Developing highly efficient catalysts for the oxygen reduction reaction (ORR) is key to the fabrication of commercially viable fuel cell devices and metal-air batteries for future energy applications. Herein, we review the most recent advances in the development of Pt-based and Pt-free materials in the field of fuel cell ORR catalysis. This review covers catalyst material selection, design, synthesis, and characterization, as well as the theoretical understanding of the catalysis process and mechanisms. The integration of these catalysts into fuel cell operations and the resulting performance/durability are also discussed. Finally, we provide insights into the remaining challenges and directions for future perspectives and research.

Herein, we report a "shape fixing via salt recrystallization" method to efficiently synthesize nitrogen-doped carbon material with a large number of active sites exposed to the three-phase zones, for use as an ORR catalyst. Self-assembled polyaniline with a 3D network structure was fixed and fully sealed inside NaCl via recrystallization of NaCl solution. During pyrolysis, the NaCl crystal functions as a fully sealed nanoreactor, which facilitates nitrogen incorporation and graphitization. The gasification in such a closed nanoreactor creates a large number of pores in the resultant samples. The 3D network structure, which is conducive to mass transport and high utilization of active sites, was found to have been accurately transferred to the final N-doped carbon materials, after dissolution of the NaCl. Use of the invented cathode catalyst in a proton exchange membrane fuel cell produces a peak power of 600 mW cm(-2), making this among the best nonprecious metal catalysts for the ORR reported so far. Furthermore, N-doped carbon materials with a nanotube or nanoshell morphology can be realized by the invented method.

High dispersion Pt nanoparticles supported on 2D Ti3C2X2 (X = OH, F) nanosheets are presented and electro-chemical measurements confirm that the Pt/Ti3C2X2 catalyst shows enhanced durability and improved ORR activity compared with the commercial Pt/C catalyst.

Oxygen vacancies (OVs) are important for changing the geometric and electronic structures as well as the chemical properties of MnO 2 . In this study, we performed a DFT+U calculation on the electronic structure and catalytic performance of a β-MnO 2 catalyst for oxygen reduction reaction (ORR) with different numbers and extents of OVs. Comparing to the experimental XRD analysis, we determined that OVs produce a new crystalline phase of β-MnO 2 . Changes in the electronic structure (Bader charges, band structure, partial density of states (PDOS), local density of states (LDOS), and frontier molecular orbital), proton insertion and oxygen adsorption in β-MnO 2 (110) were investigated as a function of the bulk OVs. The results show that a moderate concentration of bulk OVs reduced the band gap, increased the Fermi and HOMO levels of the MnO 2 (or MnOOH), and elongated the O-O bond of the adsorbed O 2 and co-adsorbed O 2 with H. These changes substantially increase the conductivity of MnO 2 for the catalysis of ORR. However, an excessively high concentration of OVs in β-MnO 2 (110) will work against the catalytic enhancement of MnO 2 for ORR. The DFT+U calculation reveals that a moderate concentration of OVs induced a large overlap of the surface Mn d z2 orbitals and thus introducing an extra donor level at the bottom of the conductive band (CB), which increased the conductivity of β-MnO 2 (110). Such a curvilinear change of the catalytic activity and electronic structure as a function of the oxygen vacancy concentration suggests that the β-MnO 2 with moderate concentration OVs exhibits the highest conductivity and catalytic activity for ORR.

Surface Al leached Ti3AlC2 particles (e-TAC) with high corrosion resistance and excellent electrical conductivity were developed as an advanced support material for Pt catalysts. Electrochemical measurements confirm that the supported Pt/e-TAC electrocatalyst shows much improved activity and enhanced durability toward the oxygen reduction reaction when compared with the commercial Pt/C catalyst.