Carbon Nanotubes/Heteroatom‐Doped Carbon Core–Sheath Nanostructures as Highly Active,Metal‐Free Oxygen Reduction Electrocatalysts for Alkaline Fuel Cells

A facile, scalable route to new nanocomposites that are based on carbon nanotubes/heteroatom‐doped carbon (CNT/HDC) core–sheath nanostructures is reported. These nanostructures were prepared by the adsorption of heteroatom‐containing ionic liquids on the walls of CNTs, followed by carbonization. The design of the CNT/HDC composite allows for combining the electrical conductivity of the CNTs with the catalytic activity of the heteroatom‐containing HDC sheath layers. The CNT/HDC nanostructures are highly active electrocatalysts for the oxygen reduction reaction and displayed one of the best performances among heteroatom‐doped nanocarbon catalysts in terms of half‐wave potential and kinetic current density. The four‐electron selectivity and the exchange current density of the CNT/HDC nanostructures are comparable with those of a Pt/C catalyst, and the CNT/HDC composites were superior to Pt/C in terms of long‐term durability and poison tolerance. Furthermore, an alkaline fuel cell that employs a CNT/HDC nanostructure as the cathode catalyst shows very high current and power densities, which sheds light on the practical applicability of these new nanocomposites.     

Hierarchically Ordered Porous Carbon with Atomically Dispersed FeN4 for Ultraefficient Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

The low catalytic activity and poor mass transport capacity of platinum group metal free (PGM-free) catalysts seriously restrict the application of proton-exchange membrane fuel cells (PEMFCs). Catalysts derived from Fe-doped ZIF-8 could in theory be as active as Pt/C thanks to the high intrinsic activity of FeN₄; however, the micropores fail to meet rapid mass transfer. Herein, an ordered hierarchical porous structure is introduced into Fe-doped ZIF-8 single crystals, which were subsequently carbonized to obtain an FeN₄-doped hierarchical ordered porous carbon (FeN₄/HOPC) skeleton. The optimal catalyst FeN₄/HOPC-c-1000 shows excellent performance with a half-wave potential of 0.80 V in 0.5 m H₂SO₄ solution, only 20 mV lower than that of commercial Pt/C (0.82 V). In a real PEMFC, FeN₄/HOPC-c-1000 exhibits significantly enhanced current density and power density relative to FeN₄/C, which does not have an optimized pore structure, implying an efficient utilization of the active sites and enhanced mass transfer to promote the oxygen reduction reaction (ORR).     

A Membrane‐Free Neutral pH Formate Fuel Cell Enabled by a Selective Nickel Sulfide Oxygen Reduction Catalyst

Polymer electrolyte membranes employed in contemporary fuel cells severely limit device design and restrict catalyst choice, but are essential for preventing short‐circuiting reactions at unselective anode and cathode catalysts. Herein, we report that nickel sulfide Ni₃S₂ is a highly selective catalyst for the oxygen reduction reaction in the presence of 1.0 m formate. We combine this selective cathode with a carbon‐supported palladium (Pd/C) anode to establish a membrane‐free, room‐temperature formate fuel cell that operates under benign neutral pH conditions. Proof‐of‐concept cells display open circuit voltages of approximately 0.7 V and peak power values greater than 1 mW cm⁻², significantly outperforming the identical device employing an unselective platinum (Pt) cathode. The work establishes the power of selective catalysis to enable versatile membrane‐free fuel cells.