With the approaching commercialization of PEM fuel cell technology, developing active, inexpensive non-precious metal ORR catalyst materials to replace currently used Pt-based catalysts is a necessary and essential requirement in order to reduce the overall system cost. This review paper highlights the progress made over the past 40 years with a detailed discussion of recent works in the area of non-precious metal electrocatalysts for oxygen reduction reaction, a necessary reaction at the PEM fuel cell cathode. Several important kinds of unsupported or carbon supported non-precious metal electrocatalysts for ORR are reviewed, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, conductive polymer-based catalysts, transition metal chalcogenides, metal oxides/carbides/nitrides/oxynitrides/carbonitrides, and enzymatic compounds. Among these candidates, pyrolyzed transition metal nitrogen-containing complexes supported on carbon materials (M–Nx/C) are considered the most promising ORR catalysts because they have demonstrated some ORR activity and stability close to that of commercially available Pt/C catalysts. Although great progress has been achieved in this area of research and development, there are still some challenges in both their ORR activity and stability. Regarding the ORR activity, the actual volumetric activity of the most active non-precious metal catalyst is still well below the DOE 2015 target. Regarding the ORR stability, stability tests are generally run at low current densities or low power levels, and the lifetime is far shorter than targets set by DOE. Therefore, improving both the ORR activity and stability are the major short and long term focuses of non-precious metal catalyst research and development. Based on the results achieved in this area, several future research directions are also proposed and discussed in this paper.

A review on non-precious metal electrocatalysts for PEM fuel cells

A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction

The notion of metal-free catalysts is used to refer to carbon materials modified with nonmetallic elements. However, some claimed metal-free catalysts are prepared using metal-containing precursors. It is highly contested that metal residues in nitrogen-doped carbon (NC) catalysts play a crucial role in the oxygen reduction reaction (ORR). In an attempt to reconcile divergent views, a definition for truly metal-free catalysts is proposed and the differences between NC and M-Nx /C catalysts are discussed. Metal impurities at levels usually undetectable by techniques such as XPS, XRD, and EDX significantly promote the ORR. Poisoning tests to mask the metal ions reveal the involvement of metal residues as active sites or as modifiers of the electronic structure of the active sites in NC. The unique merits of both M-Nx /C and NC catalysts are discussed to inspire the development of more advanced nonprecious-metal catalysts for the ORR.

On the Role of Metals in Nitrogen-Doped Carbon Electrocatalysts for Oxygen Reduction.

Three catalysts for the electroreduction of oxygen have been prepared by pyrolyzing between 400 and 1000 °C two iron precursors (Fe acetate or Fe porphyrin) adsorbed on a synthetic carbon made from the pyrolysis of PTCDA (perylene tetracarboxylic dianhydride) in a H2/NH3/Ar atmosphere. One Fe loading (0.2 wt %) has been used for the catalyst made from the salt precursor. Two Fe loadings (0.2 and 2.0 wt %) have been used for the catalyst made from the porphyrin precursor. These three catalysts have been analyzed by ToF SIMS and RDE (or GDE) in order to find correlations between ions detected by ToF SIMS and the catalytic activity. These correlations provide information about the number and the structure of the catalytic sites, which are active in these materials. By following the variation of FeNxCy+ ions, it is found that (i) two different catalytic sites exist simultaneously in all catalysts made with the Fe salt or the Fe porphyrin; (ii) one site, named FeN4/C, is at the origin of three families of FeNx...

Molecular Oxygen Reduction in PEM Fuel Cells: Evidence for the Simultaneous Presence of Two Active Sites in Fe-Based Catalysts

Reversible interconversion of water into H2 and O2, and the recombination of H2 and O2 to H2O thereby harnessing the energy of the reaction provides a completely green cycle for sustainable energy conversion and storage. The realization of this goal is however hampered by the lack of efficient catalysts for water splitting and oxygen reduction. We report exceptionally active bifunctional catalysts for oxygen electrodes comprising Mn3O4 and Co3O4 nanoparticles embedded in nitrogen-doped carbon, obtained by selective pyrolysis and subsequent mild calcination of manganese and cobalt N4 macrocyclic complexes. Intimate interaction was observed between the metals and nitrogen suggesting residual M-N(x) coordination in the catalysts. The catalysts afford remarkably lower reversible overpotentials in KOH (0.1 M) than those for RuO2, IrO2, Pt, NiO, Mn3O4, and Co3O4, thus placing them among the best non-precious-metal catalysts for reversible oxygen electrodes reported to date.

Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes.

Oxygen reduction characteristics of graphite electrodes modified with aggregated cobalt-porphyrins heat-treated at various temperatures and then impregnated in Nafion polymer were investigated systematically. The aggregated cobalt-porphyrin compound was adsorbed on graphite powder and then heat-treated at various temperatures ranging from 200 through 1200 °C. The catalysts were evaluated for electroreduction performances of oxygen on modified electrodes in sulfuric acid solutions. The electrocatalytic performances of catalysts as measured in rotating ring-disk electrodes showed that the most effective catalytic activity for oxygen reduction was attained for the aggregated cobalt-porphyrin compounds on graphite powder heat-treated at temperatures between 600 and 800 °C. The surface concentration of Co and N as measured by X-ray photoelectron spectroscopy increased as the heat-treatment temperature was increased up to 800 °C. The electrochemical performance of pyrolyzed cobalt-porphyrin catalysts changed in parallel with the surface concentration of Co and N. In the temperature range 600-800 °C, it appeared that the increased catalytic activity originated from the well-dispersed Co-N 4 moiety or from fragments of the original molecules still retaining the cobalt bound to nitrogen atoms. In the higher temperature region, Co-N 4 bonds were no longer detected, and the presence of cobalt in the metallic states (β-Co) in the catalysts was confirmed by X-ray diffraction analysis. From the results of the stability tests, the pyrolyzed cobalt porphyrin electrode systems were found to be more stable than the nonheat-treated catalysts.

https://iopscience.iop.org/article/10.1149/1.1838350/pdf

Masanori Gokita

Papers

Oxygen Reduction Characteristics of Heat‐Treated Catalysts Based on Cobalt‐Porphyrin Ion Complexes