Unreported resistance in the charge transport limits the photoconversion efficiency of aqueous dye-sensitised solar cells: An electrochemical impedance spectroscopy study

In this work, a thorough electrochemical impedance spectroscopy study is performed of both liquid and polymeric aqueous dye-sensitized solar cells (a-DSSCs), which are also compared with conventional organic solvent-based devices. The main purpose is unveiling phenomena limiting the efficiency of water-based photovoltaics. Indeed, electrochemical impedance spectroscopy spectra of a-DSSCs show two peculiar (and unreported) features that are not observed in organic-based DSSCs. The higher frequency one (R45°) is likely associated with a slowdown of the diffusion kinetics of the redox mediator: it is due to the breakdown of the hydrogen-bond network of the aqueous environment, which was also supported by density functional theory calculations. The lower-frequency feature is associated with the additional amount of energy required for the breakdown at the semiconductor/FTO interface of the adducts between protons (coming from the solvent) and electrons localized in the TiO2 surface trap-states. This ‘disruption energy’ results in a resistive element (RIC) that inversely correlates with the device efficiency. Very interestingly, RIC depends on the applied potential and becomes negligible only at much more positive values than VOC. Tailored equivalent circuits implementing simultaneously R45° and RIC are currently under investigation

NiO/ZrO2nanocomposites as photocathodes of tandem DSCs with higher photoconversion efficiency with respect to parent single-photoelectrode p-DSCs

The nanocomposites of nickel oxide (NiO) and zirconia (ZrO2) (NZNCs) are particularly effective photocathodic materials in p-type dye-sensitized solar cells (p-DSCs) and tandem DSCs (t-DSCs). The t-DSCs obtained from P1-sensitized NZNC as photocathode and nanostructured titania (TiO2) sensitized with squaraine VG10-C8 as photoanode display overall efficiencies of ca. 2% at their best and, more importantly, produced photocurrents that surpassed systematically the values obtained from the parent devices having one photoelectrochemical interface. Such a finding is a consequence of the diminished resistance of the electrolyte the thickness of which is systematically smaller in t-DSCs with respect to parent DSCs with a single photoelectrochemical junction and same interelectrodic separation. The results here reported demonstrate that a careful combination of photoelectroactive electrodes can lead to an increase in current density of more than 15% in the t-DSC with respect to single-junction DSCs employing the same photoelectrodes provided that the whole thickness of the t-DSC is the same as in the single photoelectrode DSC and the photoelectrodes in the t-DSC do not incur in short-circuit phenomena through the electrolyte. For the successful realization of t-DSCs another important aspect is the complementarity of the absorption properties of the chosen colorants with the sensitized electrodes having similar absorbance in their respective ranges of optical absorption. The latter condition in t-DSCs makes possible the achievement of photoactivity spectra with a uniform efficiency of conversion in the whole visible range. For the attainment of efficient t-DSCs the two different photoelectrodes from parent DSCs (i.e. the devices at a single photoeletrochemical interface), should generate anodic and cathodic photocurrent densities with very similar values. Such a matching of photocurrents requires a careful selection of the thickness values for the photoelectrodes especially in case of materials with considerably different characteristics of charge injection. The approach here considered is a promising one for the assembly of quasi-transparent photoelectrochemical tandem devices operating as smart windows that convert light into electrical power

Evaluation of appendicitis risk prediction models in adults with suspected appendicitis

Background Appendicitis is the most common general surgical emergency worldwide, but its diagnosis remains challenging. The aim of this study was to determine whether existing risk prediction models can reliably identify patients presenting to hospital in the UK with acute right iliac fossa (RIF) pain who are at low risk of appendicitis. Methods A systematic search was completed to identify all existing appendicitis risk prediction models. Models were validated using UK data from an international prospective cohort study that captured consecutive patients aged 16–45 years presenting to hospital with acute RIF in March to June 2017. The main outcome was best achievable model specificity (proportion of patients who did not have appendicitis correctly classified as low risk) whilst maintaining a failure rate below 5 per cent (proportion of patients identified as low risk who actually had appendicitis). Results Some 5345 patients across 154 UK hospitals were identified, of which two‐thirds (3613 of 5345, 67·6 per cent) were women. Women were more than twice as likely to undergo surgery with removal of a histologically normal appendix (272 of 964, 28·2 per cent) than men (120 of 993, 12·1 per cent) (relative risk 2·33, 95 per cent c.i. 1·92 to 2·84; P < 0·001). Of 15 validated risk prediction models, the Adult Appendicitis Score performed best (cut‐off score 8 or less, specificity 63·1 per cent, failure rate 3·7 per cent). The Appendicitis Inflammatory Response Score performed best for men (cut‐off score 2 or less, specificity 24·7 per cent, failure rate 2·4 per cent). Conclusion Women in the UK had a disproportionate risk of admission without surgical intervention and had high rates of normal appendicectomy. Risk prediction models to support shared decision‐making by identifying adults in the UK at low risk of appendicitis were identified

Innovative and sustainable materials for aqueous dye-sensitized solar cells: a focus on photoanode/electrolyte interface

Emerging photovoltaic (PV) has evolved rapidly in the past decades and they are claiming their role as valuable alternatives to Silicon-based devices, especially for building integrated and indoor application. Among them, Dye-Sensitized Solar Cells (DSSCs) gained a leading role when diffuse and low-intensity light sources are used, approaching the Shockley-Quessier limit. Additionally, they are generally recognized as a sustainable technology. To further stress the sustainability claim and to improve the long-term stability of these device, the research recently focuses on water-based electrolytes (eventually jellified) leading to the development of aqueous DSSCs. Unfortunately, the improved sustainability is associated to lower photovoltaic performances compared to conventional devices. To improve light conversion efficiency, specifically designed materials should be designed and tested. Throughout this contribution, we summarized our recent effort in the fabrication and implementation of innovative photoanodes, electrolytes and sensitizers with a dedicated attention to the interplay between these components. Electrochemical Impedance Spectroscopy analyses allow us to highlight an unexpected behavior resulting in an additional resistance at the photoanode/electrolyte interface that could justify the lower performances of aqueous devices. Overall, we will show how much water-based photovoltaics represents a challenging topic in the current energy scenario, and how it will be able to provide sustainable solar cells for building-integrated photovoltaics, indoor applications and portable electronics

Innovative approaches toward fully sustainable Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs), have been thoroughly and extensively investigated in the last three decades, as a really promising emerging photovoltaic technology. Since their first appearance in 1991, DSSCs have gained increasing attention and have been classified as feasible alternatives to conventional photovoltaic devices due to their numerous advantages, such as cheap and simple preparation methods, the possibility of being integrated in buildings and astonishing performances under indoor and diffuse illumination conditions. Photoconversion efficiencies of up to 14% and 8% have been obtained for lab-scale devices and modules, respectively, under full illumination. Albeit the efforts made, these values seem arduous to be outdone. Nevertheless, recent lab-scale systems have demonstrated photoconversion efficiencies of up to 33% under indoor illumination (i.e. 1000 lux) leading to an actual Renaissance (or Revival) of these devices. It is worth mentioning that scientists in this field are developing innovative materials aiming at long-term and efficient devices, being the concept of sustainability often set apart. However, in light of effective commercialization of this technology, stability, efficiency and sustainability should be considered as the essential keywords beside efficiency. Indeed, nowadays, DSSCs are finding their “new way back” towards sustainability and a huge number of reports focused on the preparation of green and cost-effective materials to replace the standard ones. The present contribution aims to (i) give an overview of the most adopted strategies to enhance the sustainability of materials in classical DSSC components (i.e. sensitizer, redox couple, electrolyte and counter-electrode), including smart synthesis and deposition procedures and (ii) to stress the utmost importance of this concept in the design of the next generation of DSSC materials

Mapping the human genetic architecture of COVID-19

The genetic make-up of an individual contributes to the susceptibility and response to viral infection. Although environmental, clinical and social factors have a role in the chance of exposure to SARS-CoV-2 and the severity of COVID-191,2, host genetics may also be important. Identifying host-specific genetic factors may reveal biological mechanisms of therapeutic relevance and clarify causal relationships of modifiable environmental risk factors for SARS-CoV-2 infection and outcomes. We formed a global network of researchers to investigate the role of human genetics in SARS-CoV-2 infection and COVID-19 severity. Here we describe the results of three genome-wide association meta-analyses that consist of up to 49,562 patients with COVID-19 from 46 studies across 19 countries. We report 13 genome-wide significant loci that are associated with SARS-CoV-2 infection or severe manifestations of COVID-19. Several of these loci correspond to previously documented associations to lung or autoimmune and inflammatory diseases3–7. They also represent potentially actionable mechanisms in response to infection. Mendelian randomization analyses support a causal role for smoking and body-mass index for severe COVID-19 although not for type II diabetes. The identification of novel host genetic factors associated with COVID-19 was made possible by the community of human genetics researchers coming together to prioritize the sharing of data, results, resources and analytical frameworks. This working model of international collaboration underscores what is possible for future genetic discoveries in emerging pandemics, or indeed for any complex human disease

Mapping the human genetic architecture of COVID-19

The genetic make-up of an individual contributes to the susceptibility and response to viral infection. Although environmental, clinical and social factors have a role in the chance of exposure to SARS-CoV-2 and the severity of COVID-191,2, host genetics may also be important. Identifying host-specific genetic factors may reveal biological mechanisms of therapeutic relevance and clarify causal relationships of modifiable environmental risk factors for SARS-CoV-2 infection and outcomes. We formed a global network of researchers to investigate the role of human genetics in SARS-CoV-2 infection and COVID-19 severity. Here we describe the results of three genome-wide association meta-analyses that consist of up to 49,562 patients with COVID-19 from 46 studies across 19 countries. We report 13 genome-wide significant loci that are associated with SARS-CoV-2 infection or severe manifestations of COVID-19. Several of these loci correspond to previously documented associations to lung or autoimmune and inflammatory diseases3,4,5,6,7. They also represent potentially actionable mechanisms in response to infection. Mendelian randomization analyses support a causal role for smoking and body-mass index for severe COVID-19 although not for type II diabetes. The identification of novel host genetic factors associated with COVID-19 was made possible by the community of human genetics researchers coming together to prioritize the sharing of data, results, resources and analytical frameworks. This working model of international collaboration underscores what is possible for future genetic discoveries in emerging pandemics, or indeed for any complex human disease