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Coupling atmospheric-pressure low-temperature plasmas to electrochemical reactors enables the generation of highly reactive species at plasma-liquid interfaces. This type of plasma electrochemical reactor (PEC) has been used to synthesize fluorescent nitrogen-doped graphene quantum dots (NGQDs), which are usable for multifunctional applications in a facile, simple, and sustainable way. However, the synthesis mechanism remains poorly understood, as well as the location of synthesis. To research these issues, we present an in situ diagnostics study on liquid phase chemistry during the PEC synthesis of NGQDs from chitosan. Monitoring of the photoluminescence and UV-VIS absorption at different depths in the reaction medium during plasma treatment reveals that the NGQD production initiates at the plasma-liquid interface but its completion and/or accumulation occurs at a few millimetres depth below the interface, where the liquid ceases to flow convectively, as determined by particle image velocimetry. Our study provides insights into the plasma synthesis of fluorescent GQDs/NGQDs from carbon precursors that may prove useful for achieving the scalability of PEC processes up to continuous-flow or array reactors.
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Correction for 'Hybrid 2D perovskite and red emitting carbon dot composite for improved stability and efficiency of LEDs' by Amandeep Singh Pannu et al., Nanoscale, 2023, 15, 2659-2666, https://doi.org/10.1039/D2NR06942C.
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The ability to control the porosity of thin oxide films is a key factor determining their properties. Despite the abundance of dry processes for synthesizing oxide porous layers, a high porosity range is typically achieved by spin-coating-based wet chemical methods. Besides, special techniques such as supercritical drying are required to replace the pore liquid with air while maintaining the porous network. In this study, we propose a new method for the fabrication of ultraporous titanium dioxide thin films at room or mild temperatures (T ≤ 120 °C) by a sequential process involving plasma deposition and etching. These films are conformal to the substrate topography even for high-aspect-ratio substrates and show percolated porosity values above 85% that are comparable to those of advanced aerogels. The films deposited at room temperature are amorphous. However, they become partly crystalline at slightly higher temperatures, presenting a distribution of anatase clusters embedded in the sponge-like open porous structure. Surprisingly, the porous structure remains after annealing the films at 450 °C in air, which increases the fraction of embedded anatase nanocrystals. The films are antireflective, omniphobic, and photoactive, becoming superhydrophilic when subjected to ultraviolet light irradiation. The supported, percolated, and nanoporous structure can be used as an electron-conducting electrode in perovskite solar cells. The properties of the cells depend on the aerogel-like film thickness, which reaches efficiencies close to those of commercial mesoporous anatase electrodes. This generic solvent-free synthesis is scalable and applicable to ultrahigh porous conformal oxides of different compositions, with potential applications in photonics, optoelectronics, energy storage, and controlled wetting.
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Malignant melanoma is the most lethal form of skin cancer. As a promising anti-cancer agent, plasma-activated water (PAW) rich in reactive oxygen and nitrogen species (RONS) has shown significant potential for melanoma treatment. However, rapid decay of RONS and inefficient delivery of PAW in conventional injection methods limit its practical applications. To address this issue, here we report a new approach for the production of plasma-activated cryo-microneedles (PA-CMNs) patches using custom-designed plasma devices and processes. Our innovation is to incorporate PAW into the PA-CMNs that are fabricated using a fast cryogenic micro-molding method. It is demonstrated that PA-CMNs can be easily inserted into skin to release RONS and slow the decay of RONS thereby prolonging their bioactivity and effectiveness. The new insights into the effective melanoma treatment suggest that the rich mixture of RONS within PA-CMNs prepared by custom-developed hybrid plasma-assisted configuration induces both ferroptosis and apoptosis to selectively kill tumor cells. A significant inhibition of subcutaneous A375 melanoma growth was observed in PA-CMNs-treated tumor-bearing nude mice without any signs of systemic toxicity. The new approach based on PA-CMNs may potentially open new avenues for a broader range of disease treatments.
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Li-ion batteries suffer from two key safety issues: thermal overload and compression recovery, which may lead to flammability and mechanical failure. Silica aerogels are promising solutions to both these issues owing to their excellent thermal stability and tailored mechanical properties. However, finding the optimum sol composition in sol-gel-based aerogel synthesis is needed to address these issues at industry-relevant scales. Here, we propose an innovative approach to determine the optimum sol composition for methylsilsesquioxane (MSQ) aerogel sheets, which is based on the mechanisms of the effects of molar ratios of hydrolysis water and isopropyl alcohol (IPA) to methyltrimethoxysilane (MTMS) on the physical properties of MSQ aerogel sheets and according to the ternary contour distribution of their properties. The synthesized MSQ aerogels exhibited a soft, light, and powderless texture and featured superhydrophobic properties (150.2°), low thermal conductivity of 33.6 mW/(m·K), high thermal stability temperature in nitrogen atmosphere at 479.3 °C and moderate short-term (<6 h) service temperature of 120.0 °C. Significantly, the structural stability and elasticity of the aerogels surpassed the current state-of-the-art, showing recovery to 81.3 % of the original thickness and 85.2 % of the original stress after being subjected to 400 cycles of high-speed and high-strain consecutive compression, respectively. These excellent properties make the MSQ aerogel sheets promising for applications in thermal load and compression recovery management of diverse energy storage devices, including batteries for next-generation electric vehicles.
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The release of nitrates into the environment leads to contaminated soil and water that poses a health risk to humans and animals. Due to the transition to renewable energy-based technologies, an electrochemical approach is an emerging option that can selectively produce valuable ammonia from nitrate sources. However, traditional metal-based electrocatalysts often suffer from low nitrate adsorption that reduces NH3 production rates. Here, a Ni-GaOOH-C/Ga electrocatalyst for electrochemical nitrate conversion into NH3 is synthesized via a low energy atmospheric-pressure plasma process that reduces CO2 into highly dispersed activated carbon on dispersed NiâGaOOH particles produced from a liquid metal GaâNi alloy precursor. Nitrate conversion rates of up to 26.3 µg h-1 mg-1 cat are achieved with good stability of up to 20 h. Critically, the presence of carbon centers is central to improved performance where both NiâC and NiOâC interfaces act as NO3- adsorption and reduction centers during the reaction. Density functional theory (DFT) calculations indicate that the NiOâC and NiâC reaction sites reduce the Gibbs free energy required for NO3- reduction to NH3 compared to NiO and Ni. Importantly, catalysts without carbon centers do not produce NH3, emphasizing the unique effects of incorporating carbon nanoparticles into the electrocatalyst.
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Designing a functional, conductive metal-organic framework (cMOF) is highly desired. Substantial efforts have been dedicated to increasing the intralayer conjugation of the cMOFs, while less dedication has been made to tuning the interlayer charge transport of the metal-organic nanosheets for the controllable dielectric property. Here, we construct a series of conductive bimetallic organic frameworks of (ZnxCu3-x) (hexahydroxytriphenylene)2 (ZnCu-HHTP) to allow for fine-tuned interlayer spacing of two-dimensional frameworks, by adjusting the ratios of Zn and Cu metal ions. This approach for atomistic interlayer design allows for the finely control of the charge transport, band structure, and dielectric properties of the cMOF. As a result, Zn3Cu1-HHTP, with an optimal dielectric property, exhibits high-efficiency absorption in the gigahertz microwave range, achieving an ultra-strong reflection loss of -81.62 decibels. This study not only advances the understanding of the microstructure-function relationships in cMOFs but also offers a generic nanotechnology-based approach to achieving controllable interlayer spacing in MOFs for the targeted applications.
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Biaxially-oriented polypropylene (BOPP) is one of the most commonly used materials for film-based capacitors for power electronics and pulsed power systems. To address the pressing issue of performance-limiting loss under extreme electric-fields, here a one-step, high-throughput, and environment-friendly process based on very low-dose ultra-violet irradiation from KrCl (222 nm) and Xe2 (172 nm) excimer is demonstrated. The performance of commercial BOPP is boosted in terms of withstanding electric-field extremes (Weibull breakdown strength 694 to 811 V µm-1 by 17% at 25 °C and 428 to 651 V µm-1 by 52% at 120 °C), discharged energy density, and conduction losses. Importantly, the depth profile of space charge is precisely measured in situ with a high resolution of 500 nm by laser induced pressure pulse. Consequently, the space charge effect and electric-field distortion are reduced and related to the improved polymer films. It is demonstrated that energetic UV photons act as scissors for BOPP chains and dissociate oxygen molecules leading to the more thermally stable oxygen-containing structures, as deep traps to impede charge migration. This work provides a promising approach to produce polymers with customized microscopic characteristics that is compatible with the assembly lines of polymer-based capacitors.
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Mismatch Repair (MMR) mechanisms play a pivotal role in rectifying DNA replication errors and maintaining the stability of DNA microsatellite structure. Colorectal cancer (CRC) can be characterized into microsatellite stability (MSS) and microsatellite instability (MSI) subtypes based on the functionality of MMR. MSI CRC notably exhibits enhanced chemotherapy resistance, attributable to diminished MMR-related protein expression. Cold atmospheric plasma (CAP) has emerged as a promising treatment modality, demonstrating efficacy in inducing apoptosis in various cancer cells. However, the therapeutic impact of CAP on MSI colorectal cancer, and the underlying mechanisms remain elusive. In this study, we investigated the effects of CAP on MSI (MC38, HCT116, and LOVO) and MSS (CT26 and HT29) CRC cell lines. We are probing into the products of CAP treatment. Our findings indicate that CAP treatment induces comparable effects on apoptosis, reactive oxygen species (ROS), and reactive nitrogen species (RNS), as well as the expression of apoptosis-related proteins in both MSI and MSS cells. Mechanistically, CAP treatment led to an elevation in the expression of mismatch repair proteins (MLH1 and MSH2), particularly in MSI cells, which notably have been proven to facilitate the activation of apoptosis-related proteins. Collectively, our study reveals that CAP enhances apoptotic signaling and induces apoptosis in MSI colorectal cancer cells by upregulating the expression of MMR-related proteins, thereby reinforcing MMR stabilization.
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Neoplasias Colorretais , Reparo de Erro de Pareamento de DNA , Humanos , Proteínas Adaptadoras de Transdução de Sinal/genética , Proteína 2 Homóloga a MutS/genética , Instabilidade de Microssatélites , Repetições de Microssatélites , Neoplasias Colorretais/genética , Neoplasias Colorretais/tratamento farmacológicoRESUMO
Clean water and sanitation are major global challenges highlighted by the UN Sustainable Development Goals. Water treatment using energy-efficient membrane technologies is one of the most promising solutions. Despite decades of research, the membrane permeability-selectivity trade-off remains the major challenge for synthetic membranes. To overcome this challenge, here we develop a two-dimensional cobalt-functionalized vermiculite membrane (Co@VMT), which innovatively combines the properties of membrane filtration and nanoconfinement catalysis. The Co@VMT membrane demonstrates a high water permeance of 122.4 L·m-2·h-1·bar-1, which is two orders of magnitude higher than that of the VMT membrane (1.1 L·m-2·h-1·bar-1). Moreover, the Co@VMT membrane is applied as a nanofluidic advanced oxidation process platform to activate peroxymonosulfate (PMS) for degradation of several organic pollutants (dyes, pharmaceuticals, and phenols) and shows excellent degradation performance (~100%) and stability (for over 107 h) even in real-world water matrices. Importantly, safe and non-toxic effluent water quality is ensured by the Co@VMT membrane/PMS system without brine, which is totally different from the molecular sieving-based VMT membrane with the concentrated pollutants remaining in the brine. This work can serve as a generic design blueprint for the development of diverse nanofluidic catalytic membranes to overcome the persistent membrane permeability-selectivity issue in water purification.
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Transition-metal based oxides with custom-designed phases are effective oxygen evolution reaction (OER) electrocatalysts. However, their applications in water splitting are limited because of insufficient catalytic performance in hydrogen evolution reaction (HER) in alkaline media. In this work, we engineer fabric-like rhodium-nickel-tungsten oxide nanosheets (Rh2O3-NiWO4) on plasma-treated nickel foam (PNF) with a one-step hydrothermal approach for potential applications as industry-grade HER electrocatalysts. Benefiting from rich active sites exposed on the heterostructure, low hydrogen binding energy on Rh, and enhanced charge delivery rates, Rh2O3-NiWO4/PNF catalyst exhibits superior HER activity than that achieved by a commercially available Pt/C catalyst. This is evidenced by the fact that the overpotentials of Rh2O3-NiWO4/PNF for delivering current densities of 10 (j10) and 1000 (j1000) mA cm-2 in 1.0 M KOH are merely 19 and 293 mV, respectively. Meanwhile, the small Tafel slope (18 mV dec-1) of the optimized catalyst manifests the fast HER kinetics. In addition, Rh2O3-NiWO4/PNF exhibits ultra-stable HER performance, and the current density (j100) only decrease 7.69 % after 100 h chronoamperometric curves (I-t) test. The present work provides a new approach for designing high-performance, low-cost 2D electrocatalysts for H2 production and other clean energy-related applications.
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The excessive and uncontrollable discharge of diverse organic pollutants into the environment has emerged as a significant concern, presenting a substantial risk to human health. Among the advanced oxidation processes used for the purification of wastewater, cold plasma technology is superior in fast and effective decontamination but often fails facing mixed pollutants. To address these issues, here we develop the new conceptual approach, plasma process, and proprietary reactor that ensure, for the first time, that the efficiency of treatment (114.7%) of two mixed organic dyes, methylene blue (MB) and methyl orange (MO), is higher than when the two dyes are treated separately. We further reveal the underlying mechanisms for the energy-efficient complete degradation of the mixed dyes. The contribution of plasma-induced ROS and the distinct degradation characteristics and mechanism of pollutants in mixed treatment are discussed. The electron transfer pathway revealed for the first time suggest that the mixed pollutants reduce the overall redox potentials and facilitate electron transfer during the plasma treatment, promoting synergistic degradation effects. The integrated frameworks including both direct and indirect mechanisms provide new insights into the high-efficiency mixed-contaminant treatment. The degradation products for mixed degradation are revealed based on the identification of intermediate species. The plasma-treated water is proven safe for living creatures in waterways and sustainable fishery applications, using in vivo zebrafish model bio-toxicity assay. Overall, these findings offer a feasible approach and new insights into the mechanisms for the development of highly-effective, energy-efficient technologies for wastewater treatment and reuse in agriculture, industry, and potentially in urban water networks.
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Poluentes Ambientais , Gases em Plasma , Poluentes Químicos da Água , Humanos , Animais , Águas Residuárias , Corantes/análise , Peixe-Zebra , Água , Poluentes Químicos da Água/análiseRESUMO
Heterogeneous catalysts with targeted functionality can be designed with atomic precision, but it is challenging to retain the structure and performance upon the scaled-up manufacturing. Particularly challenging is to ensure the "atomic economy", where every catalytic site is most gainfully utilized. Given the emerging synergistic integration of human- and artificial intelligence (AI)-driven augmented designs (AD), augmented analytics (AA), and augmented reality manufacturing (AM) platforms, this minireview focuses on single-atom heterogeneous catalysts (SAHCs) and examines the current status, challenges, and future perspectives of translating atomic-level structural precision and data-driven discovery to next-generation industrial manufacturing. We critically examine the atomistic insights into structure-driven SAHCs functionality and discuss the opportunities and challenges on the way towards the synergistic human-AI collaborative data-driven platform capable of monitoring, analyzing, manufacturing, and retaining the atomic-scale structure and functions. Enhanced by the atomic-level AD, AA, and AM, evolving from the current high-throughput capabilities and digital materials manufacturing acceleration, this synergistic human-AI platform is promising to enable atom-efficient and atomically precise heterogeneous catalyst production.
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Ammonia plays a crucial role in industry and agriculture worldwide, but traditional industrial ammonia production methods are energy-intensive and negatively impact the environment. Ammonia synthesis using low-temperature plasma technology has gained traction in the pursuit of environment-benign and cost-effective methods for producing green ammonia. This Review discusses the recent advances in low-temperature plasma-assisted ammonia synthesis, focusing on three main routes: N2+H2 plasma-only, N2+H2O plasma-only, and plasma coupled with other technologies. The reaction pathways involved in the plasma-assisted ammonia synthesis, as well as the process parameters, including the optimum catalyst types and discharge schemes, are examined. Building upon the current research status, the challenges and research opportunities in the plasma-assisted ammonia synthesis processes are outlined. The article concludes with the outlook for the future development of the plasma-assisted ammonia synthesis technology in real-life industrial applications.
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Cold atmospheric plasma (CAP) holds promise as a cancer-specific treatment that selectively kills various types of malignant cells. We used CAP-activated media (PAM) to utilize a range of the generated short- and long-lived reactive species. Specific antibodies, small molecule inhibitors and CRISPR/Cas9 gene-editing approaches showed an essential role for receptor tyrosine kinases, especially epidermal growth factor (EGF) receptor, in mediating triple negative breast cancer (TNBC) cell responses to PAM. EGF also dramatically enhanced the sensitivity and specificity of PAM against TNBC cells. Site-specific phospho-EGFR analysis, signal transduction inhibitors and reconstitution of EGFR-depleted cells with EGFR-mutants confirmed the role of phospho-tyrosines 992/1173 and phospholipase C gamma signaling in up-regulating levels of reactive oxygen species above the apoptotic threshold. EGF-triggered EGFR activation enhanced the sensitivity and selectivity of PAM effects on TNBC cells. The proposed approach based on the synergy of CAP and EGFR-targeted therapy may provide new opportunities to improve the clinical management of TNBC.
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Fator de Crescimento Epidérmico , Neoplasias de Mama Triplo Negativas , Humanos , Fator de Crescimento Epidérmico/farmacologia , Fator de Crescimento Epidérmico/metabolismo , Neoplasias de Mama Triplo Negativas/metabolismo , Linhagem Celular Tumoral , Receptores ErbB/metabolismo , Transdução de SinaisRESUMO
Dual single-atom catalysts (DSACs) are promising for breaking the scaling relationships and ensuring synergistic effects compared with conventional single-atom catalysts (SACs). Nevertheless, precise synthesis and optimization of DSACs with specific locations and functions remain challenging. Herein, dual single-atoms are specifically incorporated into the layer-stacked bulk-like carbon nitride, featuring in-plane three-coordinated Pd and interplanar four-coordinated Cu (Pd1-Cu1/b-CN) atomic sites, from both experimental results and DFT simulations. Using femtosecond time-resolved transient absorption (fs-TA) spectroscopy, it is found that the in-plane Pd features a charge decay lifetime of 95.6 ps which is much longer than that of the interplanar Cu (3.07 ps). This finding indicates that the in-plane Pd can provide electrons for the reaction as the catalytically active site in both structurally and dynamically favorable manners. Such a well-defined bi-functional cascade system ensures a 3.47-fold increase in CO yield compared to that of bulk-like CN (b-CN), while also exceeding the effects of single Pd1/b-CN and Cu1/b-CN sites. Furthermore, DFT calculations reveal that the inherent transformation from s-p coupling to d-p hybridization between the Pd site and CO2 molecule occurs during the initial CO2 adsorption and hydrogenation processes and stimulates the preferred CO2-to-CO reaction pathway.
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Due to ever-increasing global energy demands and dwindling resources, there is a growing need to develop materials that can fulfil the World's pressing energy requirements. Electrochemical energy storage devices have gained significant interest due to their exceptional storage properties, where the electrode material is a crucial determinant of device performance. Hence, it is essential to develop 3-D hierarchical materials at low cost with precisely controlled porosity and composition to achieve high energy storage capabilities. After presenting the brief updates on porous carbons (PCs), then this review will focus on the nitrogen (N) doped porous carbon materials (NPC) for electrochemical supercapacitors as the NPCs play a vital role in supercapacitor applications in the field of energy storage. Therefore, this review highlights recent advances in NPCs, including developments in the synthesis of NPCs that have created new methods for controlling their morphology, composition, and pore structure, which can significantly enhance their electrochemical performance. The investigated N-doped materials a wide range of specific surface areas, ranging from 181.5 to 3709â m2 g-1 , signifies a substantial increase in the available electrochemically active surface area, which is crucial for efficient energy storage. Moreover, these materials display notable specific capacitance values, ranging from 58.7 to 754.4â F g-1 , highlighting their remarkable capability to effectively store electrical energy. The outstanding electrochemical performance of these materials is attributed to the synergy between heteroatoms, particularly N, and the carbon framework in N-doped porous carbons. This synergy brings about several beneficial effects including, enhanced pseudo-capacitance, improved electrical conductivity, and increased electrochemically active surface area. As a result, these materials emerge as promising candidates for high-performance supercapacitor electrodes. The challenges and outlook in NPCs for supercapacitor applications are also presented. Overall, this review will provide valuable insights for researchers in electrochemical energy storage and offers a basis for fabricating highly effective and feasible supercapacitor electrodes.
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Interfaces of metal oxide heterojunctions display a variety of intriguing physical properties that enable novel applications in spintronics, quantum information, neuromorphic computing, and high-temperature superconductivity. One such LaAlO3 /SrTiO3 (LAO/STO) heterojunction hosts a 2D electron liquid (2DEL) presenting remarkable 2D superconductivity and magnetism. However, these remarkable properties emerge only at very low temperatures, while the heterostructure fabrication is challenging even at the laboratory scale, thus impeding practical applications. Here, a novel plasma-enabled fabrication concept is presented to develop the TiO2 /Ti3 O4 hetero-phase bilayer with a 2DEL that exhibits features of a weakly localized Fermi liquid even at room temperature. The hetero-phase bilayer is fabricated by applying a rapid plasma-induced phase transition that transforms a specific portion of anatase TiO2 thin film into vacancy-prone Ti3 O4 in seconds. The underlying mechanism relies on the screening effect of the achieved high-density electron liquid that suppresses the electron-phonon interactions. The achieved "adiabatic" electron transport in the hetero-phase bilayer offers strong potential for low-loss electric or plasmonic circuits and hot electron harvesting and utilization. These findings open new horizons for fabricating diverse multifunctional metal oxide heterostructures as an innovative platform for emerging clean energy, integrated photonics, spintronics, and quantum information technologies.