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Organic-inorganic hybrid perovskites have electronic and optoelectronic properties that make them appealing in many device applications1-4. Although many approaches focus on polycrystalline materials5-7, single-crystal hybrid perovskites show improved carrier transport and enhanced stability over their polycrystalline counterparts, due to their orientation-dependent transport behaviour8-10 and lower defect concentrations11,12. However, the fabrication of single-crystal hybrid perovskites, and controlling their morphology and composition, are challenging12. Here we report a solution-based lithography-assisted epitaxial-growth-and-transfer method for fabricating single-crystal hybrid perovskites on arbitrary substrates, with precise control of their thickness (from about 600 nanometres to about 100 micrometres), area (continuous thin films up to about 5.5 centimetres by 5.5 centimetres), and composition gradient in the thickness direction (for example, from methylammonium lead iodide, MAPbI3, to MAPb0.5Sn0.5I3). The transferred single-crystal hybrid perovskites are of comparable quality to those directly grown on epitaxial substrates, and are mechanically flexible depending on the thickness. Lead-tin gradient alloying allows the formation of a graded electronic bandgap, which increases the carrier mobility and impedes carrier recombination. Devices based on these single-crystal hybrid perovskites show not only high stability against various degradation factors but also good performance (for example, solar cells based on lead-tin-gradient structures with an average efficiency of 18.77 per cent).
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The bifunctional oxygen electrocatalyst is the Achilles' heel of achieving robust reversible Zn-air batteries (ZABs). Herein, durable bifunctional oxygen electrocatalysis in alkaline media is realized on atomic Fe-N4-C sites reinforced by NixCo3-xO4 (NixCo3-xO4@Fe1/NC). Compared with that of pristine Fe1/NC, the stability of the oxygen evolution reaction (OER) is increased 10 times and the oxygen reduction reaction (ORR) performance is also improved. The steric hindrance alters the valence electron at the Fe-N4-C sites, resulting in a shorter Fe-N bond and enhanced stability of the Fe-N4-C sites. The corresponding solid-state ZABs exhibit an ultralong lifespan (>460 h at 5 mA cm-2) and high rate performance (from 2 to 50 mA cm-2). Furthermore, the structural evolution of NixCo3-xO4@Fe1/NC before and after the OER and ORR as well as charge-discharge cycling is explored. This work develops an efficient strategy for improving bifunctional oxygen electrocatalysis and possibly other processes.
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A visible-light induced dearomative cascade cyclization of biaryl ynones with diselenides under photocatalyst and external additive-free conditions has been explored, giving a series of selenated spiro[5.5]trienones in moderate to good yields. The Se-Se bond in diselenides could be cleaved to generate arylselenyl radicals under visible light irradiation in the absence of a photocatalyst. This protocol provides a facile and green method for the synthesis of spiro[5.5]trienones.
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Compostos de Espiro , Ciclização , Luz , Compostos de Espiro/químicaRESUMO
Stable ambulatory electrophysiological sensing is widely used for smart e-healthcare monitoring, clinical diagnosis of cardiovascular diseases, treatment of neurological diseases, and intelligent human-machine interaction. As the favorable signal interaction platform of electrophysiological sensing, the conformal property of on-skin electrodes is an extremely crucial factor that can affect the stability of long-term ambulatory electrophysiological sensing. From the perspective of materials, to realize conformal contact between electrodes and skin for stable sensing, highly conformal polymers are in great demand and attracting ever-growing attention. This review focuses on the recent progress of highly conformal polymers for ambulatory electrophysiological sensing, including their synthetic methods, conformal property, and potential applications. Specifically, three main types of highly conformal polymers for stable long-term electrophysiological signals monitoring are proposed, including nature silk fibroin based conformal polymers, marine mussels bioinspired conformal polymers, and other conformal polymers such as zwitterionic polymers and polyacrylamides. Furthermore, the future challenges and opportunities in preparing highly conformal polymers for on-skin electrodes are also highlighted.
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Fibroínas , Polímeros , Eletrodos , Humanos , PeleRESUMO
The International Agency of Research on Cancer identifies high-temperature frying, which features prominently in Chinese cooking, as producing group 2A carcinogens. This study simultaneously characterized particulate and gaseous-phase cooking emissions, monitored their reactive oxygen species (ROS) concentrations, and evaluated their impact on genetic damage and expression in exposed human bronchial epithelial cells. Five types of edible oil, three kinds of seasonings, and two dishes were assessed. Among tested edible oils, heating of soybean oil released the largest particle number concentration (2.09 × 1013 particles/(g cooking material and oil)·h) and volatile organic compounds (VOCs) emissions (12103.42 µg/(g cooking material and oil)·h). Heating of lard produced the greatest particle mass concentration (0.75 mg/(g cooking material and oil)·h). The main finding was that sunflower and rapeseed oils produced the highest ROS concentrations (80.48 and 71.75 nmol/(g cooking material and oil)·h, respectively). ROS formation most likely occurred during the autoxidation of both polyunsaturated and monounsaturated fatty acids. Among all the tested parameters, only ROS concentrations exhibited consistency with cell viability and showed significant correlations with the expression levels of CYP1A1, HIF-1a, and especially with IL-8 (the marker for oxidative stress within the cell). These findings indicate that ROS concentration is potentially a suitable metric for direct assessment of exposure levels and potential toxicity.
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Compostos Orgânicos Voláteis , Culinária , Células Epiteliais , Humanos , Óleos de Plantas , Espécies Reativas de Oxigênio , Compostos Orgânicos Voláteis/análise , Compostos Orgânicos Voláteis/toxicidadeRESUMO
Cooking fume produced by oil and food at a high temperature releases large amount of fine particulate matter (PM) which have a potential hazard to human health. This chamber study investigated particle emission characteristics originated from using four types of oil (soybean oil, olive oil, peanut oil and lard) and different kinds of food materials (meat and vegetable). The corresponding emission factors (EFs) of number, mass, surface area and volume for particles were discussed. Temporal variation of size-fractionated particle concentration showed that olive oil produced the highest number PM concentration for the entire cooking process. Multiple path particle dosimetry (MPPD) model was performed to predict deposition in the human respiratory tract. Results showed that the pulmonary airway deposition fraction was the largest. It was also found that particles produced from olive oil led to the highest deposition. We strongly recommend minimizing the moisture content of ingredients before cooking and giving priority to the use of peanut oil instead of olive oil to reduce human exposure to PM.
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Poluição do Ar em Ambientes Fechados/estatística & dados numéricos , Culinária/métodos , Monitoramento Ambiental , Exposição por Inalação/estatística & dados numéricos , Material Particulado/análise , Poluição do Ar em Ambientes Fechados/análise , China , Culinária/estatística & dados numéricos , HumanosRESUMO
Stretchable organic phototransistor arrays have potential applications in artificial visual systems due to their capacity to perceive ultraweak light across a broad spectrum. Ensuring uniform mechanical and electrical performance of individual devices within these arrays requires semiconductor films with large-area scale, well-defined orientation, and stretchability. However, the progress of stretchable phototransistors is primarily impeded by their limited electrical properties and photodetection capabilities. Herein, wafer-scale and well-oriented semiconductor films were successfully prepared using a solution shearing process. The electrical properties and photodetection capabilities were optimized by improving the polymer chain alignment. Furthermore, a stretchable 10 × 10 transistor array with high device uniformity was fabricated, demonstrating excellent mechanical robustness and photosensitive imaging ability. These arrays based on highly stretchable and well-oriented wafer-scale semiconductor films have great application potential in the field of electronic eye and artificial visual systems.
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The unsatisfactory adsorption and activation of CO2 suppress electrochemical reduction over a wide potential window. Herein, the built-in electric field (BIEF) at the CeO2/In2O3 n-n heterostructure realizes the C1 (CO and HCOO-) selectivity over 90.0% in a broad range of potentials from -0.7 to -1.1 V with a maximum value of 98.7 ± 0.3% at -0.8 V. In addition, the C1 current density (-1.1 V) of the CeO2/In2O3 heterostructure with a BIEF is about 2.0- and 3.2-fold that of In2O3 and a physically mixed sample, respectively. The experimental and theoretical calculation results indicate that the introduction of CeO2 triggered the charge redistribution and formed the BIEF at the interfaces, which enhanced the interfacial adsorption and activation of CO2 at low overpotentials. Furthermore, the promoting effect was also extended to CeO2/In2S3. This work gives a deep understanding of BIEF engineering for highly efficient CO2 electroreduction over a wide potential window.
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This work reports new analytic free in-plane vibration solutions for orthotropic non-Lévy-type rectangular plates, i.e., those without two opposite edges simply supported, by the symplectic superposition method (SSM), which has never been applied to in-plane elasticity problems in any existing works. Such analytic solutions are not accessible through conventional analytic methods as seeking analytic solutions that meet both the governing partial differential equations and various non-Lévy-type boundary conditions is an acknowledged challenge in mechanical analysis of plates. The clamped and free plates are considered as two most representative cases of non-Lévy-type plates. The SSM is implemented in the Hamiltonian system-based symplectic space, where the separation of variables and the symplectic eigen expansion prove to be well-grounded. These two mathematical treatments are adopted to first gain the analytic solutions of two elementary problems. The final analytic free in-plane vibration solutions are obtained by superposition of the two elementary problems. Comprehensive new natural frequencies and vibration modes are studied and validated by reference solutions from the finite element method or other approaches. The rigorous solution procedure, fast convergence, and highly accurate results render the present framework capable of serving as benchmarks for future comparison and applicable to analytic investigation of more plate problems.
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Electrochemical CO2 reduction (ECO2R) with renewable electricity is an advanced carbon conversion technology. At present, copper is the only metal to selectively convert CO2 into multicarbon (C2+) products. Among them, atomically dispersed (AD) Cu catalysts have received great attention due to the relatively single chemical environment, which are able to minimize the negative impact of morphology, valence state, and crystallographic properties, etc. on product selectivity. Furthermore, the completely exposed atomic Cu sites not only provide space and bonding electrons for the adsorption of reactants in favor of better catalytic activity but also provide an ideal platform for studying its reaction mechanism. This review summarizes the recent progress of AD Cu catalysts as a chemically tunable platform for ECO2R, including the atomic Cu sites dynamic evolution, the catalytic performance, and mechanism. Furthermore, the prospects and challenges of AD Cu catalysts for ECO2R are carefully discussed. We sincerely hope that this review can contribute to the rational design of AD Cu catalysts with enhanced performance for ECO2R.
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It is an urgent need to improve the depth of discharge (DOD) of Zn-air batteries (ZABs), considering that most reported ZABs with long cycle life are realized at low DOD (<1%). In this work, our solid-state ZABs achieved a long cycle life of more than 220 h at 3.2% DOD (the discharge capacity of 10 mA h cm-2 per cycle). Moreover, benefiting from excellent bifunctional oxygen electrocatalysts (Fe@BNC) and robust Zn|electrolyte interface, the ZABs displayed a long cycle life of 120 h even at high DOD of 23.4% and large discharge capacity of 72 mA h cm-2. Additionally, the impact of Zn|electrolyte interface on the cycle time at different DODs is analysed and discussed. The unstable interface exacerbated the dendrite growth and uneven deposition of Zn at high DOD, leading to the decay of the cycle life. The work gives insights into the mechanism of the effect of DOD on the cycle life of the batteries.
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Electrocatalytic CO2 reduction has received great attention for alleviating environmental problems and energy crisis. SnO2-based catalysts are attractive candidates, but they still face problems such as high overpotentials and small current density due to their low intrinsic electrical conductivity and weak activation for CO2. Here, superior selectivity and activity for C1 products (HCOO- and CO) were obtained using In-doped SnO2. The maximum faradaic efficiency was 96.46% at -0.75 V and the partial current density reached -20.12 mA cm-2 at -0.95 V for C1 products. Furthermore, the selectivity for C1 products was over 90% from -0.5 to -1.0 V with a current density of -166.2 mA cm-2 at -1.0 V in flow cells. In ion doping induced electron transfer from Sn species to In and simultaneously generated oxygen vacancies, which improved electrical conductivity and regulated the oxidation state of Sn active sites and provided more active sites. This work emphasizes the role of enhanced electron transfer of catalysts in CO2 electroreduction.
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Pb-free perovskite material is considered to be a promising material utilized in next-generation X-ray detectors due to its high X-ray absorption coefficient, decent carrier transport properties, and relatively low toxicity. However, the pixelation of the perovskite material with an industry-level photolithography processing method remains challenging due to its poor structural stability. Herein, we use Cs2AgBiBr6 perovskite material as the prototype and investigate its interaction with photolithographic polar solvents. Inspired by that, we propose a wafer-scale photolithography patterning method, where the pixeled perovskite array devices for X-ray detection are successfully prepared. The devices based on pixeled Pb-free perovskite material show a high detection sensitivity up to 19118 ± 763 µC Gyair-1 cm-2, which is comparable to devices with Pb-based perovskite materials and superior to the detection sensitivity (â¼20 µC Gyair-1 cm-2) of the commercial a-Se detector. After pixelation, the devices achieve an improved spatial resolution capacity with the spatial frequency from 2.7 to 7.8 lp mm-1 at modulation-transfer-function (MTF) = 0.2. Thus, this work may contribute to the development of high-performance array X-ray detectors based on Cs2AgBiBr6 perovskite material.
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New analytic bending, buckling, and free vibration solutions of rectangular nanoplates with combinations of clamped and simply supported edges are obtained by an up-to-date symplectic superposition method. The problems are reformulated in the Hamiltonian system and symplectic space, where the mathematical solution framework involves the construction of symplectic eigenvalue problems and symplectic eigen expansion. The analytic symplectic solutions are derived for several elaborated fundamental subproblems, the superposition of which yields the final analytic solutions. Besides Lévy-type solutions, non-Lévy-type solutions are also obtained, which cannot be achieved by conventional analytic methods. Comprehensive numerical results can provide benchmarks for other solution methods.
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Mosquito-repellent incense is one of the most popular products used for dispelling mosquitos during summer in China. It releases large amounts of particulate and gaseous pollutants which constitute a potential hazard to human health. We conducted chamber experiment to characterize major pollutants from three types of mosquito-repellent incenses, further assessed the size-fractionated deposition in human respiratory system, and evaluated the indoor removing efficiency by fresh air. Results showed that the released pollutant concentrations were greater than permissible levels in regulations in GB3095-2012, as well as suggested by the World Health Organization (WHO). Formaldehyde accounted for 10-20% of the total amount of pollutants. Fine particles dominated in the total particulate concentrations. Geometric standard deviation (GSD) of particle number size distributions was in the range of 1.45-1.93. Count median diameter (CMD) ranged from 100 to 500 nm. Emission rates, burning rates and emission factors of both particulate and gaseous pollutants were compared and discussed. The deposition fractions in pulmonary airway from the disc solid types reached up to 52.7% of the total deposition, and the largest deposition appeared on juvenile group. Computational Fluid Dynamics (CFD) modellings indicated air-conditioner on and windows closed was the worst case. The highest concentration was 180-200 times over the standard limit.
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Poluentes Atmosféricos/análise , Repelentes de Insetos/análise , Poluição do Ar em Ambientes Fechados/análise , Animais , China , Culicidae , Formaldeído/análise , Humanos , Repelentes de Insetos/toxicidade , Tamanho da Partícula , Material Particulado/análise , Medição de RiscoRESUMO
Urban public parks provide a recreational environment for residents, hence more and more citizens would spend time in parks, especially elderly and kids. Therefore, it is important to evaluate the quality of ecological environment inside parks. Therefore, this study conducted the first measurements in ten public parks of Shanghai to investigate heavy metals in air, soil and leaf, growth parameters of leaf, and ambient PM2.5 and black carbon (BC) concentrations. Results showed Al and Mg appeared the highest in air. Cr, Cu, Mn and Zn were dominating in soil. Ca and Mg were much greater in leaves. It was concluded geographical locations were major reasons to explain the level of heavy metals, which mainly came from vehicle emissions. A small portion was attributing to chemical industries nearby. PM2.5 concentrations ranged from 0.01 mg/m3 to 0.10 mg/m3, which met up level I and level II of air quality standard in China. BC concentrations ranged from 1000 ng/m3 to 6000 ng/m3. Via comparing the correlation between photosynthesis and PM2.5, as well as chlorophyll content and PM2.5, it was concluded that chlorophyll can be regarded as an indicator for assessing air quality, but not photosynthesis. Unexpectedly, a positive correlation was observed between the stomatal conductance and PM2.5 as well as BC, which might be attributed to plants resisting the ambient stress. The results of this study can be used for assessments of air quality and health exposure inside parks, and also could provide urban policy maker with scientific evidences for urban park planning.