ABSTRACT
Despite the great scientific effort, there are still some aspects of a polymeric membrane-based fuel cell (PEMFC) operation that are difficult to access experimentally. This is the case of the so-called triple-phase boundary (TPB), where the ionomer (commonly Nafion) interacts with the supported nanocatalyst (commonly Pt) and is key to the catalytic activity of the system. In this work, we use molecular dynamics simulations and electrochemical experiments on a Nafion/Pt/C system. We perform a systematic analysis, at an atomistic level, to evaluate the effect of several fundamental factors and their intercorrelation on the electrochemically active area (ECSA) of the catalysts. Our results reveal that at high Nafion contents, the catalyst utilization is affected due to the strong interaction between the sulfonic groups of the ionomer and the surface of the Pt nanoparticles (NPs). On the other hand, when the hydration level of the membrane decreases, the sulfonic groups have a greater occupation on the NP surface, covering the active area with hydrophobic Nafion chains and therefore increasing the inactive area. Voltammograms can corroborate our calculations. Overall, this investigation allows us to rationalize how the catalyst utilization is affected, which is an important step in establishing the relationship between the environment and the effectiveness and durability of the PEMFC system.
ABSTRACT
Two nickel/nitrogenated graphene hybrid electrodes (Ni-NrGO NH3 and Ni-NrGO APTES ) were synthesized, and their catalytic activity with respect to the hydrogen evolution reaction (HER) in alkaline media was analyzed. Incorporation of nitrogen to the carbon structure in graphene oxide (GO) or reduced GO (rGO) flakes in aqueous solutions was carried out based on two different configurations. NrGO NH 3 particles were obtained by a hydrothermal method using ammonium hydroxide as the precursor, and NGO APTES particles were obtained by silanization (APTES functionalization) of GO sheets. Aqueous dispersions containing NrGO NH 3 and NGO APTES particles were added to the traditional nickel Watts plating bath in order to prepare the Ni-NrGO NH 3 and Ni-NrGO APTES catalysts, respectively. Nickel substrates were coated with the hybrid nickel electrodeposits and used as electrodes for hydrogen production. The Ni-NrGO catalysts show a higher activity than the conventional nickel electrodeposited electrodes, particularly the ones containing APTES molecules because they allow obtaining a hydrogen current density 130% higher than conventional Ni-plated electrodes with a Watts bath in the absence of additives. In addition, both catalysts show a low deactivation rate during the ageing treatment, which is a sign of a longer midlife for the catalyst. Cyclic voltammetry and electrochemical impedance spectroscopy measurements were used for examination of the catalytic efficiency of hybrid Ni-NrGO electrodes for HER in KOH solution. High values of exchange current densities, 8.53 × 10-4 and 2.53 × 10-5 mA cm-2 for HER in alkaline solutions on Ni-NrGO NH 3 and Ni-NrGO APTES electrodes, respectively, were obtained.
ABSTRACT
High activity mesoporous Pt/Ru catalysts with 2D-hexagonal structure were synthesized using a triblock poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) copolymer (Pluronic F127) template. The normalized mass activities for the methanol oxidation reaction (MOR) of the Pt/Ru catalysts with a regular array of pores is higher than those reported for nanoparticulated Pt/Ru catalysts. Different kinetic parameters, as Tafel slope and activation energy, were obtained for the MOR on the mesoporous catalysts. Results indicated that catalysts performance depends on pore size. Mass activities and the CO2 conversion efficiency for large pore size mesoporous catalysts (10 nm) are greater than those reported for smaller pore size mesoporous catalysts with similar composition. The effect of pore size on catalysts performance is related to the greater accessibility of methanol to the active areas inside large pores. Consequently, the overall residence time of methanol increases as compared with mesoporous catalyst with small pores.
ABSTRACT
Xanthan is a polysaccharide secreted by Xanthomonas campestris that contains pentameric repeat units. The biosynthesis of xanthan involves an operon composed of 12 genes (gumB to gumM). In this study, we analyzed the proteins encoded by gumB and gumC. Membrane fractionation showed that GumB was mainly associated with the outer membrane, whereas GumC was an inner membrane protein. By in silico analysis and specific globomycin inhibition, GumB was characterized as a lipoprotein. By reporter enzyme assays, GumC was shown to contain two transmembrane segments flanking a large periplasmic domain. We confirmed that gumB and gumC mutant strains uncoupled the synthesis of the lipid-linked repeat unit from the polymerization process. We studied the effects of gumB and gumC gene amplification on the production, composition and viscosity of xanthan. Overexpression of GumB, GumC or GumB and GumC simultaneously did not affect the total amount or the chemical composition of the polymer. GumB overexpression did not affect xanthan viscosity; however, a moderate increase in xanthan viscosity was achieved when GumC protein levels were increased 5-fold. Partial degradation of GumC was observed when only that protein was overexpressed; but co-expression of GumB and GumC diminished GumC degradation and resulted in higher xanthan viscosity than individual GumB or GumC overexpression. Compared with xanthan from the wild-type strain, longer polymer chains from the strain that simultaneously overexpressed GumB and GumC were observed by atomic force microscopy. Our results suggest that GumB-GumC protein levels modulate xanthan chain length, which results in altered polymer viscosity.
