Nanoparticle catalysts for proton exchange membrane fuel cells: can surfactant effects be beneficial for electrocatalysis?

Platinum (Pt) nanoparticles were prepared in aqueous dispersion using the non-ionic surfactant nonylphenolethoxylate (NP9) and the cationic surfactant tetradecyltrimethylammonium bromide (TTAB). The surfactants were added to give colloidal stability. Such species are generally considered to block electrochemical active sites and to be undesirable for the oxygen reduction reaction (ORR). However, the procedures used to remove them are likely to cause particle aggregation. The purpose of this work was to investigate the effect of surfactants on Pt ORR performance. The nanoparticles prepared using NP9 showed good oxygen reduction performance when compared with the commercial Pt/C catalyst TKK, without removing the surfactant. In contrast, Pt nanoparticles prepared using the cationic surfactant TTAB showed very poor ORR performance, exemplifying the importance of careful surfactant selection in catalyst synthesis.

Configuration of microbially synthesized Pd-Au nanoparticles studied by STEM-based techniques.

Bimetallic Pd-Au particles synthesized using Desulfovibrio desulfuricans bacteria are characterized using scanning transmission electron microscopy (STEM) with a high-angle annular dark field (HAADF) detector combined with energy dispersive x-ray (EDX) silicon drift detector (SDD) elemental mapping and plasmon electron energy-loss spectroscopy (EELS). When combined with EDX, theoretical considerations or EELS, the atomic-number contrast (Z-contrast) provided by HAADF-STEM is effective in characterizing the compositional configuration of the bimetallic nanoparticles. Homogeneous mixing and complex segregations have been found for different particles in this work. The EELS study has also found different behaviours corresponding to surface plasmon resonances in different regions of a single particle due to its heterogeneity and anisotropy. HAADF-STEM tomography has been performed to obtain three-dimensional (3D) visualization of the nanoparticles.

Chemical manipulation by X-rays of functionalized thiolate self-assembled monolayers on Au.

The chemical modification caused by prolonged exposure to X-rays on a series of para-substituted phenyl moieties (-NO2, -CN, -CHO, -COOH, -CO2Me, and -CO2(1)Bu) at the surface of thiolate-Au self-assembled monolayers (SAMs) has been investigated by X-ray photoelectron spectroscopy (XPS). Furthermore, the influence that the phenyl group has on the chemical modification induced by the X-ray irradiation on the SAMs was investigated by comparing the XPS results obtained from irradiation on a NO2-aromatic-terminated SAM (6-(4-nitro-phenoxy)-hexane-1-thiolate (NPHT)) and NO2-aliphatic-terminated SAM (thioacetic acid S-(12-nitrododecyl) ester (TNDDE)). The NPHT and TNDDE SAMs have been shown to behave differently to X-ray exposure. The irradiation of the NPHT SAM led to the reduction of the nitro (-NO2) moiety to the amine (-NH2) moiety, as shown by the decrease in the intensity of the N 1s photoelectron peak for -NO2 (406 eV) in the XPS spectra with the concomitant increase in the N 1s photoelectron peak for -NH2 (399 eV). On the TNDDE SAM, XPS showed the -NO2 photoelectron peak again decreasing with prolonged X-ray irradiation whereas no peak was observed at 399 eV; therefore, the -NO2 moieties are selectively cleaved. No change was observed on the other functionalized monolayers apart from the -CO2(t)Bu-functionalized monolayer, where after 100 min of X-ray irradiation approximately 11% of the carbon content was lost. The S 2p and O 1s spectra remained unchanged during the irradiation suggesting the conversion of the -CO2(t)Bu to the -COOH moiety, although the conversion was not complete because the tertiary butyl moiety contributes 25% to the total carbon content of the SAM. Also, there was no evidence of the molecules desorbing from the substrate for any of the SAMs studied during the X-ray irradiation as shown by no change in the S 2p and C 1s XPS spectra taken during the X-ray irradiation.

The influence of surface lubricity on the adhesion of Navicula perminuta and Ulva linza to alkanethiol self-assembled monolayers.

The settlement and adhesion of Navicula perminuta and Ulva linza to methyl-terminated alkanethiol self-assembled monolayers (SAMs) of increasing chain length has been investigated. Organisms were allowed to settle onto the monolayers and were subsequently exposed to hydrodynamic shear stress in order to determine their adhesion strength. Results show that as the SAM structure changes from amorphous to crystalline (C14), there is a marked change in the adhesion of N. perminuta and U. linza. Given that the SAMs in the series all exhibit similar contact angle behaviour and surface energy, it is hypothesized that the lubricity of the surface plays a role in determining the surface adhesion.

Electrostatically stabilised nanoparticles: self-organization and electron-beam patterning.

The self-organisation of citrate- and magnesium oleate-stabilised gold nanoparticles on SiO2/Si substrates was investigated. In drop deposition, nucleation of citrate-stabilised gold nanoparticles was observed at the rim of the droplet, symmetric or multibranched dendroid gold structures were found in the area between the rim and the central part of the droplet, depending on the drying temperature. Homogeneous submonolayer nanoparticle coverage was obtained by immersion of amineterminated SiO2/Si surfaces into a citrate-stabilised colloidal gold acidic solution. Drop deposition of magnesium oleate-stabilised gold nanoparticles onto the SiO2/Si surfaces resulted in the formation of uniformly close-packed nanoparticle arrays. Under electron beam irradiation, no apparent changes were found for monolayer films of citrate-stabilized particles, but sintering of the nanoparticles was observed in multilayer films. In contrast, coalescence of magnesium oleate-stabilised gold nanoparticle occurred in monolayer films after electron irradiation.

Heterosupramolecular chemistry: programmed pseudorotaxane assembly at the surface of a nanocrystal.

Gold nanocrystals, stabilized by thiols covalently bound to a dibenzo[24]crown-8 moiety, have been programmed to recognize and selectively bind dibenzylammonium cations in solution. This results in a self-organization process at the surface of a nanocrystal with the assembly of a pseudorotaxane (see picture).

Acute inhibition by ethanol of intestinal absorption of glucose and hepatic glycogen synthesis on glucose refeeding after starvation in the rat.

1. Intragastric administration of ethanol (75 mmol/kg body wt.) at 1 h before glucose refeeding of 24 h-starved rats inhibited hepatic glycogen deposition (by 69%) and synthesis (by approx. 70%), but was without significant effect on muscle glycogen deposition and synthesis. 2. Treatment of ethanol-administered rats with methylpyrazole (an inhibitor of alcohol dehydrogenase) did not significantly diminish the inhibitory effect of ethanol on hepatic glycogen deposition after glucose refeeding, suggesting that the inhibition was not dependent on ethanol metabolism. 3. Ethanol delayed and diminished intestinal glucose absorption, at least in part by delaying gastric emptying. 4. At a lower dose (10 mmol/kg body wt.), ethanol inhibited hepatic glycogen repletion and synthesis without compromising intestinal glucose absorption. Ethanol inhibited glycogen deposition (by 40%) in hepatocytes from starved rats provided with glucose + lactate + pyruvate as substrates, consistent with it having a direct effect to diminish hepatic glycogen synthesis by inhibition of gluconeogenic flux at a site(s) between phosphoenolpyruvate and triose phosphate in the pathway. 5. It is concluded that ethanol acutely impairs hepatic glycogen repletion by inhibition at at least two distinct sites, namely (a) intestinal glucose absorption and (b) hepatic gluconeogenic flux.