Lesia V. Protsailo

Synthesis and Characterization of 9 nm Pt–Ni Octahedra with a Record High Activity of 3.3 A/mgPt for the Oxygen Reduction Reaction

Nanoscale Pt-Ni bimetallic octahedra with controlled sizes have been actively explored in recent years owning to their outstanding activity for the oxygen reduction reaction (ORR). Here we report the synthesis of uniform 9 nm Pt-Ni octahedra with the use of oleylamine and oleic acid as surfactants and W(CO)6 as a source of CO that can promote the formation of {111} facets in the presence of Ni. Through the introduction of benzyl ether as a solvent, the coverage of both surfactants on the surface of resultant Pt-Ni octahedra was significantly reduced while the octahedral shape was still attained. By further removing the surfactants through acetic acid treatment, we observed a specific activity 51-fold higher than that of the state-of-the-art Pt/C catalyst for the ORR at 0.93 V, together with a record high mass activity of 3.3 A mgPt(-1) at 0.9 V (the highest mass activity reported in the literature was 1.45 A mgPt(-1)). Our analysis suggests that this great enhancement of ORR activity could be attributed to the presence of a clean, well-preserved (111) surface for the Pt-Ni octahedra.

Pt Monolayer on Porous Pd−Cu Alloys as Oxygen Reduction Electrocatalysts†

We demonstrate the synthesis of a core-shell catalyst consisting of a Pt monolayer as the shell and porous/hollow Pd-Cu alloy nanoparticles as the core. The porous/hollow Pd-Cu nanoparticles were fabricated by selectively dissolving a less noble metal, Cu, using an electrochemical dealloying process. The Pt mass activity for the oxygen reduction reaction of a Pt monolayer deposited on such a porous core is 3.5 times higher than that of a Pt monolayer deposited on bulk Pd nanoparticles and 14 times higher than that of state-of-the-art Pt/C electrocatalysts.

Durability of Perfluorosulfonic Acid and Hydrocarbon Membranes : Effect of Humidity and Temperature

The effect of humidity on the chemical stability of two types of membranes [i.e., perfluorosulfonic acid type (PFSA, Nafion 112) and biphenyl sulfone hydrocarbon type, (BPSH-35)] was studied by subjecting the membrane electrode assemblies (MEAs) to open-circuit voltage (OCV) decay and potential cycling tests at elevated temperatures and low inlet-gas relative humidities. The BPSH-35 membranes showed poor chemical stability in ex situ Fenton tests compared to that of Nafion membranes. However, under fuel cell conditions, BPSH-35 MEAs outperformed Nafion 112 MEAs in both the OCV decay and potential cycling tests. For both membranes, (i) at a given temperature, membrane degradation was more pronounced at lower humidities and (ii) at a given relative humidity operation, increasing the cell temperature accelerated membrane degradation. Mechanical stability of these two types of membranes was also studied using relative humidity (RH) cycling. Due to decreased swelling and contraction during wet-up and dry-out cycles, Nafion 112 lasted longer than BPSH-35 membranes in the RH cycling test.

Hydrogen Peroxide Formation Rates in a PEMFC Anode and Cathode Effect of Humidity and Temperature

Hydrogen peroxide (H 2 O 2 ) formation rates in a proton exchange membrane fuel cell (PEMFC) anode and cathode were estimated as a function of humidity and temperature by studying the oxygen reduction reaction (ORR) on a rotating ring disk electrode. Fuel cell conditions were replicated by depositing a film of Pt/Vulcan XC-72 catalyst onto the disk and by varying the temperature, dissolved O 2 concentration, and the acidity levels in hydrochloric acid (HClO 4 ). The HClO 4 acidity was correlated to ionomer water activity and hence fuel cell humidity. The H 2 O 2 formation rates showed a linear dependence on oxygen concentration and square dependence on water activity. The H 2 O 2 selectivity in ORR was independent of oxygen concentration but increased with the decrease in water activity (i.e., decreased humidity). Potential dependent activation energy for the H 2 O 2 formation reaction was estimated from data obtained at different temperatures.

Core–shell catalysts consisting of nanoporous cores for oxygen reduction reaction

A comprehensive experimental study was conducted on the dealloying of PdNi6 nanoparticles under various conditions. A two-stage dealloying protocol was developed to leach >95% of Ni while minimizing the dissolution of Pd. The final structure of the dealloyed particle was strongly dependent on the acid used and temperature. When H2SO4 and HNO3 solutions were used in the first stage of dealloying, solid and porous particles were generated, respectively. The porous particles have a 3-fold higher electrochemical surface area per Pd mass than the solid ones. The dealloyed PdNi6 nanoparticles were then used as a core material for the synthesis of core-shell catalysts. These catalysts were synthesized in gram-size batches and involved Pt displacement of an underpotentially deposited (UPD) Cu monolayer. The resulting materials were characterized by scanning transmission electron microscopy (STEM) and in situ X-ray diffraction (XRD). The oxygen reduction reaction (ORR) activity of the core-shell catalysts is 7-fold higher than the state-of-the-art Pt/C. The high activity was confirmed by a more than 40 mV improvement in fuel cell performance with a Pt loading of 0.1 mg cm(-2) by using the core-shell catalysts.

Oxidation Resistance of Bare and Pt-Coated Electrically Conducting Diamond Powder as Assessed by Thermogravimetric Analysis

A corrosion-resistant electrocatalyst support was prepared by overcoating high surface-area diamond powder (3-6 nm diameter, 250 m 2 /g) with a thin layer of boron-doped ultrananocrystalline diamond (B-UNCD) by microwave plasma-assisted chemical vapor deposition. This core-shell approach produces electrically conducting (0.4-0.5 S/cm) and high surface-area (150―170 m 2 /g) diamond powder (B-UNCD-D). Accelerated degradation testing was performed by thermogravimetric analysis (TGA) to assess the oxidation resistance (i.e., corrosion resistance) of powder in the absence and presence of nanoscale Pt. The oxidation onset temperature for B-UNCD-D powder decreased with the Pt loading from 0 to 30 wt % (Pt/C). However, compared with the bare powder, the rate of carbon consumption was significantly greater for Pt-(XC-72) as compared to the platinized diamond powder. For example, the temperature of the maximum carbon consumption rate, T d , occurred at 426°C for Pt-(XC-72) (20% Pt/C), which was 295°C lower than the T d for bare XC-72. In contrast, T d for Pt-(B-UNCD-D, 20% Pt/C) was 558°C; a temperature that was only 62°C lower than that for bare diamond. Isothermal oxidation at 300°C for 5 h produced negligible weight loss for Pt-UNCD-D (20% Pt/C) while a 75% weight loss was observed for Pt-(XC-72) (20% Pt/C). The results clearly demonstrate that platinized diamond is more resistant to gas phase oxidation than is platinized Vulcan at elevated temperatures.

Effect of Diphenyl Siloxane on the Catalytic Activity of Pt on Carbon

The effect of silicone on the catalytic activity of Pt for oxygen reduction and hydrogen adsorption was studied using diphenyl siloxane as a source compound at a rotating disk electrode (RDE). Diphenyl siloxane did not affect the catalytic activity of Pt when it was injected into the electrolyte. However, it blocked the oxygen reduction reaction when it was premixed with the catalyst. Proton transport was not blocked in either case. We postulate that diphenyl siloxane induces hydrophobicity and causes local water starvation, thereby blocking oxygen transport. Hence, the slow leaching of silicone seals in a fuel cell could cause silicon accumulation in the electrode, which irreversibly degrades fuel cell performance by blocking oxygen transport to the catalyst sites.

Highly Dispersed Alloy Catalyst for Durability

Achieving Department of Energys (DOEs) stated 5000-hour durability goal for light-duty vehicles by 2015 will require membrane electrode assemblies (MEAs) with characteristics that are beyond the current state of the art. Significant effort was placed on developing advanced durable cathode catalysts to arrive at the best possible electrode for high performance and durability, as well as developing manufacturing processes that yield significant cost benefit. Accordingly, the overall goal of this project was to develop and construct advanced MEAs that will improve performance and durability while reducing the cost of proton exchange membrane fuel cell (PEMFC) stacks. The project, led by UTC Power, focused on developing new catalysts/supports and integrating them with existing materials (membranes and gas diffusion layers (GDLs)) using state-of-the-art fabrication methods capable of meeting the durability requirements essential for automotive applications. Specifically, the project work aimed to lower platinum group metals (PGM) loading while increasing performance and durability. Appropriate catalysts and MEA configuration were down-selected that protects the membrane, and the layers were tailored to optimize the movements of reactants and product water through the cell to maximize performance while maintaining durability.