The interplay of metal-atom ordering, Fermi leveltuning and thermoelectric properties in cobalt shandites Co3M2S2 (M = Sn, In)

A combination of structural, physical and computational techniques including powder X-ray and neutron diffraction, SQUID magnetometry, electrical and thermal transport measurements, DFT calculations and 119Sn Mössbauer and X-ray photoelec-tron spectroscopies has been applied to Co3Sn2-xInxS2 (0 ≤ x ≤ 2) in an effort to understand the relationship between metal-atom ordering and physical properties as the Fermi level is systematically varied. Whilst solid solution behavior is found throughout the composition region, powder neutron diffraction reveals that indium preferentially occupies an inter-layer site over an alternative kagome-like intra-layer site. DFT calculations indicate that this ordering, which leads to a lowering of energy, is related to the dif-fering bonding properties of tin and indium. Spectroscopic data suggest that throughout the composition range 0 ≤ x ≤ 2, all ele-ments adopt oxidation states that are significantly reduced from expectations based on formal charges. Chemical substitution ena-bles the electrical transport properties to be controlled through tuning of the Fermi level within a region of the density of states, which comprises narrow bands of predominantly Co d-character. This leads to a compositionally-induced double metal-to-semiconductor-to-metal transition. The marked increase in the Seebeck coefficient as the semiconducting region is approached leads to a substantial improvement in the thermoelectric figure of merit, ZT, which exhibits a maximum of ZT = 0.32 at 673 K. At 425 K, the figure of merit for phases in the region 0.8 ≤ x ≤ 0.85 is amongst the highest reported for sulphide phases, suggesting these materials may have applications in low-grade waste heat recovery.

Electronic structure of porphyrin-based metal-organic frameworks and their suitability for solar fuel production photocatalysis

Metal-organic frameworks (MOFs) can be exceptionally good catalytic materials thanks to the presence of active metal centres and a porous structure that is advantageous for molecular adsorption and confinement. We present here a first-principles investigation of the electronic structure of a family of MOFs based on porphyrins connected through phenyl-carboxyl ligands and AlOH species, in order to assess their suitability for the photocatalysis of fuel production reactions using sunlight. We consider structures with protonated porphyrins and those with the protons exchanged with late 3d metal cations (Fe2+, Co2+, Ni2+, Cu2+, Zn2+), a process that we find to be thermodynamically favorable from aqueous solution for all these metals. Our band structure calculations, based on an accurate screened hybrid functional, reveal that the bandgaps are in a favorable range (2.0 to 2.6 eV) for efficient adsorption of solar light. Furthermore, by approximating the vacuum level to the pore center potential, we provide the alignment of the MOFs’ band edges with the redox potentials for water splitting and carbon dioxide reduction, and show that the structures studied here have band edges positions suitable for these reactions at neutral pH.

Heathland restoration on former agricultural land: effects of artificial acidification on the availability and uptake of toxic metal cations

Lowland heath is an internationally important habitat type that has greatly declined in abundance throughout Western Europe. In recent years this has led to a growing interest in the restoration of heathland on agricultural land. This generally requires the use of chemical treatments to return soil chemical conditions to those appropriate for the support of heathland ecosystems. However, the potential for negative impacts on the environment due to the potential of these treatments to increase the availability of trace metals via raised soil acidity requires investigation. A large-scale field study investigated the effect of two chemical treatments used in heathland restoration, elemental sulphur and ferrous sulphate, on soil acidity and whether it is possible to predict the effect of the treatments on availability of two potentially toxic cations (Al and Cd) in the soil along with their subsequent accumulation in the shoots of the grass Agrostis capillaris. Results showed that both treatments decreased soil pH, but that only elemental sulphur produced a pH similar to heathland soil. The availability of Al, measured by extraction with 1 M ammonium nitrate, could not be predicted by soil pH, depth in the soil and total Al concentration in the soil. By contrast, availability of Cd could be predicted from these three variables. Concentrations of both Al and Cd in the shoots of A. capillaris showed no significant relationship with the extractable concentration in the soil. Results are discussed in light of the possible environmental impacts of the chemical restoration techniques.

Predicting sizes of hexagonal and gyroid metal nanostructures from liquid crystal templating

We describe a method to predict and control the lattice parameters of hexagonal and gyroid mesoporous materials formed by liquid crystal templating. In the first part, we describe a geometric model with which the lattice parameters of different liquid crystal mesophases can be predicted as a function of their water/surfactant/oil volume fractions, based on certain geometric parameters relating to the constituent surfactant molecules. We demonstrate the application of this model to the lamellar (LR), hexagonal (H1), and gyroid bicontinuous cubic (V1) mesophases formed by the binary Brij-56 (C16EO10)/water system and the ternary Brij-56/hexadecane/water system. In this way, we demonstrate predictable and independent control over the size of the cylinders (with hexadecane) and their spacing (with water). In the second part, we produce mesoporous platinum using as templates hexagonal and gyroid phases with different compositions and show that in each case the symmetry and lattice parameter of the metal nanostructure faithfully replicate those of the liquid crystal template, which is itself in agreement with the model. This demonstrates a rational control over the geometry, size, and spacing of pores in a mesoporous metal.

Shape-controlled continuous synthesis of metal nanostructures

A segmented flow-based microreactor is used for the continuous production of faceted nanocrystals. Flow segmentation is proposed as a versatile tool to manipulate the reduction kinetics and control the growth of faceted nanostructures; tuning the size and shape. Switching the gas from oxygen to carbon monoxide permits the adjustment in nanostructure growth from 1D (nanorods) to 2D (nanosheets). CO is a key factor in the formation of Pd nanosheets and Pt nanocubes; operating as a second phase, a reductant, and a capping agent. This combination confines the growth to specific structures. In addition, the segmented flow microfluidic reactor inherently has the ability to operate in a reproducible manner at elevated temperatures and pressures whilst confining potentially toxic reactants, such as CO, in nanoliter slugs. This continuous system successfully synthesised Pd nanorods with an aspect ratio of 6; thin palladium nanosheets with a thickness of 1.5 nm; and Pt nanocubes with a 5.6 nm edge length, all in a synthesis time as low as 150 s.

Controlling ivy attachment to wall surfaces by applying paints, metal meshes and sheets

Growing ivy around buildings has benefits. However, ivy potentially damages buildings which limit its use. Options for preventing ivy attachment were investigated to provide ivy management alternatives. Indoor and outdoor experiments were conducted, where metals (Cu, Zn) and anti-graffiti paints were applied to model wall panels. Metal treatments, in both indoor and outdoor experiments, fully prevented ivy attachment. For Hedera helix, silane-based anti-graffiti paint prevented attachment in the laboratory and required under half the peak detachment force necessary to detach the control in the outdoor experiment. In conclusion, metals and silane-based paint are management possibilities for ivy attachment around buildings.