Computational modelling studies of the structure of perfluorosulfonic acid (PFSA) ionomer membranes consistently exhibit a nanoscopic phase-separated morphology in which the ionic side chains and aqueous counterions segregate from the fluorocarbon backbone to form clusters or channels. Although these investigations do not unambiguously predict the size or shape of the clusters, and whether or not the channels percolate the matrix or if the connections between them are more transient, the sequence of co-monomers along the main chain appears strongly to influence the domain size of the ionic regions, with more blocky sequences giving rise to larger domain sizes. The fundamental insight that substantial rearrangement of the sulfonic acid terminated side chains and fluorocarbon backbone takes place during swelling or shrinkage is borne out by both molecular and mesoscale simulations of model PFSA polymers, along with ab initio electronic structure calculations of minimally hydrated oligomeric fragments. Molecular-level modelling of proton transport in PFSA membranes attests to the complexity of the underlying mechanisms and the need to examine the chemical and physical processes at several distinct time and length scales. These investigations have revealed that the conformation of the fluorocarbon backbone, flexibility of the sidechains, and degree of aggregation and association of the sulfonic acid groups under minimally hydrated conditions collectively control the dissociation of the protons and the formation of Zundel and Eigen cations. The former appear to be the dominant charge carriers when the limiting water content allows only for the formation of a contact ion pair with the tethered sulfonate anion. As the water content increases, solvent-separated Eigen ions begin to appear, indicating that the dominant mechanism for diffusion of protons occurs over a region approximately 4 Å away from the sulfonate groups. Finally, both the vehicular and Grotthuss shuttling mechanisms contribute to the mobility of the protons but, surprisingly, they are not always correlated, resulting in a lower overall diffusion coefficient. In summary, as the preceding observations indicate, the state of computational modelling of PFSA membranes has progressed sufficiently over the last decade to enable its use as a powerful predictive tool with which to guide the process of designing novel membrane materials for fuel cell applications.

A study of 1304 data points collated over 266 papers statistically evaluates the relationships between carbon nanotube (CNT) material characteristics, including: electrical, mechanical, and thermal properties; ampacity; density; purity; microstructure alignment; molecular dimensions and graphitic perfection; and doping. Compared to conductive polymers and graphitic intercalation compounds, which have exceeded the electrical conductivity of copper, CNT materials are currently one‐sixth of copper's conductivity, mechanically on‐par with synthetic or carbon fibers, and exceed all the other materials in terms of a multifunctional metric. Doped, aligned few‐wall CNTs (FWCNTs) are the most superior CNT category; from this, the acid‐spun fiber subset are the most conductive, and the subset of fibers directly spun from floating catalyst chemical vapor deposition are strongest on a weight basis. The thermal conductivity of multiwall CNT material rivals that of FWCNT materials. Ampacity follows a diameter‐dependent power‐law from nanometer to millimeter scales. Undoped, aligned FWCNT material reaches the intrinsic conductivity of CNT bundles and single‐crystal graphite, illustrating an intrinsic limit requiring doping for copper‐level conductivities. Comparing an assembly of CNTs (forming mesoscopic bundles, then macroscopic material) to an assembly of graphene (forming single‐crystal graphite crystallites, then carbon fiber), the ≈1 µm room‐temperature, phonon‐limited mean‐free‐path shared between graphene, metallic CNTs, and activated semiconducting CNTs is highlighted, deemphasizing all metallic helicities for CNT power transmission applications.

Although many different structural models have been proposed for perfluorosulfonic acid (PFSA) ionomers such as Nafion, the very high degree of disorder in these materials makes it difficult, if not impossible, to deduce their morphology unambiguously from small angle X-ray and neutron scattering (SAXS/SANS) experiments alone. We present a combination of a model-independent procedure for obtaining structural information from SAXS patterns based on a Maximum Entropy (MaxEnt) approach coupled with mesoscale simulations of the morphology of Nafion using Dissipative Particle Dynamics (DPD) parameterized with atomistic calculations and density functional theory. These two methods show that the nanoscale ionic clustering in PFSAs is intimately linked to, but spatially separate from, the larger scale organization of the fluorocarbon backbone. Although we are unable to directly observe crystallization of the backbone in the DPD simulations, the high density regions of fluorocarbon segments correspond exactly to those regions where the density of ionic clusters is lowest, each forming an independent bicontinuous domain. We are thus able to demonstrate a unified morphological description of PFSAs based on both statistical (MaxEnt) and thermodynamic (DPD) descriptions, which broadly favours a bicontinuous network of ionic clusters embedded in a matrix of fluorocarbon chains.

The flexibility of the side chain and effects of conformational changes in the backbone on hydration and proton transfer in the short-side-chain (SSC) perfluorosulfonic acid fuel cell membrane have been investigated through first principles based molecular modelling studies. Potential energy profiles determined at the B3LYP/6-31G(d,p) level in the two pendant side chain fragments: CF₃CF(–O(CF₂)₂SO₃H)–(CF₂)₇–CF(–O(CF₂)₂SO₃H)CF₃ indicate that the largest CF₂–CF₂ rotational barrier along the backbone is nearly 28.9 kJ mol⁻¹ higher than the minimum energy staggered trans conformation. Furthermore, the calculations reveal that the stiffest portion of the side chain is near to its attachment site on the backbone, with CF–O and O–CF₂ barriers of 38.1 and 28.0 kJ mol⁻¹, respectively. The most flexible portion of the side chain is the carbon–sulfur bond, with a barrier of only 8.8 kJ mol⁻¹. Extensive searches for minimum energy structures (at the B3LYP/6-311G(d,p) level) of the same polymeric fragment with 4–7 explicit water molecules reveal that the perfluorocarbon backbone may adopt either an elongated geometry, with all carbons in a trans configuration, or a folded conformation as a result of the hydrogen bonding of the terminal sulfonic acids with the water. These electronic structure calculations show that the fragments displaying the latter ‘kinked’ backbone possessed stronger binding of the water to the sulfonic acid groups, and also undergo proton dissociation with fewer water molecules. The calculations point to the importance of the flexibility in both the backbone and side chains of PFSA membranes to effectively transport protons under low humidity conditions.

We discuss the synthesis of carbon nanotubes (CNTs) and graphene by catalytic chemical vapour deposition (CCVD) and plasma-enhanced CVD (PECVD), summarising the state-of-the-art understanding of mechanisms controlling their growth rate, chiral angle, number of layers (walls), diameter, length and quality (defects), before presenting a new model for 2D nucleation of a graphene sheet from amorphous carbon on a nickel surface. Although many groups have modelled this process using a variety of techniques, we ask whether there are any complementary ideas emerging from the different proposed growth mechanisms, and whether different modelling techniques can give the same answers for a given mechanism. Subsequently, by comparing the results of tight-binding, semi-empirical molecular orbital theory and reactive bond order force field calculations, we demonstrate that graphene on crystalline Ni(111) is thermodynamically stable with respect to the corresponding amorphous metal and carbon structures. Finally, we show in principle how a complementary heterogeneous nucleation step may play a key role in the transformation from amorphous carbon to graphene on the metal surface. We conclude that achieving the conditions under which this complementary crystallisation process can occur may be a promising method to gain better control over the growth processes of both graphene from flat metal surfaces and CNTs from catalyst nanoparticles.