen reduction reaction (ORR). The O ligand downshifts the d-band center of Zr and confers Zr sites with stable local structure and proper adsorption capability for intermediates. Consequently, the ORR performance of O−Zr−N−C prominently surpasses that of commercial Pt/C, achieving a half-wave potential of 0.91 V vs. reversible hydrogen electrode and outstanding durability (92 % current retention after 130-hour operation). Moreover, the Zr site shows good resistance towards aggregation, enabling the synthesis of Zr-based SAC with high loading (9.1 wt%). With the high-loading catalyst, the zinc-air battery (ZAB) delivers a record-high power density of 324 mW cm−2 among those of SAC-based ZABs.