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The carbon dioxide and carbon monoxide electroreduction reactions, when powered using low-carbon electricity, offer pathways to the decarbonization of chemical manufacture1,2. Copper (Cu) is relied on today for carbon-carbon coupling, in which it produces mixtures of more than ten C2+ chemicals3-6: a long-standing challenge lies in achieving selectivity to a single principal C2+ product7-9. Acetate is one such C2 compound on the path to the large but fossil-derived acetic acid market. Here we pursued dispersing a low concentration of Cu atoms in a host metal to favour the stabilization of ketenes10-chemical intermediates that are bound in monodentate fashion to the electrocatalyst. We synthesize Cu-in-Ag dilute (about 1 atomic per cent of Cu) alloy materials that we find to be highly selective for acetate electrosynthesis from CO at high *CO coverage, implemented at 10 atm pressure. Operando X-ray absorption spectroscopy indicates in situ-generated Cu clusters consisting of <4 atoms as active sites. We report a 12:1 ratio, an order of magnitude increase compared to the best previous reports, in the selectivity for acetate relative to all other products observed from the carbon monoxide electroreduction reaction. Combining catalyst design and reactor engineering, we achieve a CO-to-acetate Faradaic efficiency of 91% and report a Faradaic efficiency of 85% with an 820-h operating time. High selectivity benefits energy efficiency and downstream separation across all carbon-based electrochemical transformations, highlighting the importance of maximizing the Faradaic efficiency towards a single C2+ product11.
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CO2 electrolyzers have progressed rapidly in energy efficiency and catalyst selectivity toward valuable chemical feedstocks and fuels, such as syngas, ethylene, ethanol, and methane. However, each component within these complex systems influences the overall performance, and the further advances needed to realize commercialization will require an approach that considers the whole process, with the electrochemical cell at the center. Beyond the cell boundaries, the electrolyzer must integrate with upstream CO2 feeds and downstream separation processes in a way that minimizes overall product energy intensity and presents viable use cases. Here we begin by describing upstream CO2 sources, their energy intensities, and impurities. We then focus on the cell, the most common CO2 electrolyzer system architectures, and each component within these systems. We evaluate the energy savings and the feasibility of alternative approaches including integration with CO2 capture, direct conversion of flue gas and two-step conversion via carbon monoxide. We evaluate pathways that minimize downstream separations and produce concentrated streams compatible with existing sectors. Applying this comprehensive upstream-to-downstream approach, we highlight the most promising routes, and outlook, for electrochemical CO2 reduction.
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The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources1. However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge2. Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity3-5, and this has recently been explored for the reaction on copper by controlling morphology6, grain boundaries7, facets8, oxidation state9 and dopants10. Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far9), resulting in a low energy efficiency. Here we present a molecular tuning strategy-the functionalization of the surface of electrocatalysts with organic molecules-that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums11, adsorbed on copper. We find that the adhered molecules improve the stabilization of an 'atop-bound' CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.
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Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M' = Ru and Mâ³ = Ni in the bimetallic two-dimensional M'2(OAc)4Mâ³(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of -2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.
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Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.
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Acidic water electrolysis enables the production of hydrogen for use as a chemical and as a fuel. The acidic environment hinders water electrolysis on non-noble catalysts, a result of the sluggish kinetics associated with the adsorbate evolution mechanism, reliant as it is on four concerted proton-electron transfer steps. Enabling a faster mechanism with non-noble catalysts will help to further advance acidic water electrolysis. Here, we report evidence that doping Ba cations into a Co3O4 framework to form Co3-xBaxO4 promotes the oxide path mechanism and simultaneously improves activity in acidic electrolytes. Co3-xBaxO4 catalysts reported herein exhibit an overpotential of 278 mV at 10 mA/cm2 in 0.5 M H2SO4 electrolyte and are stable over 110 h of continuous water oxidation operation. We find that the incorporation of Ba cations shortens the Co-Co distance and promotes OH adsorption, findings we link to improved water oxidation in acidic electrolyte.
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Phase change materials that leverage the latent heat of solid-liquid transition have many applications in thermal energy transport and storage. When employed as particles within a carrier fluid, the resulting phase change slurries (PCSs) could outperform present-day single-phase working fluidsâprovided that viscous losses can be minimized. This work investigates the rheological behavior of encapsulated and nonencapsulated phase change slurries (PCSs) for applicability in flowing thermal energy systems. The physical and thermal properties of the PCS candidates, along with their rheological behavior, are investigated below and above their phase transition points at shear rates of 1-300 s-1, temperatures of 20-80 °C, and concentrations of 15-37.5 wt %. The effect of shell robustness and melting on local shear thickening and global shear thinning is discussed, followed by an analysis of the required pumping power. A hysteresis analysis is performed to test the transient response of the PCS under a range of shear rates. We assess the complex viscoelastic behavior by employing oscillatory flow tests and by delineating the flow indicesâflow consistency index (K) and flow behavior index (n). We identify a viscosity limit of 0.1 Pa·s for optimal thermal performance in high-flow applications such as renewable geothermal energy.
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Clinical semen quality assessment is critical to the treatment of infertility. Sperm DNA integrity testing provides critical information that can steer treatment and influence outcomes and offspring health. Flow cytometry is the gold standard approach to assess DNA integrity, but it is not commonly applied at the clinical level. The sperm chromatin dispersion (SCD) assay provides a simpler and cheaper alternative. However, SCD is low-throughput and non-quantitative - sperm assessment is serial, manual and suffers inter- and intra-observer variations. Here, an automated SCD analysis method is presented that enables quantitative sperm DNA quality assessment at the single-cell and population levels. Levering automated optical microscopy and a chromatin diffusion-based analysis, a sample of thousands of sperm that would otherwise require 5 hours is assessed in under 10 minutes - a clinically viable workflow. The sperm DNA diffusion coefficient (DDNA) measurement correlates (R2 = 0.96) with DNA fragmentation index (DFI) from the cytometry-based sperm chromatin structure assay (SCSA). The automated measurement of population-level sperm DNA fragmentation (% sDF) prevents inter-observer variations and shows a good agreement with the SCSA % DFI (R2 = 0.98). This automated approach standardizes and accelerates SCD-based sperm DNA analysis, enabling the clinical application of sperm DNA integrity assessment.
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Análise do Sêmen , Sêmen , Masculino , Humanos , Análise do Sêmen/métodos , Espermatozoides , DNA/genética , DNA/análise , Cromatina/genética , Fragmentação do DNARESUMO
We now know that nanoplastics can harm aquatic organisms, but understanding ecological risk starts with understanding fate. We coupled population balance and fugacity models to predict the conditions under which nanoplastics remain as single particles, aggregate, or sediment and to predict their capacity to concentrate organic pollutants. We carried out simulations across a broad range of nanoplastic concentrations, particle sizes, and particle-particle interactions under a range of salinity and organic matter conditions. The model predicts that across plastic materials and environmental conditions, nanoplastics will either remain mostly dispersed or settle as aggregates with natural colloids. Nanoplastics of different size classes respond dissimilarly to concentration, ionic strength, and organic matter content, indicating that the sizes of nanoplastics to which organisms are exposed likely shift across ecological zones. We implemented a fugacity model of the Great Lakes to assess the organic pollution payload carried by nanoplastics, generating the expectation that nanoplastics would carry nine times more pollutants than microsized plastics and a threshold concentration of 10 µg/L at which they impact pollutant distribution. Our simulations across a broad range of factors inform future experimentation by highlighting the relative importance of size, concentration, material properties, and interactions in driving nanoplastic fate in aquatic environments.
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Microplásticos , Poluentes Químicos da Água , Organismos Aquáticos , Tamanho da Partícula , Plásticos , Salinidade , Poluentes Químicos da Água/análiseRESUMO
Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.
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Anthropogenic stressors can affect individual species and alter species interactions. Moreover, species interactions or the presence of multiple stressors can modify the stressor effects, yet most work focuses on single stressors and single species. Plant-microbe interactions are a class of species interactions on which ecosystems and agricultural systems depend, yet may be affected by multiple global change stressors. Here, we use duckweed and microbes from its microbiome to model responses of interacting plants and microbes to multiple stressors: climate change and tire wear particles. Climate change is occurring globally, and microplastic tire wear particles from roads now reach many ecosystems. We paired perpendicular gradients of temperature and carbon dioxide (CO2) treatments with factorial manipulation of leachate from tire wear particles and duckweed microbiomes. We found that tire leachate and warmer temperatures enhanced duckweed and microbial growth, but caused effects of microbes on duckweed to become negative. However, induced negative effects of microbes were less than additive with warming and leachate. Without tire leachate, we observed that higher CO2 and temperature induced positive correlations between duckweed and microbial growth, which can strengthen mutualisms. In contrast, with tire leachate, growth correlations were never positive, and shifted negative at lower CO2, again suggesting leachate disrupts this plant-microbiome mutualism. In summary, our results demonstrate that multiple interacting stressors can affect multiple interacting species, and that leachate from tire wear particles could potentially disrupt plant-microbe mutualisms.
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Microbiota , Microplásticos , Efeitos Antropogênicos , Dióxido de Carbono , Mudança Climática , Plásticos , Simbiose , TemperaturaRESUMO
Nanofluidics is the study of fluids under nanoscale confinement, where small-scale effects dictate fluid physics and continuum assumptions are no longer fully valid. At this scale, because of large surface-area-to-volume ratios, the fluid interaction with boundaries becomes more pronounced, and both short-range steric/hydration forces and long-range van der Waals forces and electrostatic forces dictate fluid behavior. These forces lead to a spectrum of anomalous transport and thermodynamic phenomena such as ultrafast water flow, enhanced ion transport, extreme phase transition temperatures, and slow biomolecule diffusion, which have been the subject of extensive computational studies. Experimental quantification of these phenomena was also enabled by the advent of nanofluidic technology, which has transformed challenging nanoscale fluid measurements into facile optical and electrical recordings. Our groups' focus is to investigate nanoscale (2 to 103 nm) fluid behaviors in the context of fluid mechanics and thermodynamics through the development of novel nanofluidic tools, to examine the applicability of classical equations at the nanoscale, to identify the source of deviations, and to explore new physics emerging at this scale. In this Account, we summarize our recent findings regarding liquid transport, vaporization, and condensation of nanoscale-confined liquids. Our study of nanoscale water transport identified an additional resistance in hydrophilic nanochannels, attributed to the reduced cross-sectional area caused by the formation of an immobile hydration layer on the surfaces. In contrast, a reduction in flow resistance was discovered in graphene-coated hydrophobic nanochannels, due to water slippage on the graphene surface. In the context of vaporization, the kinetic-limited evaporation flux was measured and found to exceed the classical theoretical prediction by an order of magnitude in hydrophilic nanochannels/nanopores as a result of the thin film evaporation outside of the apertures. This factor was eliminated by modifying the hydrophobicity of the aperture's exterior surface, enabling the identification of the true kinetic limits inside nanoconfinements and a crucial confinement-dependent evaporation coefficient. The transport-limited evaporation dynamics was also quantified, where experimental results confirmed the parallel diffusion-convection resistance model in both single nanoconduits and nanoporous systems at high accuracy. Furthermore, we have extended our studies to different aspects of condensation in nanoscale-confined spaces. The initiation of condensation for a single-component hydrocarbon was observed to follow the Kelvin equation, whereas for hydrocarbon mixtures it deviated from classical theory because of surface-selective adsorption, which has been corroborated by simulations. Moreover, the condensation dynamics deviates from the bulk and is governed by either vapor transport or liquid transport depending on the confinement scale. Overall, by using novel nanofluidic devices and measurement strategies, our work explores and further verifies the applicability of classical fluid mechanics and thermodynamic equations such as the Navier-Stokes, Kelvin, and Hertz-Knudsen equations at the nanoscale. The results not only deepen our understanding of the fundamental physical phenomena of nanoscale fluids but also have important implications for various industrial applications such as water desalination, oil extraction/recovery, and thermal management. Looking forward, we see tremendous opportunities for nanofluidic devices in probing and quantifying nanoscale fluid thermophysical properties and more broadly enabling nanoscale chemistry and materials science.
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The electroreduction of carbon dioxide (CO2RR) to valuable chemicals is a promising avenue for the storage of intermittent renewable electricity. Renewable methane, obtained via CO2RR using renewable electricity as energy input, has the potential to serve as a carbon-neutral fuel or chemical feedstock, and it is of particular interest in view of the well-established infrastructure for its storage, distribution, and utilization. However, CO2RR to methane still suffers from low selectivity at commercially relevant current densities (>100 mA cm-2). Density functional theory calculations herein reveal that lowering *CO2 coverage on the Cu surface decreases the coverage of the *CO intermediate, and then this favors the protonation of *CO to *CHO, a key intermediate for methane generation, compared to the competing step, C-C coupling. We therefore pursue an experimental strategy wherein we control local CO2 availability on a Cu catalyst by tuning the concentration of CO2 in the gas stream and regulate the reaction rate through the current density. We achieve as a result a methane Faradaic efficiency (FE) of (48 ± 2)% with a partial current density of (108 ± 5) mA cm-2 and a methane cathodic energy efficiency of 20% using a dilute CO2 gas stream. We report stable methane electrosynthesis for 22 h. These findings offer routes to produce methane with high FE and high conversion rate in CO2RR and also make direct use of dilute CO2 feedstocks.
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Electrochemical conversion of nitrate (NO3-) into ammonia (NH3) recycles nitrogen and offers a route to the production of NH3, which is more valuable than dinitrogen gas. However, today's development of NO3- electroreduction remains hindered by the lack of a mechanistic picture of how catalyst structure may be tuned to enhance catalytic activity. Here we demonstrate enhanced NO3- reduction reaction (NO3-RR) performance on Cu50Ni50 alloy catalysts, including a 0.12 V upshift in the half-wave potential and a 6-fold increase in activity compared to those obtained with pure Cu at 0 V vs reversible hydrogen electrode (RHE). Ni alloying enables tuning of the Cu d-band center and modulates the adsorption energies of intermediates such as *NO3-, *NO2, and *NH2. Using density functional theory calculations, we identify a NO3-RR-to-NH3 pathway and offer an adsorption energy-activity relationship for the CuNi alloy system. This correlation between catalyst electronic structure and NO3-RR activity offers a design platform for further development of NO3-RR catalysts.
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While the combined presence of global climate change and nanosized plastic particle (i.e., nanoplastic) pollution is clear, the potential for interactions between climate-change-shifting environmental parameters and nanoplastics is largely unknown. Here, we aim to understand how nanoplastics will affect species in concert with climate change in freshwater ecosystems. We utilized a high-throughput full-factorial experimental system and the model photosynthetic microorganism Scenedesmus obliquus to capture the complexity of interacting environmental stressors, including CO2, temperature, light, and nanoplastics. Under a massive number of conditions (2000+), we consistently found concentration-dependent inhibition of algal growth in the presence of polystyrene nanoparticles, highlighting a threat to primary productivity in aquatic ecosystems. Our high-treatment experiment also identified crucial interactions between nanoplastics and climate change. We found that relatively low temperature and ambient CO2 exacerbated damage induced by nanoplastics, while elevated CO2 and warmer temperatures reflecting climate change scenarios somewhat attenuated nanoplastic toxicity. Further, we revealed that nanoplastics may modulate light responses, implying that risks of nanoplastic pollution may also depend on local irradiation conditions. Our study highlights the coupled impacts of nanoplastics and climate change, as well as the value of full-factorial screening in predicting biological responses to multifaceted global change.
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Mudança Climática , Ecossistema , Água Doce , Plásticos , PoliestirenosRESUMO
Tire particles are of concern as a stressor due to the combination of their chemical constituents, high emission rates, and global distribution. Once in the environment, they will interact with physical parameters (e.g., UV, temperature). The interaction of chemical pollution with changing physical environmental parameters is often underestimated in ecotoxicology. Here, we investigate the role of temperature, mechanical stress (i.e., turbulence), UV, and CO2 on the effects of tire leachates on fish. Two samples of tire particles were exposed to four different levels of each physical stressor. A toxicological assessment was performed with fathead minnow embryos assessing five end points (hatching success, time to hatch, length, deformities, and heart rate). Results showed that variations of temperature and mechanical stress affect the toxicological impact of tire leachates. Zn and/or polycyclic aromatic hydrocarbons (pyrene, phenanthrene, chrysene, benzo[a]pyrene, anthracene, naphthalene, fluoranthene, and benzo[ghi]perylene) were identified in the leachate and tire samples by Raman/surface-enhanced Raman spectroscopy and gas chromatography with mass spectroscopy, respectively.
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Cyprinidae , Hidrocarbonetos Policíclicos Aromáticos , Animais , Cromatografia Gasosa , Ecotoxicologia , TemperaturaRESUMO
The electrochemical reduction of CO2 has seen many record-setting advances in C2 productivity in recent years. However, the selectivity for ethanol, a globally significant commodity chemical, is still low compared to the selectivity for products such as ethylene. Here we introduce diverse binding sites to a Cu catalyst, an approach that destabilizes the ethylene reaction intermediates and thereby promotes ethanol production. We develop a bimetallic Ag/Cu catalyst that implements the proposed design toward an improved ethanol catalyst. It achieves a record Faradaic efficiency of 41% toward ethanol at 250 mA/cm2 and -0.67 V vs RHE, leading to a cathodic-side (half-cell) energy efficiency of 24.7%. The new catalysts exhibit an in situ Raman spectrum, in the region associated with CO stretching, that is much broader than that of pure Cu controls, a finding we account for via the diversity of binding configurations. This physical picture, involving multisite binding, accounts for the enhanced ethanol production for bimetallic catalysts, and presents a framework to design multimetallic catalysts to control reaction paths in CO2 reductions toward desired products.
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Infectious diseases are a major global health issue. Diagnosis is a critical first step in effectively managing their spread. Paper-based microfluidic diagnostics first emerged in 2007 as a low-cost alternative to conventional laboratory testing, with the goal of improving accessibility to medical diagnostics in developing countries. In this review, we examine the advances in paper-based microfluidic diagnostics for medical diagnosis in the context of global health from 2007 to 2016. The theory of fluid transport in paper is first presented. The next section examines the strategies that have been employed to control fluid and analyte transport in paper-based assays. Tasks such as mixing, timing, and sequential fluid delivery have been achieved in paper and have enabled analytical capabilities comparable to those of conventional laboratory methods. The following section examines paper-based sample processing and analysis. The most impactful advancement here has been the translation of nucleic acid analysis to a paper-based format. Smartphone-based analysis is another exciting development with potential for wide dissemination. The last core section of the review highlights emerging health applications, such as male fertility testing and wearable diagnostics. We conclude the review with the future outlook, remaining challenges, and emerging opportunities.
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Técnicas e Procedimentos Diagnósticos/instrumentação , Dispositivos Lab-On-A-Chip , Papel , HumanosRESUMO
Microfibers, characterized as small fibers shed from textiles that are less than 5 mm in size, are a prominent contaminant in the environment. Thus, it is important that we have methods to accurately quantify and characterize them, including in water, sediment, wildlife, seafood, and drinking water samples. Unfortunately, their small size and the presence of different dyes on the microfibers themselves cause difficulties in identification via conventional spectroscopic methods of total attenuated resonance-Fourier transform infrared and Raman. To help solve some of these methodological challenges, we developed a new method employing polymer-dye binding chemistry, density tests, unique surface morphological traits, and fluorescent staining to identify microfibers in environmental samples. The identification method introduced here was tested in our laboratory via trials using microfibers shed from new textiles and environmental samples. We found that the method can be successfully applied to identify the different polymer types of microfibers, which can ultimately help source apportion microfiber contamination in the environment.
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Plásticos , Poluentes Químicos da Água , Têxteis , Águas Residuárias , ÁguaRESUMO
Over a broad range of operating conditions, many CO2 electroreduction catalysts can maintain selectivity toward certain reduction products, leading to materials and surfaces being categorized according to their products; here we ask, is product selectivity truly a property of the catalyst? Silver is among the best electrocatalysts for CO in aqueous electrolytes, where it reaches near-unity selectivity. We consider the hydrogenations of the oxygen and carbon atoms via the two proton-coupled-electron-transfer processes as chief determinants of product selectivity; and find using density functional theory (DFT) that the hydronium (H3O+) intermediate plays a key role in the first oxygen hydrogenation step and lowers the activation energy barrier for CO formation. When this hydronium influence is removed, the activation energy barrier for oxygen hydrogenation increases significantly, and the barrier for carbon hydrogenation is reduced. These effects make the formate reaction pathway more favorable than CO. Experimentally, we then carry out CO2 reduction in highly concentrated potassium hydroxide (KOH), limiting the hydronium concentration in the aqueous electrolyte. The product selectivity of a silver catalyst switches from entirely CO under neutral conditions to over 50% formate in the alkaline environment. The simulated and experimentally observed selectivity shift provides new insights into the role of hydronium on CO2 electroreduction processes and the ability for electrolyte manipulation to directly influence transition state (TS) kinetics, altering favored CO2 reaction pathways. We argue that selectivity should be considered less of an intrinsic catalyst property, and rather a combined product of the catalyst and reaction environment.