The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

/pdf/high-performance-electrocatalysts-for-oxygen-reduction-3w5qtsq9yn.pdf

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt

Fuel cell catalysts synthesized from abundant metals approach the performance and durability of platinum at lower cost. The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non–precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non–precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.

http://repository.ust.hk/ir/bitstream/1783.1-77094/1/acs.chemrev.5b00462_withlink.pdf

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction

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

While platinum has hitherto been the element of choice for catalysing oxygen electroreduction in acidic polymer fuel cells, tremendous progress has been reported for pyrolysed Fe-N-C materials. However, the structure of their active sites has remained elusive, delaying further advance. Here, we synthesized Fe-N-C materials quasi-free of crystallographic iron structures after argon or ammonia pyrolysis. These materials exhibit nearly identical Mossbauer spectra and identical X-ray absorption near-edge spectroscopy (XANES) spectra, revealing the same Fe-centred moieties. However, the much higher activity and basicity of NH3-pyrolysed Fe-N-C materials demonstrates that the turnover frequency of Fe-centred moieties depends on the physico-chemical properties of the support. Following a thorough XANES analysis, the detailed structures of two FeN4 porphyrinic architectures with different O2 adsorption modes were then identified. These porphyrinic moieties are not easily integrated in graphene sheets, in contrast with Fe-centred moieties assumed hitherto for pyrolysed Fe-N-C materials. These new insights open the path to bottom-up synthesis approaches and studies on site-support interactions.

Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials.

Iron-based catalysts for the oxygen reduction reaction (ORR) were produced by pyrolysis of iron-acetate and Ketjenblack ® carbon with varying amounts of 2,2′-bipyridine in a closed, constant-volume vessel. The total surface nitrogen content detected by XPS varied from 0.6 to 2.2 at% when the nitrogen precursor loading was varied from 1.5 to 11.3 wt%. The amount of nitrogen in the Fe-pyridinic form is estimated to vary between 0.12 and 0.24 at%, correlating to catalytic activity (current density) variation from 0.07 to 1.9 mA cm −2 at a catalyst loading of 0.5 mg cm −2 . These results support the theory that iron associated with pyridinic nitrogen is a component of the catalytic active site responsible for oxygen reduction.

Non-precious oxygen reduction catalysts prepared by high-pressure pyrolysis for low-temperature fuel cells

Nitrogen Precursor Effects in Iron-Nitrogen-Carbon Oxygen Reduction Catalysts

Carboxylated carbon nanotubes were coated onto carbon microfiber electrodes to create a micron-scale bioelectrode. This material has a high surface area and can serve as a support for immobilization of enzymes such as glucose oxidase. A typical carbon nanotube loading of 13 μg cm−1 yields a coating thickness of 17 μm and a 2000-fold increase in surface capacitance. The modified electrode was further coated with a biocatalytic hydrogel composed of a conductive redox polymer, glucose oxidase, and a crosslinker to create a glucose bioelectrode. The current density on oxidation of glucose is 16.6 mA cm−2 at 0.5 V (vs. Ag/AgCl) in oxygen-free glucose solution. We consider this approach to be useful for designing and characterizing surface treatments for carbon mats and papers by mimicking their local microenvironment.

Carbon fiber microelectrodes modified with carbon nanotubes as a new support for immobilization of glucose oxidase

A method for making a carbon-metal-nitrogen oxygen reducing cathode catalyst, the method comprising mixing a carbon source with a transition metal precursor to form a metal precursor loaded carbon substrate; adding a nitrogen precursor compound to the metal precursor loaded carbon substrate to form a carbon-metal-nitrogen precursor; and pyrolyzing the carbon-metal-nitrogen precursor in a closed vessel, thereby forming an oxygen reducing cathode catalyst. The carbon-metal-nitrogen catalyst requires no precious metal such as Pt, and also provides benefits such as controlled deposition of catalytically active nitrogenous compounds that can increase the catalytic activity of the catalyst when compared to gaseous deposition of nitrogen to the surface of the carbon support.

Novel catalyst for oxygen reduction reaction in fuel cells

http://jes.ecsdl.org/content/160/8/F788.full.pdf

Vijayadurga Nallathambi

Papers

Non-precious oxygen reduction catalysts prepared by high-pressure pyrolysis for low-temperature fuel cells

Nitrogen Precursor Effects in Iron-Nitrogen-Carbon Oxygen Reduction Catalysts

Carbon fiber microelectrodes modified with carbon nanotubes as a new support for immobilization of glucose oxidase

Novel catalyst for oxygen reduction reaction in fuel cells

Carbon Supports for Non-Precious Metal Oxygen Reducing Catalysts