(Invited) Synthesis and Characterization of New Catalyst Materials for Electrocatalysis

In this talk I will discuss some of our recent explorations of new catalyst materials for electrocatalysis for renewable fuels and energy, including the synthesis and characterization of these materials. First, I will briefly describe our report of an efficient acid-stable N 2 -plasma treated hafnium oxyhydroxide electrocatalyst for hydrogen evolution and oxidation reactions (HER and HOR). Lack of a highly active, stable, earth-abundant electrocatalyst for carrying out HER and HOR in strongly acidic conditions is a major technical challenge for developing economical polymer electrolyte membrane (PEM)-based electrolyzers and fuel cells. We found that processing Hf oxide with an atmospheric N 2 plasma forms an acid-insoluble hafnium oxynitride material, and we propose that under electrochemical environments this material is transformed into an active oxynitride hydroxide that demonstrates unprecedented high catalytic activity and stability for both HER and HOR in strong acidic media for earth-abundant materials. The zero onset potentials and high current densities demonstrate that this material is a promising alternative to Pt group metal (PGM) catalysts, opening new opportunities to develop technologically and economically viable unitized regenerative fuel cell (URFC) systems and cost-effective PEM electrolyzers. Furthermore, these results have broad implications for using nitrogen incorporation (e.g. by N 2 plasma treatment) to activate other non-conductive compounds and films to form new active electrocatalysts. I will discuss our recent observations on the reaction-driven restructuring of defective PtSe 2 into an ultrastable electrocatalyst for the oxygen reduction reaction (ORR), which is of interest for accelerating the commercialization of PEM fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs). We have found that the restructured defective PtSe 2 electrocatalyst had 1.3 times the specific activity and 2.6 times the mass activity of a commercial Pt/C catalyst, and maintained this superior ORR activity even after 126,000 cycles in accelerated durability tests. I will describe our report of a highly active hafnium-modified iridium oxide (IrHf x O y ) electrocatalyst for the oxygen evolution reaction (OER), a reaction that limits development of energy efficient and economically viable a wide range of energy conversion devices. Iridium oxide (IrO x ) is the current benchmark electrocatalyst for OER due to its superior performance and excellent stability, but large scale applications using IrO x are impractical due to its low abundance and high cost. We have found an IrHf x O y electrocatalyst that demonstrated ten times higher activity in alkaline conditions (pH = 11) and four times higher activity in acid conditions (pH = 1) than an IrO x electrocatalyst. The highest intrinsic mass activity of the IrHf x O y catalyst in acid conditions was calculated as 6950 A g IrOx -1 at an overpotential (η) of 0.3 V. I will also discuss our research on phosphorus-doped Hf-Ru oxide (denoted here as Hf x Ru y PO) electrocatalysts for OER in which we demonstrated a strategy for efficiently promoting the durability of RuO 2 . This research was motivated by the need to address the rapid corrosion and precipitation of highly efficient precious metal (Ir, Ru, and Rh) nanoparticle catalysts in the harsh environment of OER in PEM electrolyzers for hydrogen fuel generation. We found that when the Hf x Ru y PO catalysts possessed a Hf:Ru atomic ratio of 1:2, they exhibited a highly efficient and stable OER activity over 40 hours. By XPS and Raman analyses, the HfPO component was found to play a significant role in improving the durability of RuO 2 through the formation of a HfOOH phase, which also possessed a higher OER activity and lower impedance. Most recently we are investigating metal-organic frameworks (MOFs) and MOF-derived (MOF-d) materials as electrocatalysts for renewable fuels and energy applications.