Petra J. Cameron

Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells?

The hypothesis that ion motion is responsible for anomalous hysteresis in the current–voltage curves of perovskite solar cells is investigated through a combination of electrical transport modelling and experimental measurements. In a combined computational and experimental study, good agreement is obtained between experiment and the results of a charge transport model covering mixed ionic-electronic conduction. Our model couples electrons, holes and defect mediated ion motion suggesting that slow moving ions are indeed the origin of the hysteresis. The magnitude of the ion diffusion coefficient required to match experiment and theory, ∼10−12 cm2 s−1, depends on the cell, but is similar to that predicted by microscopic theory of vacancy mediated diffusion. The investigation is extended to preconditioning procedures which are known to substantially influence the hysteresis. The method developed for solving the stiff equations in the drift diffusion model is widely applicable to other double layer problems occurring in electrochemical applications such as the evolution of transmembrane potentials in living cells.

Peptide based low molecular weight gelators

Over the last 12 months a number of papers have been published which shed light on the processes that control the self-assembly of peptides into fibrous hydrogel networks. A number of new properties of dipeptide hydrogels have also been reported. This article highlights recent activity in the area of peptide self-assembly, with a particular focus on tri-peptides, di-peptides and protected amino acids.

A small-scale air-cathode microbial fuel cell for on-line monitoring of water quality.

The heavy use of chemicals for agricultural, industrial and domestic purposes has increased the risk of freshwater contamination worldwide. Consequently, the demand for efficient new analytical tools for on-line and on-site water quality monitoring has become particularly urgent. In this study, a small-scale single chamber air-cathode microbial fuel cell (SCMFC), fabricated by rapid prototyping layer-by-layer 3D printing, was tested as a biosensor for continuous water quality monitoring. When acetate was fed as the rate-limiting substrate, the SCMFC acted as a sensor for chemical oxygen demand (COD) in water. The linear detection range was 3-164 ppm, with a sensitivity of 0.05 μA mM(-1) cm(-2) with respect to the anode total surface area. The response time was as fast as 2.8 min. At saturating acetate concentrations (COD>164 ppm), the miniature SCMFC could rapidly detect the presence of cadmium in water with high sensitivity (0.2 μg l(-1) cm(-2)) and a lower detection limit of only 1 μg l(-1). The biosensor dynamic range was 1-25 μg l(-1). Within this range of concentrations, cadmium affected only temporarily the electroactive biofilm at the anode. When the SCMFCs were again fed with fresh wastewater and no pollutant, the initial steady-state current was recovered within 12 min.

Air-stable photoconductive films formed from perylene bisimide gelators

We show that amino acid-PBIs can form one-dimensional structures at high pH and then gels at low pH. Both the dried solutions and dried gels are photoconductive. Interestingly, photoconductivity of these materials requires that the incident light has a wavelength shorter than 400 nm, in stark contrast with the absorption maxima of the PBIs. The photoconductivity correlates with the formation of the perylene radical anion, which is unusually highly stable in air for many hours.

Surface morphology and surface energy of anode materials influence power outputs in a multi-channel mediatorless bio-photovoltaic (BPV) system

Bio-photovoltaic cells (BPVs) are a new photo-bio-electrochemical technology for harnessing solar energy using the photosynthetic activity of autotrophic organisms. Currently power outputs from BPVs are generally low and suffer from low efficiencies. However, a better understanding of the electrochemical interactions between the microbes and conductive materials will be likely to lead to increased power yields. In the current study, the fresh-water, filamentous cyanobacterium Pseudanabaena limnetica (also known as Oscillatoria limnetica) was investigated for exoelectrogenic activity. Biofilms of P. limnetica showed a significant photo response during light-dark cycling in BPVs under mediatorless conditions. A multi-channel BPV device was developed to compare quantitatively the performance of photosynthetic biofilms of this species using a variety of different anodic conductive materials: indium tin oxide-coated polyethylene terephthalate (ITO), stainless steel (SS), glass coated with a conductive polymer (PANI), and carbon paper (CP). Although biofilm growth rates were generally comparable on all materials tested, the amplitude of the photo response and achievable maximum power outputs were significantly different. ITO and SS demonstrated the largest photo responses, whereas CP showed the lowest power outputs under both light and dark conditions. Furthermore, differences in the ratios of light : dark power outputs indicated that the electrochemical interactions between photosynthetic microbes and the anode may differ under light and dark conditions depending on the anodic material used. Comparisons between BPV performances and material characteristics revealed that surface roughness and surface energy, particularly the ratio of non-polar to polar interactions (the CQ ratio), may be more important than available surface area in determining biocompatibility and maximum power outputs in microbial electrochemical systems. Notably, CP was readily outperformed by all other conductive materials tested, indicating that carbon may not be an optimal substrate for microbial fuel cell operation.

Electrochemically-triggered spatially and temporally resolved multi-component gels

Spatial control over gelation with low molecular weight gelators is possible using an electrochemically-driven pH triggering method. Gelation occurs at the electrode surface. We show here that composition control in multi-component low molecular weight hydrogels can also be achieved, allowing simultaneous spatial, temporal and compositional control.

Porous ceramic anode materials for photo-microbial fuel cells

This study focuses on porous ceramics as a promising new type of anode material for photo-microbial fuel cells (p-MFCs). The anodes were made from titanium dioxide and chemical vapour deposition was used to coat them with a layer of fluorine doped tin oxide (FTO) to make them conducting. Chlorella vulgaris biofilms were grown in the millimetre sized pores of the ceramic electrodes, producing an extensive extra cellular matrix that was anchored directly to the electrode surface. In contrast algal cells grown on carbon felt appeared misshapen and lacked a continuous extra cellular matrix. A preliminary comparison of different anodes in p-MFCs showed that the power density was ∼16 times higher on a ceramic anode compared to the best performing carbon anode. Good power densities were also found for algae grown directly onto FTO coated glass, but in contrast to the ceramic anodes the biofilm did not adhere strongly to the planar surface and was easily removed or damaged.

A Comparative Plasmonic Study of Nanoporous and Evaporated Gold Films

Previously, we have reported that nanoporous gold (NPG) films prepared by a chemical dealloying method have distinctive plasmonic properties, i.e., they can simultaneously support localized and propagating surface plasmon resonance modes (l-SPR and p-SPR, respectively). In this study, the plasmonic properties of NPG are quantified through direct comparison with thermally evaporated gold (EG) films. Cyclic voltammetry and electrochemical impedance spectroscopy experiments reveal that the NPG films have 4–8.5 times more accessible surface area than EG films. Assemblies of streptavidin–latex beads generate p-SPR responses on both NPG and EG films that correlate well with the bead density obtained from scanning electron microscopy (SEM) images. A layer-by-layer assembly experiment on NPG involving biotinylated anti-avidin IgG and avidin, studied by l-SPR and SEM, shows that the l-SPR signal is directly linked to the accessibility of the interior of the NPG porosity, an adjustable experimental parameter that can be set by the dealloying condition and time.

Cs+ incorporation into CH3NH3PbI3 perovskite: substitution limit and stability enhancement

In this study we systematically explored the mixed cation perovskite Csx(CH3NH3)1−xPbI3. We exchanged the A-site cation by dipping MAPbI3 films into a CsI solution, thereby incrementally replacing the MA+ in a time-resolved dipping process and analysed the resulting thin-films with UV-Vis, XRD, EDAX, SEM and optical depth-analysis in a high-throughput fashion. Additional in situ UV-Vis and time-resolved XRD measurements allowed us to look at the kinetics of the formation process. The results showed a discontinuity during the conversion. Firstly, small amounts of Cs+ are incorporated into the structure. After a few minutes, the Cs content approaches a limit and grains of δ-CsPbI3 occur, indicating a substitution limit. We compared this cation exchange to a one-step crystallisation approach and found the same effect of phase segregation, which shows that the substitution limit is an intrinsic feature rather than a kinetic effect. Optical and structural properties changed continuously for small Cs incorporations. Larger amounts of Cs result in phase segregation. We estimate the substitution limit of CsxMA1−xPbI3 to start at a Cs ratio x = 0.13, based on combined measurements of EDAX, UV-Vis and XRD. The photovoltaic performance of the mixed cation perovskite shows a large increase in device stability from days to weeks. The initial efficiency of mixed CsxMA1−xPbI3 devices decreases slightly, which is compensated by stability after a few days.

Sensing of pathogenic bacteria based on their interaction with supported bilayer membranes studied by impedance spectroscopy and surface plasmon resonance

Pathogenic bacteria secrete various virulence factors, including toxins, lipases and proteases that allow them to infect, breakdown and colonize host tissue. Among various modes of action that the pathogenic bacteria use to damage the host, pore formation (by pore forming toxins (PFTs)) and lipid hydrolysis (by phospholipases) modes are common in damaging the eukaryotic cell membrane. PFTs in their monomeric form are extracellular diffusible and able to form hydrophilic pores in cell membrane while phospholipases cleaves and hydrolyzes the ester bonds of most phospholipids in cell membrane. Both modes of action cause uncontrolled permeation of ions and molecules across cell membrane, leading to cell death by apoptosis or necrosis. In this work, the toxins secreted by two clinically important human pathogens, methicillin susceptible Staphylococcus aureus (MSSA476) and Pseudomonas aeruginosa (PAO1) were studied via their interaction with a planar tethered bilayer lipid membrane (pTBLM) using surface plasmon resonance spectroscopy (SPR) and electrochemical impedance spectroscopy (EIS). Detection and discrimination is based on lipid-loss (lipid hydrolysis by phospholipases) or non lipid-loss (pore formation by PFTs) from pTBLM upon interaction with supernatant of pathogenic bacteria. Using EIS and SPR, it is demonstrated that major toxins of S. auerus are PFTs while most of toxin associated with P. aeruginosa are more lipid damaging lipolytic enzymes. Such a format might have future utility as a simple assay for measuring the presence membrane lytic virulence factors in clinical samples.