A Novel Cryogenic Approach to 3D Printing Cytocompatible, Conductive, Hydrogel-Based Inks.

In the field of tissue engineering and regenerative medicine, developing cytocompatible 3D conductive scaffolds that mimic the native extracellular matrix is crucial for the engineering of excitable cells and tissues. In this study, a custom cryogenic extrusion 3D printer was developed, which afforded control over both the ink and printing surface temperatures. Using this approach, aqueous inks were printed into well-defined layers with high precision. A conductive hydrogel ink was developed from chitosan (CS) and edge-functionalised expanded graphene (EFXG). Different EFXG:CS ratios (between 60:40 and 80:20) were evaluated to determine both conductivity and printability. Using the novel customized cryogenic 3D printer, conductive structures of between 2 and 20 layers were produced, with feature sizes as small as 200 µm. The printed structures are mechanically robust and are electrically conducting. The highest Young's modulus and conductivity in a hydrated state were 2.6 MPa and ∼45 S/m, respectively. Cytocompatibility experiments reveal that the developed material supports NSC-34 mouse motor neuron-like cells in terms of viability, attachment, and proliferation. The distinctive mechanical and electrical properties of the 3D-printed structures would make them good candidates for the engineering of 3D-structured excitable cells. Moreover, this novel printing setup can be used to print other hydrogel-based inks with high precision and resolution.

Enhanced photoactivity and selectivity over BiOI-decorated Bi2WO6 microflower for selective oxidation of benzylamine: Role of BiOI and mechanism.

The importance of developing effective and selective photocatalytic materials to realize efficient renewable energy-based organic synthetic processes, such as selective oxidation of benzylamines and its derivatives to the corresponding imines has become more apparent in recent years. Here we present the first reported BiOI/Bi2WO6 (BI/BW) microflower heterostructure as a visible-light-driven photocatalyst for such reactions. By decorating the hydrothermally prepared BW with BI via successive ionic layer adsorption and reaction (SILAR) method, benzylamine conversion is improved from 68 % to 92 % as compared to undecorated. Furthermore, selectivity to desired imine product is substantially increased from 59 % to 95 %. These outstanding performances are attributed to enhanced electron-hole separation and transfer efficiency as well as a greater preference for adsorption of benzylamine compared to the imine products and extended visible-light absorption range inherited from BI component as supported by competitive adsorption studies, ultraviolet-visible diffuse reflectance spectroscopy, and photoelectrochemical experiments. Possible mechanisms, band energy diagram, and decisive roles of O2- and h+ in the selective transformation of benzylamine were proposed based on Mott-Schottky, scavenging, and electron paramagnetic resonance radical trapping experiments. This work highlights a simple approach for improving photocatalytic activity and selectivity which are highly desirable in renewable energy-based chemical synthetic processes.

LED PEDD Discharge Photometry: Effects of Software Driven Measurements for Sensing Applications.

This work explores the effects of embedded software-driven measurements on a sensory target when using a LED as a photodetector. Water turbidity is used as the sensory target in this study to explore these effects using a practical and important water quality parameter. Impacts on turbidity measurements are examined by adopting the Paired Emitter Detector Diode (PEDD) capacitive discharge technique and comparing common embedded software/firmware implementations. The findings show that the chosen software method can (a) affect the detection performance by up to 67%, (b) result in a variable sampling frequency/period, and (c) lead to an disagreement of the photo capacitance by up to 23%. Optimized code is offered to correct for these issues and its effectiveness is shown through comparative analyses, with the disagreement reduced significantly from 23% to 0.18%. Overall, this work demonstrates that the embedded software is a key and critical factor for PEDD capacitive discharge measurements and must be considered carefully for future measurements in sensor related studies.

Flexible Polymer X-ray Detectors with Non-fullerene Acceptors for Enhanced Stability: Toward Printable Tissue Equivalent Devices for Medical Applications.

There is growing interest in the development of novel materials and devices capable of ionizing radiation detection for medical applications. Organic semiconductors are promising candidates to meet the demands of modern detectors, such as low manufacturing costs, mechanical flexibility, and a response to radiation equivalent to human tissue. However, organic semiconductors have typically been employed in applications that convert low energy photons into high current densities, for example, solar cells and LEDs, and thus existing design rules must be re-explored for ionizing radiation detection where high energy photons are converted into typically much lower current densities. In this work, we report the optoelectronic and X-ray dosimetric response of a tissue equivalent organic photodetector fabricated with solution-based inks prepared from polymer donor poly(3-hexylthiophene) (P3HT) blended with either a non-fullerene acceptor (5Z,5'Z)-5,5'-((7,7'-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene))bis(3-ethyl-2-thioxothiazolidin-4-one) (o-IDTBR) or a fullerene acceptor, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Indirect detection of X-rays was achieved via coupling of organic photodiodes with a plastic scintillator. Both detectors displayed an excellent response linearity with dose, with sensitivities to 6 MV photons of 263.4 ± 0.6 and 114.2 ± 0.7 pC/cGy recorded for P3HT:PCBM and P3HT:o-IDTBR detectors, respectively. Both detectors also exhibited a fast temporal response, able to resolve individual 3.6 µs pulses from the linear accelerator. Energy dependence measurements highlighted that the photodetectors were highly tissue equivalent, though an under-response in devices compared to water by up to a factor of 2.3 was found for photon energies of 30-200 keV due to the response of the plastic scintillator. The P3HT:o-IDTBR device exhibited a higher stability to radiation, showing just an 18.4% reduction in performance when exposed to radiation doses of up to 10 kGy. The reported devices provide a successful demonstration of stable, printable, flexible, and tissue-equivalent radiation detectors with energy dependence similar to other scintillator-based detectors used in radiotherapy.

Effect of exposed facets of bismuth vanadate, controlled by ethanolamine, on oxidative coupling of primary amines.

This work firstly demonstrates the ethanolamine (ETA)-assisted hydrothermal synthesis of BiVO4, with different ratios of exposed {110}/{010} planes and relates this to performance in photocatalytic oxidative coupling of benzylamine under visible light. {110}-dominant BiVO4 exhibits outstanding photocatalytic activity at room temperature owing to synergistic effects of largely exposed {110}-oxidative facet along with excellent charge generation and migration abilities, as evidenced by X-ray diffraction patterns, electrochemical impedance spectra, and photocurrent responses. The catalyst can successfully transform benzylamine derivatives to corresponding imines with selectivities of >85%, indicating a wide scope of amine substrates that can be used with the developed catalyst. Based on radical scavenging, spin-trapping EPR, and Mott-Schottky results, a plausible oxidative coupling mechanism via a O2--assisted route and band energy diagram of the catalyst are proposed. This work highlights the influence of ETA in controlling resultant exposed crystal facets of the final BiVO4, which is the main factor governing oxidative amine coupling activity. Importantly, the tunability of exposed {110}/{010} facet of BiVO4 controlled by ETA as well as a correlation between {110} facet and the coupling activity of benzylamine firstly disclosed in this work could be readily extended for designing functional catalysts with desired performances.

Solvothermally synthesized anatase TiO2 nanoparticles for photoanodes in dye-sensitized solar cells.

Many researchers working on the development of Dye-sensitized solar cells (DSCs) continue to focus on the synthesis of photoanode materials with high surface area, along with high light scattering ability to enhance light harvesting efficiency (LHE). On the other hand, dye packing density, which can also affect the LHE significantly, is often overlooked. Solvothermally synthesized anatase TiO2 nanoparticles (SANP) were obtained by a new and simple approach using a mixed solvent, ethanol and acetic acid. SANP were applied as a photoanodes material in DSCs using a metal-free organic dye (D149) or organometallic dye (N719) dyes. The dye loading (packing density) was examined in term of the isoelectric point (IEP) and the contribution of this, in addition to light scattering effects were shown to control the devices photovoltaic efficiency of the devices; specifically when compared with ones employing commercially available TiO2 nanoparticles (either transparent or a bilayer structure with a transparent layer and a scattering one). SANP photoanodes sensitized with D149 dye were found to be optimised at 10 µm, yielding photovoltaic conversion efficiencies of 6.9%, superior to for transparent or transparent + scattering films from the commercial source (5.6% and 5.9%, respectively). Further to this, an efficiency of 7.7% PCE was achieved using a SANP photoanode sensitized with N719 dye, with 7.2% seen for the transparent photoanode and 7.9% with a scattering layer. The high efficiencies of devices based on of SANP photoanode are attributed to the high dye loading capability in addition to good light scattering. A further point of interest is that even with the increased reactivity of the surface towards dye adsorption, we did not observe any significant increase in recombination with the redox mediator, presumably due to this increased dye loading providing better shielding.

Advances in Optical Based Turbidity Sensing Using LED Photometry (PEDD).

Turbidity is one of the primary metrics to determine water quality in terms of health and environmental concerns, however analysis typically takes place in centralized facilities, with samples periodically collected and transported there. Large scale autonomous deployments (WSNs) are impeded by both initial and per measurement costs. In this study we employ a Paired Emitter-Detector Diode (PEDD) technique to quantitatively measure turbidity using analytical grade calibration standards. Our PEDD approach compares favorably against more conventional photodiode-LED arrangements in terms of spectral sensitivity, cost, power use, sensitivity, limit of detection, and physical arrangement as per the ISO 7027 turbidity sensing standard. The findings show that the PEDD technique was superior in all aforementioned aspects. It is therefore more ideal for low-cost, low-power, IoT deployed sensors. The significance of these findings can lead to environmental deployments that greatly lower the device and per-measurement costs.

The effect of amorphous TiO2 in P25 on dye-sensitized solar cell performance.

P25 is one of the most widely used forms of titanium(iv) oxide (TiO2), routinely utilised in dye-sensitised solar cells (DSCs), where it is often employed as a control, in spite of its poorly defined nature and the typically low device efficiency (or possibly because of this). Work by Park in 2000 and later by Lin et al. suggests that the rutile component might not be to blame for this, as has often been claimed. Recently it has been observed that P25 has quite a sizable amorphous content. A method to selectively remove this non-crystalline material has been developed, allowing for scrutiny of the role this amorphous material plays. Here we compare hydrothermally treated P25 (H-P25) with the as-received material, realizing solar-to-electric conversion efficiencies of 5.3% and 3.2% respectively. More importantly, this reveals important information about the detrimental effect of amorphous TiO2 on DSC performance, with broader implications, as most researchers do not actively examine their synthesized materials for the presence of an amorphous component.

Aggregated mesoporous nanoparticles for high surface area light scattering layer TiO2 photoanodes in Dye-sensitized Solar Cells.

Hierarchically structured aggregates, consisting of TiO2 nanoparticles were produced via one-step solvothermal syntheses with a mixed solvent system containing both acetic acid and ethanol. Two of the resulting structures, one ~700 nm and the other ~300 nm in diameter, were found to be comprised of 8.5 nm and 10.5 nm anatase crystals, and possess specific surface areas of 138 and 106 m2 g-1 respectively. These particles were incorporated into Dye-sensitized Solar Cells (DSCs) as high surface area scattering layers, along with a layer of a transparent material. Solar-to-electric conversion efficiencies (PCE) of 9.1% and 8.2% were recorded using these aggregated particles as compared to those of commonly used large particles scattering layer 7.4%.

Composite Photocatalysts Containing BiVO4 for Degradation of Cationic Dyes.

The creation of composite structures is a commonly employed approach towards enhanced photocatalytic performance, with one of the key rationales for doing this being to separate photoexcited charges, affording them longer lifetimes in which to react with adsorbed species. Here we examine three composite photocatalysts using either WO3, TiO2 or CeO2 with BiVO4 for the degradation of model dyes Methylene Blue and Rhodamine B. Each of these materials (WO3, TiO2 or CeO2) has a different band edge energy offset with respect to BiVO4, allowing for a systematic comparison of these different arrangements. It is seen that while these offsets can afford beneficial charge transfer (CT) processes, they can also result in the deactivation of certain reactions. We also observed the importance of localized dye concentrations, resulting from a strong affinity between it and the surface, in attaining high overall photocatalytic performance, a factor not often acknowledged. It is hoped in the future that these observations will assist in the judicious selection of semiconductors for use as composite photocatalysts.

Understanding chemically processed solar cells based on quantum dots.

Photovoltaic energy conversion is one of the best alternatives to fossil fuel combustion. Petroleum resources are now close to depletion and their combustion is known to be responsible for the release of a considerable amount of greenhouse gases and carcinogenic airborne particles. Novel third-generation solar cells include a vast range of device designs and materials aiming to overcome the factors limiting the current technologies. Among them, quantum dot-based devices showed promising potential both as sensitizers and as colloidal nanoparticle films. A good example is the p-type PbS colloidal quantum dots (CQDs) forming a heterojunction with a n-type wide-band-gap semiconductor such as TiO2 or ZnO. The confinement in these nanostructures is also expected to result in marginal mechanisms, such as the collection of hot carriers and generation of multiple excitons, which would increase the theoretical conversion efficiency limit. Ultimately, this technology could also lead to the assembly of a tandem-type cell with CQD films absorbing in different regions of the solar spectrum.

Increased upconversion performance for thin film solar cells: a trimolecular composition.

Photochemical upconversion based on triplet-triplet annihilation (TTA-UC) is employed to enhance the short-circuit currents generated by two varieties of thin-film solar cells, a hydrogenated amorphous silicon (a-Si:H) solar cell and a dye-sensitized solar cell (DSC). TTA-UC is exploited to harvest transmitted sub-bandgap photons, combine their energies and re-radiate upconverted photons back towards the solar cells. In the present study we employ a dual-emitter TTA-UC system which allows for significantly improved UC quantum yields as compared to the previously used single-emitter TTA systems. In doing so we achieve record photo-current enhancement values for both the a-Si:H device and the DSC, surpassing 10-3 mA cm-2 sun-2 for the first time for a TTA-UC system and marking a record for upconversion-enhanced solar cells in general. We discuss pertinent challenges of the TTA-UC technology which need to be addressed in order to achieve its viable device application.

Trap-Assisted Transport and Non-Uniform Charge Distribution in Sulfur-Rich PbS Colloidal Quantum Dot-based Solar Cells with Selective Contacts.

This study reports evidence of dispersive transport in planar PbS colloidal quantum dot heterojunction-based devices as well as the effect of incorporating a MoO3 hole selective layer on the charge extraction behavior. Steady state and transient characterization techniques are employed to determine the complex recombination processes involved in such devices. The addition of a selective contact drastically improves the device efficiency up to 3.15% (especially due to increased photocurrent and decreased series resistance) and extends the overall charge lifetime by suppressing the main first-order recombination pathway observed in device without MoO3. The lifetime and mobility calculated for our sulfur-rich PbS-based devices are similar to previously reported values in lead-rich quantum dots-based solar cells. Nevertheless, strong Shockley-Read-Hall mechanisms appear to keep restricting charge transport, as the equilibrium voltage takes more than 1 ms to be established.

An intermediate band dye-sensitised solar cell using triplet-triplet annihilation.

A new mechanism of charge photogeneration is demonstrated for the first time, based on organic molecular structures. This intermediate band approach, integrated into a dye-sensitised solar cell configuration is shown to generate charges upon illumination with low energy photons. Specifically 610 nm photoexcitation of Pt porphyrins, through a series of energy transfer steps and triplet-triplet annihilation, excites a higher energy absorption onset molecule, which is then capable of charge injection into TiO2. Transient absorption measurements reveal further detail of the processes involved.

The effect of surface passivation on the structure of sulphur-rich PbS colloidal quantum dots for photovoltaic application.

The use of PbS colloidal quantum dots in photovoltaic devices is very promising because of their simple and low cost production processes and their unique properties, such as bandgap tunability and potential multiple exciton generation. Here we report the synthesis of PbS nanocrystals used for application in solar cells. The sulphur-rich nature of their surface appears to be caused by the exposure to ambient conditions. The use of methanol as medium during the ligand exchange process has a crucial role in the removal of native oleate ligands. Without proper ligand exchange, the unpassivated surface is subject to ambient hydroxylation leading to the depletion of Pb atoms and the formation of a polysulfide phase. Devices assembled with this material showed good performance with an efficiency of 3.2%.

N719- and D149-sensitized 3D hierarchical rutile TiO2 solar cells--a comparative study.

Poor dye loading on rutile TiO2 is one of the chief reasons for lower solar-to-electric conversion efficiency (η) in dye-sensitized solar cells (DSCs), compared to their anatase based counterparts. Previously, we showed that similar light harvesting for both rutile and anatase was realized by using a metal-free organic indoline dye, D149 [Sci. Rep., 2014, 4, 5769]. This was in contrast to the bulk of previous studies, which employed ruthenium based N719, leading to significant differences in light harvesting. To date, there has been no report directly comparing N719 and D149 for rutile based DSCs. In this work, three-dimensional hierarchical rutile TiO2 architecture (HRTA), consisting of one-dimensional nanorods, was successfully prepared via a facile hydrothermal method, and subsequently optimized as effective photoelectrodes for DSCs. Two dyes, N719 and D149, were used as sensitizers of the HRTA-based DSCs, with maximum η of 5.6% and 5.8% achieved, respectively. The higher η of the D149-sensitized DSC is ascribed to its higher extinction co-efficient, allowing a greater amount of light to be harvested with a thinner TiO2 layer. This study suggests that some of the limitations typically observed for rutile TiO2 based DSCs can be overcome through the use of strongly absorbing metal-free organic sensitizers. Furthermore, it reemphasises the importance of viewing DSCs as whole systems, rather than individual components.

Integrating a triplet-triplet annihilation up-conversion system to enhance dye-sensitized solar cell response to sub-bandgap light.

The poor response of dye-sensitized solar cells (DSCs) to red and infrared light is a significant impediment to the realization of higher photocurrents and hence higher efficiencies. Photon up-conversion by way of triplet-triplet annihilation (TTA-UC) is an attractive technique for using these otherwise wasted low energy photons to produce photocurrent, while not interfering with the photoanodic performance in a deleterious manner. Further to this, TTA-UC has a number of features, distinct from other reported photon up-conversion technologies, which renders it particularly suitable for coupling with DSC technology. In this work, a proven high performance TTA-UC system, comprising a palladium porphyrin sensitizer and rubrene emitter, is combined with a high performance DSC (utilizing the organic dye D149) in an integrated device. The device shows an enhanced response to sub-bandgap light over the absorption range of the TTA-UC sub-unit resulting in the highest figure of merit for up-conversion assisted DSC performance to date.

3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency.

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Enhanced visible-light photocatalytic activity of g-C3N4/TiO2 films.

Enhanced photocatalytic degradation of methylene blue (MB) using graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) catalyst films has been demonstrated in this present work. The g-C3N4/TiO2 composites were prepared by directly heating the mixture of melamine and pre-synthesized TiO2 nanoparticles in Ar gas flow. The g-C3N4 contents in the g-C3N4/TiO2 composites were varied as 0, 20, 50 and 70 wt%. It was found that the visible-light-induced photocatalytic degradation of MB was remarkably increased upon coupling TiO2 with g-C3N4 and the best degradation performance of ~70% was obtained from 50 wt% g-C3N4 loading content. Results from UV-vis absorption study, Electron microscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggest that the improved photoactivity is due to a decrease in band gap energy, an increased light absorption in visible light region and possibly an enhanced electron-hole separation efficiency as a result of effective interfacial electron transfer between TiO2 and g-C3N4 of the g-C3N4/TiO2 composite film. Based on the obtained results, the possible MB degradation mechanism is ascribed mainly to the generation of active species induced by the photogenerated electrons.

Carbon nanotube - reduced graphene oxide composites for thermal energy harvesting applications.

By controlling the SWNT-rGO electrode composition and thickness to attain the appropriate porosity and tortuosity, the electroactive surface area is maximized while rapid diffusion of the electrolyte through the electrode is maintained. This leads to an increase in exchange current density between the electrode and electrolyte which results in enhanced thermocell performance.