One-Pot Synthesis of Pd Nanoparticles Supported on Carbide-Derived Carbon for Oxygen Reduction Reaction.

We explored two methods for synthesizing Pd nanoparticles using three different carbide-derived carbon (CDC) support materials, one of which was nitrogen-doped. These materials were studied for oxygen reduction reaction (ORR) in 0.1 M KOH solution, and the resulting CDC/Pd catalysts were characterized using TEM, XRD, and XPS. The citrate method and the polyol method using polyvinylpyrrolidone (PVP) as a capping agent were employed to elucidate the impact of the support material on the final catalyst. The N-doping of the CDC material resulted in smaller Pd nanoparticles, but only in the case of the citrate method. This suggests that the influence of support is weaker when using the polyol method. The citrate method with CDC1, which is predominantly microporous, led to a higher degree of agglomeration and formation of larger particles in comparison to supports, which possessed a higher degree of mesoporosity. We achieved smaller Pd particle sizes using citrate and NaBH4 compared to the ethylene glycol PVP method. Pd deposited on CDC2 and CDC3 supports showed similar specific activity (SA), suggesting that the N-doping did not significantly influence the ORR process. The highest SA value was observed for CDC1/Pd_Cit, which could be attributed to the formation of larger Pd particles and agglomerates.

Stability of Carbon Supported Silver Electrocatalysts for Alkaline Oxygen Reduction and Evolution Reactions.

Ag-based electrocatalysts are promising candidates to catalyze the sluggish oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFC) and oxygen evolution reaction (OER) in unitized regenerative fuel cells. However, to be competitive with existing technologies, the AEMFC with Ag electrocatalyst must demonstrate superior performance and long-term durability. The latter implies that the catalyst must be stable, withstanding harsh oxidizing conditions. Moreover, since Ag is typically supported by carbon, the strict stability requirements extend to the whole Ag/C catalyst. In this work, Ag supported on Vulcan carbon (Ag/VC) and mesoporous carbon (Ag/MC) materials is synthesized, and their electrochemical stability is studied using a family of complementary techniques. We first employ an online scanning flow cell combined with inductively coupled plasma mass spectrometry (SFC-ICP-MS) to estimate the kinetic dissolution stability window of Ag. Strong correlations between voltammetric features and the dissolution processes are discovered. Very high silver dissolution during the OER renders this material impractical for regenerative fuel cell applications. To address Ag stability during AEMFC load cycles, accelerated stress tests (ASTs) in O2-saturated solutions are carried out in rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) setups. Besides tracking the ORR performance evolution, an ex situ long-term Ag dissolution study is performed. Moreover, morphological changes in the catalyst/support are tracked by identical-location transmission electron microscopy (RDE-IL-TEM). Voltammetry analysis before and after AST reveals a smaller change in ORR activity for Ag/MC, confirming its higher stability. RRDE results reveal a higher increase in the H2O2 yield for Ag/VC after the ASTs. The RDE-IL-TEM measurements demonstrate different degradation processes that can explain the changes in the long term performance. The results in this work point out that the stability of carbon-supported Ag catalysts depends strongly on the morphology of the Ag nanoparticles, which, in turn, can be tuned depending on the chosen carbon support and synthesis method.

Oxygen reduction reaction on Pd nanocatalysts prepared by plasma-assisted synthesis on different carbon nanomaterials.

In this work He/H2 plasma jet treatment was used to reduce Pd ions in the aqueous solution with simultaneous deposition of created Pd nanoparticles to support materials. Graphene oxide (GO) and nitrogen-doped graphene oxide (NrGO) were both co-reduced with the Pd ions to formulate catalyst materials. Pd catalyst was also deposited on the surface of carbon black. The prepared catalyst materials were physically characterized using transmission electron microscopy, scanning electron microscopy and x-ray photoelectron spectroscopy. The plasma jet method yielded good dispersion of small Pd particles with average sizes of particles being: Pd/rGO 2.9 ± 0.6 nm, Pd/NrGO 2.3 ± 0.5 nm and Pd/Vulcan 2.8 ± 0.6 nm. The electrochemical oxygen reduction reaction (ORR) kinetics was explored using the rotating disk electrode method. Pd catalyst deposited on nitrogen-doped graphene material showed slightly improved ORR activity as compared to that on the nondoped substrate, however Vulcan carbon-supported Pd catalyst exhibited a higher specific activity for oxygen electroreduction.

Stabilizer-free silver nanoparticles as efficient catalysts for electrochemical reduction of oxygen.

In this work we demonstrated the potential of the He+5% H2+1% N2 plasma jet treatment for the synthesis of surfactant-free silver nanoparticles (Ag NPs) with narrow size distribution. The obtained colloidal solutions of electrostatically stabilized Ag NPs do not show any agglomeration for several months. Apart from an atomic thin oxide layer and the relatively weakly bound OH- ions, the surface of Ag NPs can be considered as stabilizer-free. The surface charge (characterized by the zeta potential) of Ag NPs in solution was measured by electrophoretic light scattering technique. Plasmonic band position and width in the UV/VIS extinction spectra was utilized for the assessment of Ag NPs size distribution. Highly concentrated Ag NPs were uniformly deposited on the surface of the glassy carbon (GC) electrodes by vacuum-drying technique. The deposition process was monitored with a digital camera attached to a microscope. The assemblies of Ag NPs on the electrode surface were characterized by scanning electron microscopy. The Ag NP/GC catalysts were electrochemically tested in alkaline solution using the rotating disk electrode method. The Ag NP/GC electrodes exhibited high electrocatalytic activity toward the oxygen reduction reaction (ORR) in 0.1M KOH solution, indicating their potential applicability as cathode materials for alkaline fuel cells.