Scalable Sacrificial Templating to Increase Porosity and Platinum Utilisation in Graphene-Based Polymer Electrolyte Fuel Cell Electrodes.

Polymer electrolyte fuel cells hold great promise for a range of applications but require advances in durability for widespread commercial uptake. Corrosion of the carbon support is one of the main degradation pathways; hence, corrosion-resilient graphene has been widely suggested as an alternative to traditional carbon black. However, the performance of bulk graphene-based electrodes is typically lower than that of commercial carbon black due to their stacking effects. This article reports a simple, scalable and non-destructive method through which the pore structure and platinum utilisation of graphene-based membrane electrode assemblies can be significantly improved. Urea is incorporated into the catalyst ink before deposition, and is then simply removed from the catalyst layer after spraying by submerging the electrode in water. This additive hinders graphene restacking and increases porosity, resulting in a significant increase in Pt utilisation and current density. This technique does not require harsh template etching and it represents a pathway to significantly improve graphene-based electrodes by introducing hierarchical porosity using scalable liquid processes.

Alloyed Pt3M (M = Co, Ni) nanoparticles supported on S- and N-doped carbon nanotubes for the oxygen reduction reaction.

Sulfur- (S-CNT) and nitrogen-doped (N-CNT) carbon nanotubes have been produced by catalytic chemical vapor deposition (c-CVD) and were subject to an annealing treatment. These CNTs were used as supports for small (≈2 nm) Pt3M (M = Co or Ni) alloyed nanoparticles that have a very homogeneous size distribution (in spite of the high metal loading of ≈40 wt % Pt), using an ionic liquid as a stabilizer. The electrochemical surface area, the activity for the oxygen reduction reaction and the amount of H2O2 generated during the oxygen reduction reaction (ORR) have been evaluated in a rotating ring disk electrode experiment. The Pt3M/N-CNT catalysts revealed excellent electrochemical properties compared to a commercial Pt3Co/Vulcan XC-72 catalyst. The nature of the carbon support plays a key role in determining the properties of the metal nanoparticles, on the preparation of the catalytic layer, and on the electrocatalytic performance in the ORR. On N-CNT supports, the specific activity followed the expected order Pt3Co > Pt3Ni, whereas on the annealed N-CNT support, the order was reversed.

Comparison of two tetrapodal N,O ligands: impact of the softness of the heterocyclic N-donors pyridine and pyrazine on the selectivity for Am(III) over Eu(III).

To quantify the impact of the N-donor softness on the coordination of f elements in aqueous solution, and in particular on the selectivity for Am(III) over Eu(III), we have designed the two tetrapodal hexadentate ligands N,N-bis(2-pyridylmethyl)ethylenediamine-N',N'-diacetic acid (Lpy) and N,N-bis(2-pyrazylmethyl)ethylenediamine-N',N'-diacetic acid (Lpz). These ligands bear two hard acetate groups to provide stability to the An(III) and Ln(III) complexes and two N-heterocyclic soft groups to provide Am(III) versus Eu(III) selectivity. They only differ in their N-donor moieties, pyridine or pyrazine. The proton NMR and potentiometric analyses performed on the lanthanide complexes of the two ligands indicate that a unique metallic complex, LnL, is formed and that LnLpy+ and LnLpz+ have the same structure in water. Furthermore, the hydration numbers of the europium and terbium ions in these complexes, measured by luminescence decay, have the same value (q = 3), indicating that the two ligands act as hexadentate donors in both systems. As expected, the softer pyrazine-based ligand gives less stable complexes than the pyridine-based ligand with the hard Ln(III) cations. The fragment N(CH2pz)2 containing two pyrazine functions has a very low contribution to the stability of the lanthanide complexes, even though the pyrazine groups are coordinated to the cation in water. The stabilities of the americium(III) complexes were determined by potentiometry and are greater than those found for the isoelectronic europium complexes. The selectivity for Am(III) over Eu(III) increases from 60 to 500 when the pyridine-containing fragment N(CH2py)2 is substituted by the pyrazine-containing fragment N(CH2pz)2, which demonstrates that the selectivity for Am(III) over Eu(III) is significantly enhanced when the softness of the N-heterocycle increases from pyridine to pyrazine. These new hydrophilic ligands present attractive selectivities for Am(III) over Eu(III) that could make them good candidates for the selective back extraction of Am(III) from organic solutions containing 4f and 5f elements.