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The reaction kinetics of hydrogen evolution reaction (HER) is largely determined by balancing the Volmer step in alkaline media. Bifunctionality as a proposed strategy can divide the work of water dissociation and intermediates (OH* and H*) adsorption/desorption. However, sluggish OH* desorption plagues water re-adsorption, which leads to poisoning effects of active sites. Some active sites may even directly act as spectators and do not participate in the reaction. Furthermore, the activity comparison under approximate nanostructure between bifunctional effect and single-exposed active sites is not fully understood. Here, a facile three-step strategy is adopted to successfully grow molybdenum disulfide (MoS2 ) on cobalt-containing nitrogen-doped carbon nanotubes (Co-NCNTs), forming obvious dual active domains. The active sites on domains of Co-NCNTs and MoS2 and the tuned electronic structure at the heterointerface trigger the bifunctional effect to balance the Volmer step and improve the catalytic activity. The HER driven by the bifunctional effect can significantly optimize the Gibbs free energy of water dissociation and hydrogen adsorption, resulting in fast reaction kinetics and superior catalytic performance. As a result, the Co-NCNTs/MoS2 catalyst outperforms other HER electrocatalysts with low overpotential (58 and 84 mV at 10 mA cm-2 in alkaline and neutral conditions, respectively), exceptional stability, and negligible degradation.
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Solar carbon dioxide (CO2) conversion is an emerging solution to meet the challenges of sustainable energy systems and environmental/climate concerns. However, the construction of isolated active sites not only influences catalytic activity but also limits the understanding of the structure-catalyst relationship of CO2 reduction. Herein, we develop a universal synthetic protocol to fabricate different single-atom metal sites (e.g., Fe, Co, Ni, Zn, Cu, Mn, and Ru) anchored on the triazine-based covalent organic framework (SAS/Tr-COF) backbone with the bridging structure of metal-nitrogen-chlorine for high-performance catalytic CO2 reduction. Remarkably, the as-synthesized Fe SAS/Tr-COF as a representative catalyst achieved an impressive CO generation rate as high as 980.3 µmol g-1 h-1 and a selectivity of 96.4%, over approximately 26 times higher than that of the pristine Tr-COF under visible light irradiation. From X-ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to the synergic effect of atomically dispersed metal sites and Tr-COF host, decreasing the reaction energy barriers for the formation of *COOH intermediates and promoting CO2 adsorption and activation as well as CO desorption. This work not only affords rational design of state-of-the-art catalysts at the molecular level but also provides in-depth insights for efficient CO2 conversion.
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Photocatalysis is regarded as one of the most promising technologies for indoor volatile organic compounds (VOCs) elimination due to its low cost, safe operation, energy efficiency, and high mineralization efficiency under ambient conditions. However, the practical applications of this technology are limited, despite considerable research efforts in recent decades. Until now, most of the works were carried out in the laboratory and focused on exploring new catalytic materials. Only a few works involved the immobilization of catalysts and the design of reactors for practical applications. Therefore, this review systematically summarizes the research and development on photocatalytic oxidation (PCO) of VOCs, with emphasis on recent catalyst's immobilization and reactor designs in detail. First, different types of photocatalytic materials and the mechanisms for PCO of VOCs are briefly discussed. Then, both the catalyst's immobilization techniques and reactor designs are reviewed in detail. Finally, the existing challenges and future perspectives for PCO of VOCs are proposed. This work aims to provide updated information and research inspirations for the commercialization of this technology in the future.
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Poluição do Ar em Ambientes Fechados , Compostos Orgânicos Voláteis , Poluição do Ar em Ambientes Fechados/análise , Fotoquímica/métodos , Catálise , OxirreduçãoRESUMO
Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M-N4 ) to accelerate overall reaction dynamics of the electrochemical CO2 reduction reaction (CO2 RR) has attracted extensive attention. Herein, we develop an axial traction strategy to optimize the electronic structure of the M-N4 moiety and construct atomically dispersed nickel sites coordinated with four nitrogen atoms and one axial oxygen atom, which are embedded within the carbon matrix (Ni-N4 -O/C). The Ni-N4 -O/C electrocatalyst exhibited excellent CO2 RR performance with a maximum CO Faradic efficiency (FE) close to 100 % at -0.9â V. The CO FE could be maintained above 90 % in a wide range of potential window from -0.5 to -1.1â V. The superior CO2 RR activity is due to the Ni-N4 -O active moiety composed of a Ni-N4 site with an additional oxygen atom that induces an axial traction effect.
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Atomically dispersed transition metal active sites have emerged as one of the most important fields of study because they display promising performance in catalysis and have the potential to serve as ideal models for fundamental understanding. However, both the preparation and determination of such active sites remain a challenge. The structural engineering of carbon- and nitrogen-coordinated metal sites (M-N-C, M = Fe, Co, Ni, Mn, Cu, etc.) via employing new heteroatoms, e.g., P and S, remains challenging. In this study, carbon nanosheets embedded with nitrogen and phosphorus dual-coordinated iron active sites (denoted as Fe-N/P-C) were developed and determined using cutting edge techniques. Both experimental and theoretical results suggested that the N and P dual-coordinated iron sites were favorable for oxygen intermediate adsorption/desorption, resulting in accelerated reaction kinetics and promising catalytic oxygen reduction activity. This work not only provides efficient way to prepare well-defined single-atom active sites to boost catalytic performance but also paves the way to identify the dual-coordinated single metal atom sites.
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Developing efficient earth-abundant MoS2 based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high-performance MoS2 based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate-limited water dissociation step for the HER mechanism in alkaline media. The as-obtained MoS2 /Ni2 O3 H catalyst exhibits a low overpotential of 84 mV at 10 mA cm-2 and small charge-transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm-2 ) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS2 , respectively. Additionally, these MoS2 /metal oxides heterostructure catalysts show outstanding long-term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d-band in different transition oxides, in which Ni-3d of Ni2 O3 H is evidently activated to achieve fast electron transfer for HER as the electron-depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS2 /Ni2 O3 H in the adsorption and dissociation of H2 O for highly efficient HER in alkaline media.
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Many organic molecules have unique magnetic properties and can potentially serve as excellent molecular spin devices, which is worth exploring deeply. Here, the spin transport properties of Mn, Fe, Co and Cu porphyrin dimer devices are investigated based on the first principles method. The spin filtering efficiencies of these molecular devices are maintained at 100% within certain applied voltage ranges and magnetoresistance ratios are higher than 108% which increase as the voltage increases. To explain the excellent spin-filtering and giant magnetoresistance effects, analysis of spin electron densities and transmission spectra indicates that magnetic properties are mainly contributed by the metal atoms and their neighbouring N atoms. From the transmission pathway studies, spin electrons come mainly through the π-conjugated structure of the metal porphyrin ring. Interestingly, in the Cu porphyrin dimer device, magnetic moments of the Cu-N structure in the Cu porphyrin dimer device show spin behaviors different from those of Mn, Fe and Co porphyrin dimer devices.
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Motivation: Processing of transcripts at the 3'-end involves cleavage at a polyadenylation site followed by the addition of a poly(A)-tail. By selecting which site is cleaved, the process of alternative polyadenylation enables genes to produce transcript isoforms with different 3'-ends. To facilitate the identification and treatment of disease-causing mutations that affect polyadenylation and to understand the sequence determinants underlying this regulatory process, a computational model that can accurately predict polyadenylation patterns from genomic features is desirable. Results: Previous works have focused on identifying candidate polyadenylation sites and classifying tissue-specific sites. By training on how multiple sites in genes are competitively selected for polyadenylation from 3'-end sequencing data, we developed a deep learning model that can predict the tissue-specific strength of a polyadenylation site in the 3' untranslated region of the human genome given only its genomic sequence. We demonstrate the model's broad utility on multiple tasks, without any application-specific training. The model can be used to predict which polyadenylation site is more likely to be selected in genes with multiple sites. It can be used to scan the 3' untranslated region to find candidate polyadenylation sites. It can be used to classify the pathogenicity of variants near annotated polyadenylation sites in ClinVar. It can also be used to anticipate the effect of antisense oligonucleotide experiments to redirect polyadenylation. We provide analysis on how different features affect the model's predictive performance and a method to identify sensitive regions of the genome at the single-based resolution that can affect polyadenylation regulation. Supplementary information: Supplementary data are available at Bioinformatics online.
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Poliadenilação , Regiões 3' não Traduzidas , Regulação da Expressão Gênica , Genoma Humano , Genômica , Humanos , Poli ARESUMO
Increasing utilization of solar energy is an effective strategy to tackle our energy and energy-related environmental issues. Both solar photocatalysis (PC) and solar photovoltaics (PV) have high potential to develop technologies of many practical applications. Substantial research efforts are devoted to enhancing visible light activation of the photoelectrocatalytic reactions by various modifications of nanostructured semiconductors. This review paper emphasizes the recent advancement in material modifications by means of the promising localized surface plasmonic resonance (LSPR) mechanisms. The principles of LSPR and its effects on the photonic efficiency of PV and PC are discussed here. Many research findings reveal the promise of Au and Ag plasmonic nanoparticles (NPs). Continual investigation for increasing the stability of the plasmonic NPs will be fruitful.
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Nanopartículas/química , Energia Solar , Catálise , Eletroquímica , Processos Fotoquímicos , Semicondutores , Luz SolarRESUMO
MOTIVATION: Alternative splicing (AS) is a regulated process that directs the generation of different transcripts from single genes. A computational model that can accurately predict splicing patterns based on genomic features and cellular context is highly desirable, both in understanding this widespread phenomenon, and in exploring the effects of genetic variations on AS. METHODS: Using a deep neural network, we developed a model inferred from mouse RNA-Seq data that can predict splicing patterns in individual tissues and differences in splicing patterns across tissues. Our architecture uses hidden variables that jointly represent features in genomic sequences and tissue types when making predictions. A graphics processing unit was used to greatly reduce the training time of our models with millions of parameters. RESULTS: We show that the deep architecture surpasses the performance of the previous Bayesian method for predicting AS patterns. With the proper optimization procedure and selection of hyperparameters, we demonstrate that deep architectures can be beneficial, even with a moderately sparse dataset. An analysis of what the model has learned in terms of the genomic features is presented.
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Processamento Alternativo , Inteligência Artificial , Algoritmos , Animais , Teorema de Bayes , Genômica/métodos , Humanos , Camundongos , Redes Neurais de Computação , Análise de Sequência de RNARESUMO
Ag-Ag2S hybrid nanoparticles were deposited onto Anatase anodic TiO2 nanotubular arrays via a one-step in situ hydrothermal method. Characterization was carried out using FE-SEM, HRTEM, XRD, XPS and UV-vis DRS. The fabricated nano-composites exhibit high visible light-sensitivity and photocurrent output as photoanodes in photoelectrochemical applications. The outstanding performance of the final composite is attributed to the surface plasmonic resonance effect of Ag, which is further enhanced by an Ag2S outer-layer.
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Photocatalytic solar-to-fuel conversion over metal halide perovskites (MHPs) has recently attracted much attention, while the roles of defects in MHPs are still under debate. Specifically, the mainstream viewpoint is that the defects are detrimental to photocatalytic performance, while some recent studies show that certain types of defects contribute to photoactivity enhancement. However, a systematic summary of why it is contradictory and how the defects in MHPs affect photocatalytic performance is still lacking. In this review, the innovative roles of defects in MHP photocatalysts are highlighted. First, the origins of defects in MHPs are elaborated, followed by clarifying certain benefits of defects in photocatalysts including optical absorption, charge dynamics, and surface reaction. Afterward, the recent progress on defect-related MHP photocatalysis, i.e., CO2 reduction, H2 generation, pollutant degradation, and organic synthesis is systematically discussed and critically appraised, putting emphasis on their beneficial effects. With defects offering peculiar sets of merits and demerits, the personal opinion on the ongoing challenges is concluded and outlining potentially promising opportunities for engineering defects on MHP photocatalysts. This critical review is anticipated to offer a better understanding of the MHP defects and spur some inspiration for designing efficient MHP photocatalysts.
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Slippery liquid-infused porous surfaces (SLIPS) have received widespread attention in the antifouling field. However, the reduction in antifouling performance caused by lubricant loss limits their application in marine antifouling. Herein, inspired by the skin of a poison dart frog which contains venom glands and mucus, a porous liquid (PL) based on ZIF-8 is prepared as a lubricant and injected into a silicone polyurethane (SPU) matrix to construct a new type of SLIPS for marine antifouling applications: the slippery porous-liquid-infused porous surface (SPIPS). The SPIPS consists of a responsive antifoulant-releasing switch between "defensive" and "offensive" antifouling modes to intelligently enhance the antifouling effect after lubricant loss. The SPIPS can adjust antifouling performance to meet the antifouling requirements under different light conditions. The wastage of antifoulants is reduced, thereby effectively maintaining the durability and service life of SLIPS materials. The SPIPS exhibits efficient lubricant self-replenishment, self-cleaning, anti-protein, anti-bacterial, anti-algal, and self-healing (97.48%) properties. Furthermore, it shows satisfactory 360-day antifouling performance in actual marine fields during boom seasons, demonstrating the longest antifouling lifespan in the field tests of reported SLIPS coatings. Hence, the SPIPS can effectively promote the development of SLIPS for neritic antifouling.
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Incrustação Biológica , Animais , Incrustação Biológica/prevenção & controle , Porosidade , Lubrificantes , Rãs Venenosas , PoliuretanosRESUMO
Environmental pollution and energy crises have garnered global attention. The substantial discharge of organic waste into water bodies has led to profound environmental contamination. Photocatalytic fuel cells (PFCs) enabling the simultaneous removal of refractory contaminants and recovery of the chemical energy contained in organic pollutants provides a potential strategy to solve environmental issues and the energy crisis. This review will discuss the fundamentals, working principle, and configuration development of PFCs and photocatalytic microbial fuel cells (PMFCs). We particularly focus on the strategies for improving the wastewater treatment performance of PFCs/PMFCs in terms of coupled advanced oxidation processes, the rational design of high-efficiency electrodes, and the strengthening of the mass transfer process. The significant potential of PFCs/PMFCs in various fields is further discussed in detail. This review is intended to provide some guidance for the better implementation and widespread adoption of PFC wastewater treatment technologies.
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Ammonia (NH3) plays a significant role in the manufacture of fertilizers, nitrogen-containing chemical production, and hydrogen storage. The electrochemical nitrogen reduction reaction (e-NRR) is an attractive prospect for achieving clean and sustainable NH3 production, under mild conditions driven by renewable energy. The sluggish cleavage of N≡N bonds and poor selectivity of e-NRR are the primary challenges for e-NRR, over the competitive hydrogen evolution reaction (HER). The rational design of e-NRR electrocatalysts is of vital significance and should be based on a thorough understanding of the structure-activity relationship and mechanism. Among the various explored e-NRR catalysts, metal-based electrocatalysts have drawn increasing attention due to their remarkable performances. This review highlighted the recent progress and developments in metal-based electrocatalysts for e-NRR. Different kinds of metal-based electrocatalysts used in NH3 synthesis (including noble-metal-based catalysts, non-noble-metal-based catalysts, and metal compound catalysts) were introduced. The theoretical screening and the experimental practice of rational metal-based electrocatalyst design with different strategies were systematically summarized. Additionally, the structure-function relationship to improve the NH3 yield was evaluated. Finally, current challenges and perspectives of this burgeoning area were provided. The objective of this review is to provide a comprehensive understanding of metal-based e-NRR electrocatalysts with a focus on enhancing their efficiency in the future.
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Quantum dot (QD) contrast-enhanced molecular imaging has potential for early cancer detection and image guided treatment, but there is a lack of quantitative image contrast data to determine optimum QD administered doses, affecting the feasibility, risk and cost of such procedures, especially in vivo. Vascular fluorescence contrast-enhanced imaging is performed on nude mice bearing dorsal skinfold window chambers, injected with 4 different QD solutions emitting in the visible and near infrared. Linear relationships are observed among the vascular contrast, injected contrast agent volume, and QD concentration in blood. Due primarily to differential light absorption by blood, the vasculature is optimally visualized when exciting in the 435-480 nm region in 81% of the cases (89 out of 110 regions of interest in 22 window chambers). The threshold dose, defined here as the quantity of injected nanoparticles required to yield a vascular target-to-autofluorescence ratio of 2, varies from 10.6 to 0.15 pmol g(-1) depending on the QD emission wavelength. The wavelength optimization maximum and broadband gain, defined as the ratio of threshold doses estimated for optimal and suboptimal (worst wavelength or broadband) spectral illumination, has average values of 4.5 and 1.9, respectively. This study demonstrates, for the first time, optimized QD imaging in vivo. It also proposes and validates a theoretical framework for QD dose estimation and quantifies the effects of blood absorption, QD emission wavelength, and vessel diameter relative to the threshold dose.
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Imagem Molecular/métodos , Pontos Quânticos , Animais , Feminino , Fluorescência , Humanos , Camundongos , Espectrometria de FluorescênciaRESUMO
The rapid development of electrochemical power systems has prompted high demand for nonprecious trifunctional electrocatalysts with superior performance, prolonged stability, and low cost for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, a valence engineering strategy is devised to construct a morphology with polyvalent cobalt encapsulated in nitrogen-doped carbon nanofibers (Co/N-CNFs). The diverse cobalt valence states of the Co/N-CNF catalysts contribute to their excellent catalytic effect and high durability in multiple electrochemical processes. The optimal Co/N-CNF catalyst fabricated exhibits a high half-wave potential of ORR (0.86 V) and low overpotentials of OER (380 mV) and HER (241 mV) at 10 mA cm-2. The Co/N-CNF-based Zn-air battery possesses a high charge-discharge efficiency as well as a good cycle stability (50 h at 10 mA cm-2 and 120 h at 20 mA cm-2), much superior to the Pt/C-based batteries. Furthermore, the Co/N-CNF catalyst could perform efficient overall water splitting.
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High relative permittivity and low dielectric loss are two desired parameters of a triboelectric layer to enhance its mechanical-to-electrical energy conversion efficiency in a triboelectric nanogenerator (TENG). However, the elevated permittivity of the triboelectric layer is always accompanied by increasing dielectric loss, limiting further improvement or even reducing the electrical output. Herein, we report a method for improving the relative permittivity and suppressing the dielectric loss of the triboelectric layer via nanoscale design at the particle-polymer interface. When incorporated with 2 wt % Ag@C, the triboelectric-layer-enhanced TENG (TLE-TENG) presents a 2.6-fold increment in relative permittivity and a 302% current enhancement. An instantaneous peak power density of 1.22 W m-2, an excellent pressure sensitivity of 90.95 V kPa-1, and an optimized sheet resistance (â¼0.14 Ω/sq) are attributes of this greatly enhanced device. Such improvements bode well for the implementation of these enhancing strategies to help position TLE-TENGs as pervasive and sustainable power sources and active self-powered sensors in the era of the Internet of Things.
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Electrostatic adsorption is an important complement to the mechanical filtration for high-efficiency air filtering. However, the electrostatic charge decays with time, especially in humid conditions. In this work, a self-charging air filter is presented to capture airborne particles in an efficient and long-lasting manner without the need of external power sources. Leveraging the triboelectric effect between the electrospun poly(vinylidene fluoride) nanofiber film and nylon fabric, the self-charging air filter-based mask excited by breathing can continuously replenish electrostatic charges. As a result, its effective lifespan is up to 60 hours (including 30 hours of wearing), with a minimum filtration efficiency of 95.8% for 0.3-µm particles. The filtration efficiency and lifespan are significantly higher than those of a commercial surgical mask. Furthermore, we uncover the quantitative relation between filtration efficiency and surface electrostatic potential. This work provides an effective strategy to significantly prolong the electrostatic adsorption efficacy for high-performance air-filtering masks.
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Filtros de Ar , Máscaras , Eletricidade Estática , Filtração , TêxteisRESUMO
PURPOSE: The aim of this study is to understand the characteristics of secondary electrons generated from the interaction of gold nanoparticles (GNPs) with x-rays as a function of nanoparticle size and beam energy and thereby further the understanding of GNP-enhanced radiotherapy. METHODS: The effective range, deflection angle, dose deposition, energy, and interaction processes of electrons produced from the interaction of x-rays with a GNP were calculated by Monte Carlo simulations. The GEANT4 code was used to simulate and track electrons generated from a 2, 50, and 100 nm diameter GNP when it is irradiated with a 50 kVp, 250 kVp, cobalt-60, and 6 MV photon beam in water. RESULTS: When a GNP was present, depending on the beam energies used, secondary electron production was increased by 10- to 2000-fold compared to an absence of a GNP. Low-energy photon beams were much more efficient at interacting with the GNP by two to three orders of magnitude compared to MV energies and increased the deflection angle. GNPs with larger diameters also contributed more dose. The majority of the energy deposition was outside the GNP, rather than self-absorbed by the nanoparticle. The mean effective range of electron tracks for the beams tested ranged from approximately 3 microm to 1 mm. CONCLUSIONS: These simulated results yield important insights concerning the spatial distributions and elevated dose in GNP-enhanced radiotherapy. The authors conclude that the irradiation of GNP at lower photon energies will be more efficient for cell killing. This conclusion is consistent with published studies.