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With the increasing focus on decarbonisation of the transport sector, it is imperative to consider routes to electrify vehicles beyond those achievable using lithium-ion battery technology. These include heavy goods vehicles and aerospace applications that require propulsion systems that can provide gravimetric energy densities, which are more likely to be delivered by fuel cell systems. While the discussion of light-duty vehicles is abundant in the literature, heavy goods vehicles are under-represented. This paper presents an overview of the electrochemical degradation of a proton exchange membrane fuel cell integrated into a simulated Class 8 heavy goods range-extender fuel cell hybrid electric vehicle operating in urban driving conditions. Electrochemical degradation data such as polarisation curves, cyclic voltammetry values, linear sweep voltammetry values, and electrochemical impedance spectroscopy values were collected and analysed to understand the expected degradation modes in this application. In this application, the proton exchange membrane fuel cell stack power was designed to remain constant to fulfil the mission requirements, with dynamic and peak power demands managed by lithium-ion batteries, which were incorporated into the hybridised powertrain. A single fuel cell or battery cell can either be operated at maximum or nominal power demand, allowing four operational scenarios: maximum fuel cell maximum battery, maximum fuel cell nominal battery, nominal fuel cell maximum battery, and nominal fuel cell nominal battery. Operating scenarios with maximum fuel cell operating power experienced more severe degradation after endurance testing than nominal operating power. A comparison of electrochemical degradation between these operating scenarios was analysed and discussed. By exploring the degradation effects in proton exchange membrane fuel cells, this paper offers insights that will be useful in improving the long-term performance and durability of proton exchange membrane fuel cells in heavy-duty vehicle applications and the design of hybridised powertrains. [ABSTRACT FROM AUTHOR]

The combustion of mercury(II) thiocyanate to form 'Pharaoh's serpents' is a spectacular reaction first described nearly two centuries ago. The large volume of distinctive yellow branches that grow from a tiny quantity of flaming reactants makes this an enchanting demonstration, often used to depict the magic of chemistry. In recent years several videos of this bizarre process have 'gone viral' online. Formally, the reaction should yield a carbon nitride with the ideal formula C3N4 along with HgS. However, since early characterization attempts there has been little further study of the materials produced. Herein we apply modern characterization techniques to reinvestigate the nature of the carbon nitride and its intimate relationship to the HgS produced. The HgS phase forms nanoparticles that decorate the surfaces of a C3N4 foam matrix. Both of these compounds are important wide-gap semiconductors and we propose that the 'Pharaoh's serpents reaction' could be used to produce a potentially important heterojunction nanocomposite materials that could be useful optoelectronic and photocatalytic applications. [ABSTRACT FROM AUTHOR]

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60-125 nm in diameter and Li+ and Br- ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4-6 Å -1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br - close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Crystalline two-dimensional carbon nitrides with polytriazine imide (PTI) structure are shown to act amphoterically, buffering both HCl and NaOH aqueous solutions, resulting in charged PTI layers that dissolve spontaneously in their aqueous media, particularly for the alkaline solutions. This provides a low energy, green route to their scalable solution processing. Protonation in acid is shown to occur at pyridinic nitrogens, stabilized by adjacent triazines, whereas deprotonation in base occurs primarily at basal plane NH bridges, although NH 2 edge deprotonation is competitive. We conclude that mildly acidic or basic pHs are necessary to provide sufficient net charge on the nanosheets to promote dissolution, while avoiding high ion concentrations which screen the repulsion of like-charged PTI sheets in solution. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

The development of processes to tune the properties of materials is essential for the progression of next-generation technologies for catalysis, optoelectronics and sustainability including energy harvesting and conversion. Layered carbon nitrides have also been identified as of significant interest within these fields of application. However, most carbon nitride materials studied to date have poor crystallinity and therefore their properties cannot be readily controlled or easily related to their molecular level or nanoscale structures. Here we report a process for forming a range of crystalline layered carbon nitrides with polytriazine imide (PTI) structures that can be interconverted by simple ion exchange processes, permitting the tunability of their optoelectronic and chemical properties. Notable outcomes of our work are (a) the creation of a crystalline, guest-ion-free PTI compound that (b) can be re-intercalated with ions or molecules using "soft chemistry" approaches. This includes the intercalation of HCl, demonstrating a new ambient pressure route to the layered PTI· x HCl material that was previously only available by a high-pressure-high-temperature route (c). Our work also shows (d) that the intercalant-free (IF-) PTI material spontaneously absorbs up to 10 weight% H 2 O from the ambient atmosphere and that this process is reversible, leading to potential applications for membranes and water capture in dry environments.

Two-dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one-pot reductive method to produce solutions of single- and few-layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High-resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)