Conductive polymer-based complex catalysts

Pt-based catalysts are two necessary approaches at the current technology stage. It is believed that non-noble metal electrocatalysts is probably the sustainable solution for PEM fuel cell commercialization. In the past several decades, various nonnoble metal catalysts for ORR have been explored, including non-pyrolyzed and pyrolyzed transition metal nitrogen-containing complexes, transition metal chalcogenides, conductive polymer-based catalysts, metal oxides/carbides/nitrides/ oxynitrides/carbonitrides, and enzymatic compoimds. The major effort in non-noble metal electrocatalysts for ORR is to increase both the catalytic activity and stability. 

The principle is to activate molecular oxygen, by the Mn porphyrin entrapped in the conductive polymer (polypyrrole), and thus to form oxo species at the electrode surface. Then, these oxo complexes can oxidize the hydrocarbons or phenol. The catalyst should be regenerated and this can be done by electroreduction at a constant potential (typically at — 0.5 V/SCE in acetonitrile). Moreover, the solution should contain an axial base (i.e. imidazole), and an activator (benzoic anhydride) [165,172]. 

This chapter focuses on the theoretical modeling studies of ORR catalysts for PEMFC. Theoretical methods, such as density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulation, are presented. Current understanding of ORR mechanism in acidic medium is briefly discussed. Recent theoretical investigations on oxygen reduction electrocatalysts, such as Pt-based catalysts, non-Pt metal catalysts (Pd, Ir, CuCl), and non-precious metal catalysts (transitional metal macrocyclic complexes, conductive polymer materials, and carbon-based materials), are reviewed. The oxygen reduction mechanisms catalyzed by these catalysts are discussed based on the results. 

Three papers have appeared in the past two years on catalysts that are either supported on polymers or are heterogeneous. Djakovitch first reported animation reactions catalyzed by palladium particles immobilized on metal oxide supports, as well as by palladium complexes contained in NaY zeolites [172]. In most cases, these reactions were conducted at high temperatures, generally 135 °C. When NaOtBu was used as the base, competing amination through a benzyne intermediate was observed. Thus, para meta regioselectivity was not high, and reaction yields were modest. 

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