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Many journals in ecology and evolutionary biology encourage or require authors to make their data and code available alongside articles. In this study we investigated how often this data and code could be used together, when both were available, to computationally reproduce results published in articles. We surveyed the data and code sharing practices of 177 meta-analyses published in ecology and evolutionary biology journals published between 2015-17: 60% of articles shared data only, 1% shared code only, and 15% shared both data and code. In each of the articles which had shared both (n = 26), we selected a target result and attempted to reproduce it. Using the shared data and code files, we successfully reproduced the targeted results in 27-73% of the 26 articles, depending on the stringency of the criteria applied for a successful reproduction. The results from this sample of meta-analyses in the 2015-17 literature can provide a benchmark for future meta-research studies gauging the computational reproducibility of published research in ecology and evolutionary biology.
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Ecologia , Publicações , Reprodutibilidade dos Testes , Evolução BiológicaRESUMO
This paper explores judgements about the replicability of social and behavioural sciences research and what drives those judgements. Using a mixed methods approach, it draws on qualitative and quantitative data elicited from groups using a structured approach called the IDEA protocol ('investigate', 'discuss', 'estimate' and 'aggregate'). Five groups of five people with relevant domain expertise evaluated 25 research claims that were subject to at least one replication study. Participants assessed the probability that each of the 25 research claims would replicate (i.e. that a replication study would find a statistically significant result in the same direction as the original study) and described the reasoning behind those judgements. We quantitatively analysed possible correlates of predictive accuracy, including self-rated expertise and updating of judgements after feedback and discussion. We qualitatively analysed the reasoning data to explore the cues, heuristics and patterns of reasoning used by participants. Participants achieved 84% classification accuracy in predicting replicability. Those who engaged in a greater breadth of reasoning provided more accurate replicability judgements. Some reasons were more commonly invoked by more accurate participants, such as 'effect size' and 'reputation' (e.g. of the field of research). There was also some evidence of a relationship between statistical literacy and accuracy.
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Overcoming the sluggish electrode kinetics of both oxygen reduction and evolution reactions (ORR/OER) with non-precious metal electrocatalysts will accelerate the development of rechargeable metal-air batteries and regenerative fuel cells. The authors investigated the electrochemical behavior and ORR/OER catalytic activity of core-porous shell Mn/Mn3 O4 nanoparticles in comparison with other manganese dioxides (ß- and γ-MnO2 ), and benchmarked against Pt/C and Pt/C-IrO2 . Under reversible operation in O2 -saturated 5 M KOH at 22 °C, the early stage activity of core-shell Mn/Mn3 O4 shows two times higher ORR and OER current density compared to the other MnO2 structures at 0.32 and 1.62 V versus RHE, respectively. It is revealed that Mn(III) oxidation to Mn(IV) is the primary cause of Mn/Mn3 O4 activity loss during ORR/OER potential cycling. To address it, an electrochemical activation method using Co(II) is proposed. By incorporating Co(II) into MnOx , new active sites are introduced and the content of Mn(II) is increased, which can stabilize the Mn(III) sites through comproportionation with Mn(IV). The Co-incorporated Mn/Mn3 O4 has superior activity and durability. Furthermore, it also surpassed the activity of Pt/C-IrO2 with similar durability. This study demonstrates that cost-effective ORR/OER catalysis is possible.
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As replications of individual studies are resource intensive, techniques for predicting the replicability are required. We introduce the repliCATS (Collaborative Assessments for Trustworthy Science) process, a new method for eliciting expert predictions about the replicability of research. This process is a structured expert elicitation approach based on a modified Delphi technique applied to the evaluation of research claims in social and behavioural sciences. The utility of processes to predict replicability is their capacity to test scientific claims without the costs of full replication. Experimental data supports the validity of this process, with a validation study producing a classification accuracy of 84% and an Area Under the Curve of 0.94, meeting or exceeding the accuracy of other techniques used to predict replicability. The repliCATS process provides other benefits. It is highly scalable, able to be deployed for both rapid assessment of small numbers of claims, and assessment of high volumes of claims over an extended period through an online elicitation platform, having been used to assess 3000 research claims over an 18 month period. It is available to be implemented in a range of ways and we describe one such implementation. An important advantage of the repliCATS process is that it collects qualitative data that has the potential to provide insight in understanding the limits of generalizability of scientific claims. The primary limitation of the repliCATS process is its reliance on human-derived predictions with consequent costs in terms of participant fatigue although careful design can minimise these costs. The repliCATS process has potential applications in alternative peer review and in the allocation of effort for replication studies.
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Ciências do Comportamento , Confiabilidade dos Dados , Humanos , Reprodutibilidade dos Testes , Custos e Análise de Custo , Revisão por ParesRESUMO
The ever-increasing demand for flexible and portable electronics has stimulated research and development in building advanced electrochemical energy devices which are lightweight, ultrathin, small in size, bendable, foldable, knittable, wearable, and/or stretchable. In such flexible and portable devices, semi-solid/solid electrolytes besides anodes and cathodes are the necessary components determining the energy/power performances. By serving as the ion transport channels, such semi-solid/solid electrolytes may be beneficial to resolving the issues of leakage, electrode corrosion, and metal electrode dendrite growth. In this paper, the fundamentals of semi-solid/solid electrolytes (e.g., chemical composition, ionic conductivity, electrochemical window, mechanical strength, thermal stability, and other attractive features), the electrode-electrolyte interfacial properties, and their relationships with the performance of various energy devices (e.g., supercapacitors, secondary ion batteries, metal-sulfur batteries, and metal-air batteries) are comprehensively reviewed in terms of materials synthesis and/or characterization, functional mechanisms, and device assembling for performance validation. The most recent advancements in improving the performance of electrochemical energy devices are summarized with focuses on analyzing the existing technical challenges (e.g., solid electrolyte interphase formation, metal electrode dendrite growth, polysulfide shuttle issue, electrolyte instability in half-open battery structure) and the strategies for overcoming these challenges through modification of semi-solid/solid electrolyte materials. Several possible directions for future research and development are proposed for going beyond existing technological bottlenecks and achieving desirable flexible and portable electrochemical energy devices to fulfill their practical applications. It is expected that this review may provide the readers with a comprehensive cross-technology understanding of the semi-solid/solid electrolytes for facilitating their current and future researches on the flexible and portable electrochemical energy devices.
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Fontes de Energia Elétrica , Eletrólitos , Eletrodos , Eletrônica , SoftwareRESUMO
Nano-carbon-based materials are widely reported as lithium host materials in lithium metal batteries (LMBs); however, researchers report contradictory claims as to where the lithium plating occurs. Herein, the use of pure hollow core-carbon spheres coated on Cu (PHCCSs@Cu) to study the lithium deposition behavior with respect to this type of structure in lithium anode-free cells is described. It is demonstrated that the lithium showed some initial and limited intercalation into the PHCCSs and then plated on the external carbon walls and the top surface of the carbon coating during the charging process. The unfavorable deposition of lithium inside the PHCCSs is discussed from the viewpoint of lithium-ion transport and lithium nucleation. The application potential of PHCCSs and the data from these LMB studies are also discussed.
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In photocatalytic water splitting, fluidization is known to minimize the adverse effects of mass-transfer, poor radiation distribution, parasitic back-reactions and photocatalyst handling difficulties, which limit the scalability of immobilized-film and suspended slurry photocatalysts. Fluidization of one-dimensional TiO2 photocatalyst particles, such as nanorods, -wires and -ribbons, is highly desired as it further enhances the efficiency of photocatalytic reaction, due to their peculiar photo-electrochemical characteristics that result in more effective separation of photo-generated charges and absorption of photons. However, the harsh physical environment of a fluidized bed reactor does not readily allow for nanostructured TiO2 photocatalysts, as the fine features would be quickly removed from the particle surface. Here, we propose a scalable method for fabrication of rutile TiO2 nanorods on porous glass beads as a 3D protective substrate to reduce the attrition rate caused by fluidization. The quality of the synthesized nanorod films was optimized through controlling a growth quality factor, R q, allowing for good quality films to be grown in different batch amounts and different hydrothermal reactor sizes. The utilization of porous glass beads substrate has reduced the attrition rate, and the protective features of the particles reduced the rate of attrition by an order of magnitude, compared to a particulate photocatalyst, to near negligible levels. Such considerably reduced attrition makes the as-developed porous glass beads supported rutile TiO2 nanorods a viable fluidizable photocatalyst candidate for various applications, including water splitting and degradation of organic compounds.
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The Arctic is among the fastest-warming areas of the globe. Understanding the impact of climate change on foundational Arctic marine species is needed to provide insight on ecological resilience at high latitudes. Marine forests, the underwater seascapes formed by seaweeds, are predicted to expand their ranges further north in the Arctic in a warmer climate. Here, we investigated whether northern habitat gains will compensate for losses at the southern range edge by modelling marine forest distributions according to three distribution categories: cryophilic (species restricted to the Arctic environment), cryotolerant (species with broad environmental preferences inclusive but not limited to the Arctic environment), and cryophobic (species restricted to temperate conditions) marine forests. Using stacked MaxEnt models, we predicted the current extent of suitable habitat for contemporary and future marine forests under Representative Concentration Pathway Scenarios of increasing emissions (2.6, 4.5, 6.0, and 8.5). Our analyses indicate that cryophilic marine forests are already ubiquitous in the north, and thus cannot expand their range under climate change, resulting in an overall loss of habitat due to severe southern range contractions. The extent of marine forests within the Arctic basin, however, is predicted to remain largely stable under climate change with notable exceptions in some areas, particularly in the Canadian Archipelago. Succession may occur where cryophilic and cryotolerant species are extirpated at their southern range edge, resulting in ecosystem shifts towards temperate regimes at mid to high latitudes, though many aspects of these shifts, such as total biomass and depth range, remain to be field validated. Our results provide the first global synthesis of predicted changes to pan-Arctic coastal marine forest ecosystems under climate change and suggest ecosystem transitions are unavoidable now for some areas.
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Mudança Climática , Ecossistema , Regiões Árticas , Canadá , FlorestasRESUMO
Accumulation of water at the interface of the cathode catalyst layer (CCL) and the diffusion media is a major cause of performance loss in H2/air fuel cells. Proper engineering of the interface by the use of advanced materials and preparation methods can effectively reduce the extent of this loss by improving the transport of water and gas across this interface. Herein, we present detailed modeling results of water and gas transport across this interface for in-house synthesized carbon material with multiple levels of porosity and by considering the interfacial properties of the carbon material and the microporous layer (MPL). The oxygen reduction reaction and the counter-flow transport of oxygen and water within the CCL and MPL pores were modeled considering a partially flooded interface. Well-characterized multimodal porous carbon was chosen as a candidate material for this study, and the effects of all the various levels of porosity in the MPL, wettability, permeability, and the quality of contact between the MPL and CCL on the transport phenomena of fluids were investigated. This study provides new insights into the balance of opposing transport phenomena on the local and overall performance of the catalyst layer and rationalizes the design parameters for an MPL material based on both the material and interfacial properties.
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An innovative strategy is presented to engineer supported-Pt nanowire (NW) electrocatalysts with a high Pt content for the cathode of hydrogen fuel cells. This involves deposition of graphitic carbon nitride (g-CN) onto 3D multimodal porous carbon (MPC) (denoted as g-CN@MPC) and using the g-CN@MPC as an electrocatalyst support. The protective coating of g-CN on the MPC provides good stability for the electrocatalyst support against electrochemical oxidation, and also enhances oxygen adsorption and provides additional active sites for the oxygen reduction reaction. Compared with commercial carbon black Vulcan XC-72R (denoted as VC) support material, the larger hydrophobic surface area of the g-CN@MPC enables the supported high-content Pt NWs to disperse uniformly on the support. In addition, the unique 3D interconnected pore networks facilitate improved mass transport within the g-CN@MPC support material. As a result, the g-CN@MPC-supported high-content Pt catalysts show improved performance with respect to their counterparts, namely, MPC, VC, and g-CN@VC-supported Pt NW catalysts and the conventional Pt nanoparticle (NP) catalyst (i.e., Pt(20 wt%)NPs/VC (Johnson Matthey)) used as the benchmark. More importantly, the g-CN-tailored high-content Pt NW (≈60 wt%) electrocatalyst demonstrates high PEM fuel cell power/performance at a very low cathode catalyst loading (≈0.1 mgPt cm-2 ).
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Unreliable research programmes waste funds, time, and even the lives of the organisms we seek to help and understand. Reducing this waste and increasing the value of scientific evidence require changing the actions of both individual researchers and the institutions they depend on for employment and promotion. While ecologists and evolutionary biologists have somewhat improved research transparency over the past decade (e.g. more data sharing), major obstacles remain. In this commentary, we lift our gaze to the horizon to imagine how researchers and institutions can clear the path towards more credible and effective research programmes.
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Evolução Biológica , EcossistemaRESUMO
Adoption of proton exchange membrane (PEM) water electrolysis technology on a global level will demand a significant reduction of today's iridium loadings in the anode catalyst layers of PEM electrolyzers. However, new catalyst and electrode designs with reduced Ir content have been suffering from limited stability caused by (electro)chemical degradation. This has remained a serious impediment to a wider commercialization of larger-scale PEM electrolysis technology. In this combined DFT computational and experimental study, we investigate a novel family of iridium-niobium mixed metal oxide thin-film catalysts for the oxygen evolution reaction (OER), some of which exhibit greatly enhanced stability, such as minimized voltage degradation and reduced Ir dissolution with respect to the industry benchmark IrOx catalyst. More specifically, we report an unusually durable IrNbOx electrocatalyst with improved catalytic performance compared to an IrOx benchmark catalyst prepared in-house and a commercial benchmark catalyst (Umicore Elyst Ir75 0480) at significantly reduced Ir catalyst cost. Catalyst stability was assessed by conventional and newly developed accelerated degradation tests, and the mechanistic origins were analyzed and are discussed. To achieve this, the IrNbOx mixed metal oxide catalyst and its water splitting kinetics were investigated by a host of techniques such as synchrotron-based NEXAFS analysis and XPS, electrochemistry, and ab initio DFT calculations as well as STEM-EDX cross-sectional analysis. These analyses highlight a number of important structural differences to other recently reported bimetallic OER catalysts in the literature. On the methodological side, we introduce, validate, and utilize a new, nondestructive XRF-based catalyst stability monitoring technique that will benefit future catalyst development. Furthermore, the present study identifies new specific catalysts and experimental strategies for stepwise reducing the Ir demand of PEM water electrolyzers on their long way toward adoption at a larger scale.
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High temperature proton exchange membrane fuel cells (HT-PEMFCs) are one type of promising energy device with the advantages of fast reaction kinetics (high energy efficiency), high tolerance to fuel/air impurities, simple plate design, and better heat and water management. They have been expected to be the next generation of PEMFCs specifically for application in hydrogen-fueled automobile vehicles and combined heat and power (CHP) systems. However, their high-cost and low durability interposed by the insufficient performance of key materials such as electrocatalysts and membranes at high temperature operation are still the challenges hindering the technology's practical applications. To develop high performance HT-PEMFCs, worldwide researchers have been focusing on exploring new materials and the related technologies by developing novel synthesis methods and innovative assembly techniques, understanding degradation mechanisms, and creating mitigation strategies with special emphasis on catalysts for oxygen reduction reaction, proton exchange membranes and bipolar plates. In this paper, the state-of-the-art development of HT-PEMFC key materials, components and device assembly along with degradation mechanisms, mitigation strategies, and HT-PEMFC based CHP systems is comprehensively reviewed. In order to facilitate further research and development of HT-PEMFCs toward practical applications, the existing challenges are also discussed and several future research directions are proposed in this paper.
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Three spectrophotometric methods have been developed and compared for the quantification of low concentrations (0.03-63 µM) of aqueous permanganate in neutral pH conditions. Although permanganate is a widely used oxidant in drinking water and wastewater treatment, no widely accepted method of quantification has been reported to date. While one method presented does not require the need for any reagent chemicals (direct spectrophotometric analysis), it yielded a relatively low molar absorption coefficient of 3340 M-1 cm-1 at 525 nm and a level of detection (LOD) and quantification (LOQ) of 0.45 and 1.51 µM, respectively. Some instability of permanganate species during direct quantification was found to occur over 60 min, with a total decrease of 0.002 (arbitrary units) of absorbance, equivalent to a decrease in concentration of 0.6 µM. Beyond 60 min, no further degradation was observed. Indirect spectrophotometric analyses using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and sodium iodide (NaI) provided a significantly more sensitive method for permanganate quantification, yielding molar absorption coefficients of 140,030 and 61,130 M-1 cm-1, respectively. The LOD and LOQ were determined to be 0.01 and 0.03 µM for the ABTS method and 0.02 and 0.08 µM for the NaI method, respectively. Although conservative and accurate limits of quantification for both the ABTS and NaI methods are presented, which should be sufficient of most practical applications, lower limits may be possible with further refinement of the methods.
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Compostos de Manganês/análise , Óxidos/análise , Espectrofotometria/métodos , Águas Residuárias/química , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Concentração de Íons de Hidrogênio , Indicadores e Reagentes , Limite de Detecção , Padrões de Referência , Espectrofotometria/instrumentaçãoRESUMO
Electrocoagulation is a burgeoning technology now being considered for niche water treatment applications. Although much research has been conducted to determine the efficacy of electrocoagulation to remove various contaminants, the more fundamental electrochemical aspects of the technology are often overlooked. This research provides insight into the fundamental relationship of water flow, electrochemical metal dissolution and current density distribution through computational fluid dynamic (CFD) models, mathematical models and in-situ current density distribution identification experiments. Theoretically, it was determined that current distributed along the electrode was inversely proportional to the water flowrate. The turbulent flow through the EC reactor was simulated with varying inter-electrode gaps and flowrates, while the average velocity segments across the electrode surface was calculated, corresponding to the same segments used to experimentally determine the current distribution. Through the CFD models and current distribution determining technique, it was observed that current density was distributed unevenly and followed the trend predicted by theory. Areas of lower current density were generally accompanied by higher velocity flow. More uniform current was yielded with larger inter-electrode gaps, due to the greater flow uniformity. While operating with a 1 mm gap, the current and water velocity varied across the electrode by Δ27.6 mA/cm2 and Δ0.220 m/s, and was minimized to Δ3.6 mA/cm2 and Δ0.062 m/s at a 10 mm gap. Although current uniformity was increased, the overall current density decreased significantly due to the greater ohmic resistance associated with the larger gap. The removal of natural organic matter was reduced as much as 79% when the inter-electrode gap was reduced from 10 to 1 mm.
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Água Potável , Purificação da Água , Eletrocoagulação , Eletrodos , Concentração de Íons de Hidrogênio , Eliminação de Resíduos LíquidosRESUMO
The efficacy of electrocoagulation at a pilot-scale as an alternative drinking water treatment technology to conventional coagulation is explored. A novel reactor was integrated into a pilot plant at the surface water supply of a small, remote community. Using iron anodes, the effect of metal loading (ML), current density and inter-electrode gap on the reduction of natural organic matter (NOM) was studied. Dissolved organics were characterized by large fractions of low molecular weight (<750â Da) hydrophilic carbon structures with lower charge density. A greater reduction in UV254 was yielded compared to dissolved organic carbon, indicating better removal of larger molecular weight fractions of NOM. As ML dosages increased from 27.8 to 60.8â mg/L, specific ultraviolet absorbance decreased from 1.92 ± 0.14 to 1.60 ± 0.10â L/mâ¢mg respectively, from an initial raw water value of 2.21â L/mâ¢mg. No clear trend was observed for the effect of current density and inter-electrode gap for NOM, however ML was the primary variable dictating the process' effectiveness. Energy requirements were observed to vary greatly and were highly dependent on ML, current density and inter-electrode gap; variables that all effect the operating potential and resistance. In general, conditions that yielded the greatest reduction of NOM, a 1â mm gap and 4-cell configuration, had energy requirements between 0.480 and 0.602â kWh/m3 of water treated.
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Ferro , Purificação da Água , Carbono , Eletrocoagulação , Abastecimento de ÁguaRESUMO
Chemically-prepared MnO2 containing a highly crystalline ramsdellite phase was tested as a cathode material in aqueous Zn-salt (ZnSO4 and Zn(CF3SO3)2) based electrolytes for the first time. This aqueous MnO2/Zn cell has shown excellent performance and reversibility, retaining ≈65% of its initial capacity for more than 1000 cycles. The charge storage mechanism is complex and includes a ramsdellite/tetragonal spinel two-phase reaction.
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A proof-of-concept for the fabrication of genetically customizable biogenic materials for photovoltaic applications is presented. E. coli is first genetically engineered to heterologously express the carotenoid biosynthetic pathway from plants. This modification yields a strain that overproduces the photoactive pigment lycopene. The pigment-producing cells are then coated with TiO2 nanoparticles via a tryptophan-mediated supramolecular interface, and subsequent incorporation of the resulting biogenic material (cells@TiO2 ) as an anode in an I- /I3- -based dye-sensitized solar cell yields an excellent photovoltaic (PV) response. This work lays strong foundations for the development of bio-PV materials and next-generation organic optoelectronics that are green, inexpensive, and easy to manufacture.
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Materiais Biocompatíveis/química , Energia Solar , Eletroquímica , Escherichia coli/efeitos dos fármacos , Escherichia coli/metabolismo , Escherichia coli/ultraestrutura , Licopeno/análise , Titânio/farmacologia , Difração de Raios XRESUMO
An innovative Pt-free counter electrode was developed through which an electrolyte solution could be circulated in dye-sensitized solar cells (DSCs) to facilitate mass transfer, resulting in greatly suppressed charge recombination and a considerably enhanced electron lifetime, and accordingly much higher power conversion efficiency than a DSC with a stationary electrolyte.