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1.
ACS Sens ; 9(8): 4134-4142, 2024 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-39096509

RESUMEN

Nitrogen dioxide (NO2) is a significant environmental and human health hazard. Current NO2 sensors often lack sensitivity and selectivity under ambient conditions. This study investigates ammonia pyrolysis modification of monolayer Ti3C2Tx MXene to enhance NO2 detection at room temperature. Nitrogen-doped Ti3C2Tx demonstrates a substantial improvement in sensitivity, with a response of 8.87% to 50 ppm of NO2 compared to 0.65% for the original sensor, representing a 13.8-fold increase. The nitrogen-doped sensor also exhibits superior selectivity and linearity for NO2 under ambient conditions. Theoretical analysis shows that nitrogen incorporation promotes enhanced interaction between Ti3C2Tx and its surface oxygen-containing functional groups through electronic hybridization, resulting in improved adsorption energy (1.80 |eV|) and electron transfer efficiency (0.67 |e|) for NO2, thereby enhancing its gas-sensing performance. This study highlights the potential of ammonia pyrolysis-treated Ti3C2Tx MXene for advancing NO2 sensor technologies with heightened performance at room temperature.


Asunto(s)
Dióxido de Nitrógeno , Nitrógeno , Temperatura , Titanio , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Nitrógeno/química , Titanio/química , Amoníaco/química , Amoníaco/análisis
2.
Environ Sci Technol ; 58(36): 16087-16099, 2024 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-39205652

RESUMEN

This study aims to fine-tune the plasma composition with a particular emphasis on reactive nitrogen species (RNS) including nitrogen dioxide (NO2), dinitrogen pentoxide (N2O5), and nitrous oxide (N2O), produced by a self-constructed cylindrical dielectric barrier discharge (CDBD). We demonstrated the effective manipulation of the plasma chemical profile by optimizing electrical properties, including the applied voltage and frequency, and by adjusting the nitrogen and oxygen ratios in the gas mixture. Additionally, quantification of these active species was achieved using Fourier transform infrared spectroscopy. The study further extends to exploring the aerosol polymerization of acrylamide (AM) into polyacrylamide (PAM), serving as a model reaction to evaluate the reactivity of different plasma-generated species, highlighting the significant role of NO2 in achieving high polymerization yields. Complementing our experimental data, molecular dynamics (MD) simulations, based on the ReaxFF reactive force field potential, explored the interactions between reactive oxygen species, specifically hydroxyl radicals (OH) and hydrogen peroxide (H2O2), with water molecules. Understanding these interactions, combined with the optimization of plasma chemistry, is crucial for enhancing the effectiveness of DBD plasma in environmental applications like air purification and water treatment.


Asunto(s)
Simulación de Dinámica Molecular , Óxido Nitroso , Especies de Nitrógeno Reactivo , Especies de Nitrógeno Reactivo/química , Óxido Nitroso/química , Gases em Plasma/química , Dióxido de Nitrógeno/química , Peróxido de Hidrógeno/química
3.
ACS Sens ; 9(8): 4079-4088, 2024 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-39057835

RESUMEN

Ambient pressure X-ray photoelectron spectroscopy (APXPS) is combined with simultaneous electrical measurements and supported by density functional theory calculations to investigate the sensing mechanism of tungsten disulfide (WS2)-based gas sensors in an operando dynamic experiment. This approach allows for the direct correlation between changes in the surface potential and the resistivity of the WS2 sensing active layer under realistic operating conditions. Focusing on the toxic gases NO2 and NH3, we concurrently demonstrate the distinct chemical interactions between oxidizing or reducing agents and the WS2 active layer and their effect on the sensor response. The experimental setup mimics standard electrical measurements on chemiresistors, exposing the sample to dry air and introducing the target gas analyte at different concentrations. This methodology applied to NH3 concentrations of 100, 230, and 760 and 14 ppm of NO2 establishes a benchmark for future APXPS studies on sensing devices, providing fast acquisition times and a 1:1 correlation between electrical response and spectroscopy data in operando conditions. Our findings contribute to a deeper understanding of the sensing mechanism in 2D transition metal dichalcogenides, paving the way for optimizing chemiresistor sensors for various industrial applications and wireless platforms with low energy consumption.


Asunto(s)
Amoníaco , Espectroscopía de Fotoelectrones , Amoníaco/análisis , Amoníaco/química , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Compuestos de Tungsteno/química , Teoría Funcional de la Densidad , Presión , Gases/análisis , Gases/química , Tungsteno/química
4.
ACS Sens ; 9(7): 3641-3651, 2024 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-38967239

RESUMEN

Limited by insufficient active sites and restricted mechanical strength, designing reliable and wearable gas sensors with high activity and ductility remains a challenge for detecting hazardous gases. In this work, a thermally induced and solvent-assisted oxyanion etching strategy was implemented for selective pore opening in a rigid microporous Cu-based metal-organic framework (referred to as CuM). A conductive CuM/MXene aerogel was then self-assembled through cooperative hydrogen bonding interactions between the carbonyl oxygen atom in PVP grafted on the surface of defect-rich Cu-BTC and the surface functional hydroxyl group on MXene. A flexible NO2 sensing performance using the CuM/MXene aerogel hybridized sodium alginate hydrogel is finally achieved, demonstrating extraordinary sensitivity (S = 52.47 toward 50 ppm of NO2), good selectivity, and rapid response/recovery time (0.9/4.5 s) at room temperature. Compared with commercial sensors, the relative error is less than 7.7%, thereby exhibiting significant potential for application in monitoring toxic and harmful gases. This work not only provides insights for guiding rational synthesis of ideal structure models from MOF composites but also inspires the development of high-performance flexible gas sensors for potential multiscenario applications.


Asunto(s)
Enlace de Hidrógeno , Estructuras Metalorgánicas , Temperatura , Estructuras Metalorgánicas/química , Geles/química , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Cobre/química , Gases/química , Gases/análisis , Alginatos/química
5.
ACS Sens ; 9(7): 3707-3719, 2024 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-38985951

RESUMEN

Gas sensors based on ambipolar materials offer significant advantages in reducing the size of the analytical system and enhancing its efficiency. Here, bilayer heterojunction devices are constructed using different octafluorinated phthalocyanine complexes, with Zn and Co as metal centers, combined with a lutetium bisphthalocyanine complex (LuPc2). Stable p-type behavior is observed for the ZnF8Pc/LuPc2 device under both electron-donating (NH3) and -oxidizing (NO2 and O3) gaseous species, while the CoF8Pc/LuPc2 device exhibits n-type behavior under reducing gases and p-type behavior under oxidizing gases. The nature of majority of the charge carriers of Co-based devices varies depending on the nature of target gases, displaying an ambipolar behavior. Both heterojunction devices demonstrate stable and observable response toward all three toxic gases in the sub-ppm range. Remarkably, the Co-based device is highly sensitive toward ammonia with a limit of detection (LOD) of 200 ppb, whereas the Zn-based device demonstrates exceptional sensitivity toward oxidizing gases, with excellent LOD values of 4.9 and 0.75 ppb toward NO2 and O3, respectively, which makes it one of the most effective organic heterojunction sensors reported so far for oxidizing gases.


Asunto(s)
Gases , Indoles , Zinc , Indoles/química , Gases/análisis , Gases/química , Zinc/química , Zinc/análisis , Isoindoles , Límite de Detección , Cobalto/química , Lutecio/química , Amoníaco/análisis , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Compuestos Organometálicos/química , Contaminantes Atmosféricos/análisis
6.
ACS Sens ; 9(7): 3741-3753, 2024 Jul 26.
Artículo en Inglés | MEDLINE | ID: mdl-38996081

RESUMEN

The persistent challenge of poor recovery characteristics of NO2 sensors operated at room temperature remains significant. However, the development of In2O3-based gas sensing materials provides a promising approach to accelerate response and recovery for sub-ppm of NO2 detection at room temperature. Herein, we propose a simple two-step method to synthesize a one-dimensional (1D) In2O3@ZnO heterostructure material with hollow microtubes, by coupling metal-organic frameworks (MOFs) (MIL-68 (In)) and zinc ions. Meanwhile, the In2O3@ZnO composite-based gas sensor exhibits superior sensitivity performance to NO2 under visible light activation. The response value to 5 ppm of NO2 at room temperature is as high as 1800, which is 35 times higher than that of the pure In2O3-based sensor. Additionally, the gas sensor based on the In2O3@ZnO heterostructure demonstrates a significantly reduced response/recovery time of 30 s/67 s compared to the sensor based on pure In2O3 (74 s/235 s). The outstanding gas sensing properties of the In2O3@ZnO heterostructure-based sensors can be attributed to the enhanced photogenerated charge separation efficiency resulting from the heterostructure effect, and the improved receptor function toward NO2, which can increase the reactive sites and gas adsorption capacity. In summary, this work proposes a low-cost and efficient method to synthesize a 1D heterostructure material with microtube structures, which can serve as a fundamental technique for developing high-performance room-temperature gas sensors.


Asunto(s)
Indio , Luz , Dióxido de Nitrógeno , Temperatura , Óxido de Zinc , Óxido de Zinc/química , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Indio/química , Estructuras Metalorgánicas/química , Gases/análisis , Gases/química
7.
ACS Sens ; 9(8): 4037-4046, 2024 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-39039775

RESUMEN

Exploration of novel self-powered gas sensors free of external energy supply restrictions, such as light illumination and mechanical vibration, for flexible and wearable applications is in urgent need. Herein, this work constructs a flexible and self-powered NO2 gas sensor based on zinc-air batteries (ZABs) with the cathode of the ZABs also acting as the gas-sensitive layer. Furthermore, the SiO2 coating film, serving as a hydrophobic layer, increases the three-phase interfaces for the NO2 reduction reaction. The constructed sensors exhibit a high sensing response (0.3 V @ 5 ppm), an ultralow detection limit (61 ppb), a fast sensing process (129 and 103 s), and excellent selectivity. Moreover, the sensors also possess a wide working temperature range and a low working temperature tolerance (0.34 V at -15 °C). Simulations indicate that the hydrophobic surface at the cathode-hydrogel interface will accommodate more NO2 gas molecules at the reaction sites and prevent the influence of inner water evaporation and direct dissolution of NO2 in the electrolyte, which is beneficial to the enhanced gas sensing abilities. Finally, the self-powered sensing device is incorporated into a smart sensing system for practical applications. This work will pave a new insight into the construction of integrated and energy self-sufficient smart gas sensing systems.


Asunto(s)
Suministros de Energía Eléctrica , Dióxido de Nitrógeno , Zinc , Zinc/química , Zinc/análisis , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Aire , Electrodos , Límite de Detección , Gases/análisis , Gases/química , Dióxido de Silicio/química
8.
Chemosphere ; 362: 142669, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38906186

RESUMEN

Exposure to ozone (O3) and nitrogen dioxide (NO2) are related to pulmonary dysfunctions and various lung diseases, but the underlying biochemical mechanisms remain uncertain. Herein, the effect of inhalable oxidizing gas pollutants on the pulmonary surfactant (PS, extracted from porcine lungs), a mixture of active lipids and proteins that plays an important role in maintaining normal respiratory mechanics, is investigated in terms of the interfacial chemistry using in-vitro experiments; and the oxidative stress induced by oxidizing gases in the simulated lung fluid (SLF) supplemented with the PS is explored. The results showed that O3 and NO2 individually increased the surface tension of the PS and reduced its foaming ability; this was accompanied by the surface pressure-area isotherms of the PS monolayers shifting toward lower molecular areas, with O3 exhibiting more severe effects than NO2. Moreover, both O3 and NO2 produced reactive oxygen species (ROS) resulting in lipid peroxidation and protein damage to the PS. The formation of superoxide radicals (O2•-) was correlated with the decomposition of O3 and the reactions of O3 and NO2 with antioxidants in the SLF. These radicals, in the presence of antioxidants, led to the formation of hydrogen peroxide and hydroxyl radicals (•OH). Additionally, the direct oxidation of unsaturated lipids by O3 and NO2 further caused an increase in the ROS content. This change in the ROS chemistry and increased •OH production tentatively explain how inhalable oxidizing gases lead to oxidative stress and adverse health effects. In summary, our results indicated that inhaled O3 and NO2 exposure can significantly alter the interfacial properties of the PS, oxidize its active ingredients, and induce ROS formation in the SLF. The results of this study provide a basis for the elucidation of the potential hazards of inhaled oxidizing gas pollutants in the human respiratory system.


Asunto(s)
Pulmón , Dióxido de Nitrógeno , Estrés Oxidativo , Ozono , Surfactantes Pulmonares , Especies Reactivas de Oxígeno , Estrés Oxidativo/efectos de los fármacos , Animales , Surfactantes Pulmonares/química , Porcinos , Dióxido de Nitrógeno/química , Ozono/química , Ozono/toxicidad , Especies Reactivas de Oxígeno/metabolismo , Pulmón/efectos de los fármacos , Pulmón/metabolismo , Contaminantes Atmosféricos/toxicidad , Contaminantes Atmosféricos/química , Peroxidación de Lípido/efectos de los fármacos , Antioxidantes/química , Oxidación-Reducción
9.
Bioorg Chem ; 149: 107531, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-38850779

RESUMEN

Nitroreductase (NTR) overexpression often occurs in tumors, highlighting the significance of effective NTR detection. Despite the utilization of various optical methods for this purpose, the absence of an efficient tumor-targeting optical probe for NTR detection remains a challenge. In this research, a novel tumor-targeting probe (Cy-Bio-NO2) is developed to perform dual-modal NTR detection using near-infrared fluorescence and photoacoustic techniques. This probe exhibits exceptional sensitivity and selectivity to NTR. Upon the reaction with NTR, Cy-Bio-NO2 demonstrates a distinct fluorescence "off-on" response at 800 nm, with an impressive detection limit of 12 ng/mL. Furthermore, the probe shows on-off photoacoustic signal with NTR. Cy-Bio-NO2 has been successfully employed for dual-modal NTR detection in living cells, specifically targeting biotin receptor-positive cancer cells for imaging purposes. Notably, this probe effectively detects tumor hypoxia through dual-modal imaging in tumor-bearing mice. The strategy of biotin incorporation markedly enhances the probe's tumor-targeting capability, facilitating its engagement in dual-modal imaging at tumor sites. This imaging capacity holds substantial promise as an accurate tool for cancer diagnosis.


Asunto(s)
Colorantes Fluorescentes , Nitrorreductasas , Imagen Óptica , Animales , Humanos , Ratones , Colorantes Fluorescentes/química , Colorantes Fluorescentes/síntesis química , Ratones Endogámicos BALB C , Ratones Desnudos , Estructura Molecular , Neoplasias/diagnóstico por imagen , Neoplasias Experimentales/diagnóstico por imagen , Neoplasias Experimentales/metabolismo , Nitrorreductasas/metabolismo , Nitrorreductasas/análisis , Técnicas Fotoacústicas , Dióxido de Nitrógeno/síntesis química , Dióxido de Nitrógeno/química
10.
Int J Mol Sci ; 25(10)2024 May 17.
Artículo en Inglés | MEDLINE | ID: mdl-38791510

RESUMEN

α-CD:N2O "host-guest" type complexes were formed by a simple solid-gas reaction (N2O sorption into α-CD) under different gas pressures and temperatures. The new N2O inclusion method applied in the present study was compared with the already known technique based on the crystallization of clathrates from a water solution of α-CD saturated with N2O. A maximum storage capacity of 4.5 wt.% N2O was achieved when charging the cyclodextrin from a gas phase. The amount of included gas decreases to 1.3 wt.% when the complex is stored in air at 1 atm and room temperature, analogous to that achieved by the crystallization of α-CD:N2O. Furthermore, it was shown that the external coordination of N2O to either the upper or lower rim of α-CD without hydration water displacement is the preferred mode of binding, due to hydrogen bonds with neighboring -OH groups from the host macrocycle and three of the hydration water molecules nearby. The capacity of α-CD to store N2O and the thermal stability of the α-CD:N2O complex demonstrated promising applications of these types of complexes in food and beverages.


Asunto(s)
alfa-Ciclodextrinas , alfa-Ciclodextrinas/química , Enlace de Hidrógeno , Temperatura , Dióxido de Nitrógeno/química , Agua/química , Adsorción
11.
ACS Sens ; 9(6): 3178-3186, 2024 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-38778734

RESUMEN

Large emissions of nitrogen dioxide (NO2) pose a significant threat to human health, Monitoring its content and implementing timely measures are crucial. Utilizing oxide semiconductors, such as tin dioxide (SnO2), has proven to be an effective way to detect and analyze NO2. The design and preparation of sensing materials with high sensitivity and excellent selectivity is the key to improve the detection efficiency. SnO2 nanopowders with small and uniform particle size, large specific surface area, adjustable defect content, and no impurities were prepared by a new plasma spraying method. The SnO2 nanopowders exhibit outstanding performance in detecting NO2 at a low temperature of 100 °C, the response to 5 ppm of NO2 reaches 48, and the material demonstrates rapid response and recovery times, coupled with excellent selectivity. The exceptional gas-sensitive properties can be attributed to the superior morphology and structure of SnO2. It provides more reaction sites for gas sensitive reactions, fast electron transport, a large number of charge carriers, and improved adsorption of the material to the target gas. This study provides valuable insights into nanomaterial preparation and the enhancement of gas-sensitive properties for SnO2.


Asunto(s)
Dióxido de Nitrógeno , Compuestos de Estaño , Compuestos de Estaño/química , Dióxido de Nitrógeno/química , Dióxido de Nitrógeno/análisis , Gases/química , Tamaño de la Partícula
12.
ACS Sens ; 9(6): 3187-3197, 2024 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-38809143

RESUMEN

Ultrasensitive photoelectric detection of nitrogen dioxide (NO2) with PHI under visible light irradiation at room temperature (RT) remains an ongoing challenge due to the low charge separation and scarce adsorption sites. In this work, a dimensionally matched ultrathin CoNiHHTP MOF/PHI Z-scheme heterojunction is successfully constructed by taking advantage of the π-π interactions existing between the CoNiHHTP MOF and PHI. The amount-optimized heterojunction possesses a record detection limit of 1 ppb (response = 15.6%) for NO2 under 405 nm irradiation at RT, with reduced responsive (3.6 min) and recovery (2.7 min) times, good selectivity and reversibility, and long-time stability (150 days) compared with PHI, even superior to others reported at RT. Based on the time-resolved photoluminescence spectra, in situ X-ray photoelectron spectra, and diffuse reflectance infrared Fourier transform spectroscopy results, the resulting sensing performance is attributed to the favorable Z-scheme charge transfer and separation. Moreover, the Ni nodes favorably present in adjacent metal sites between the lamellae contribute to charge transfer and redistribution, whereas Co nodes could act as selective centers for promoted adsorption of NO2. Interestingly, it is confirmed that the CoNiHHTP MOF/PHI heterojunction could effectively reduce the influence of O2 in the gas-sensitive reaction due to their unique bimetallic (Co and Ni) nodes, which is also favorable for the improved sensing performances for NO2. This work provides a feasible strategy to develop promising PHI-based optoelectronic gas sensors at RT.


Asunto(s)
Estructuras Metalorgánicas , Dióxido de Nitrógeno , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Estructuras Metalorgánicas/química , Estructuras Metalorgánicas/efectos de la radiación , Luz , Límite de Detección , Temperatura
13.
Int J Mol Sci ; 25(8)2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38674006

RESUMEN

The aim of this study was to obtain nitrogen-enriched activated carbons from orthocoking coal. The initial material was subjected to a demineralisation process. The demineralised precursor was pyrolysed at 500 °C and then activated with sodium hydroxide at 800 °C. Activated carbon adsorbents were subjected to the process of ammoxidation using a mixture of ammonia and air at two different temperature variants (300 and 350 °C). Nitrogen introduction was carried out on stages of demineralised precursor, pyrolysis product, and oxidising activator. The elemental composition, acid-base properties, and textural parameters of the obtained carbon adsorbents were determined. The activated carbons were investigated for their ability to remove nitrogen dioxide. The results demonstrated that the ammoxidation process incorporates new nitrogen-based functional groups into the activated carbon structure. Simultaneously, the ammoxidation process modified the acid-base characteristics of the surface and negatively affected the textural parameters of the resulting adsorbents. Furthermore, the study showed that all of the obtained carbon adsorbents exhibited a distinct microporous texture. Adsorption tests were carried out against NO2 and showed that the carbon adsorbents obtained were highly effective in removing this gaseous pollutant. The best sorption capacity towards NO2 was 23.5 mg/g under dry conditions and 75.0 mg/g under wet conditions.


Asunto(s)
Carbón Orgánico , Dióxido de Nitrógeno , Nitrógeno , Adsorción , Dióxido de Nitrógeno/química , Nitrógeno/química , Carbón Orgánico/química , Carbono/química , Temperatura , Carbón Mineral
14.
Environ Sci Technol ; 58(18): 7904-7915, 2024 May 07.
Artículo en Inglés | MEDLINE | ID: mdl-38661303

RESUMEN

Nitrogen dioxide (NO2) hydrolysis in deliquesced aerosol particles forms nitrous acid and nitrate and thus impacts air quality, climate, and the nitrogen cycle. Traditionally, it is considered to proceed far too slowly in the atmosphere. However, the significance of this process is highly uncertain because kinetic studies have only been made in dilute aqueous solutions but not under high ionic strength conditions of the aerosol particles. Here, we use laboratory experiments, air quality models, and field measurements to examine the effect of the ionic strength on the reaction kinetics of NO2 hydrolysis. We find that high ionic strengths (I) enhance the reaction rate constants (kI) by more than an order of magnitude compared to that at infinite dilution (kI=0), yielding log10(kI/kI=0) = 0.04I or rate enhancement factor = 100.04I. A state-of-the-art air quality model shows that the enhanced NO2 hydrolysis reduces the negative bias in the simulated concentrations of nitrous acid by 28% on average when compared to field observations over the North China Plain. Rapid NO2 hydrolysis also enhances the levels of nitrous acid in other polluted regions such as North India and further promotes atmospheric oxidation capacity. This study highlights the need to evaluate various reaction kinetics of atmospheric aerosols with high ionic strengths.


Asunto(s)
Aerosoles , Aerosoles/química , Hidrólisis , Concentración Osmolar , Dióxido de Nitrógeno/química , Cinética , Atmósfera/química , Contaminantes Atmosféricos/química
15.
ACS Sens ; 9(4): 1967-1977, 2024 04 26.
Artículo en Inglés | MEDLINE | ID: mdl-38494643

RESUMEN

Bimetallic nanocrystals (NCs) have obtained significant attention due to their unique advantages of the intrinsic properties of individual metals and synergistic enhancements resulting from the electronic coupling between two constituent metals. In this work, Pd@Pt core-shell NCs were prepared through a facile one-pot solution-phase method, which had excellent dispersion and uniform size. Concurrently, ZnO nanosheets were prepared via a hydrothermal method. To explore their potential in nitrogen dioxide (NO2) gas sensing applications, sensitive materials based on ZnO nanosheets with varying mass percentages of Pd@Pt NCs were generated through an impregnation process. The sensor based on 0.3 wt % Pd@Pt-ZnO exhibited remarkable performance, demonstrating a substantial response (Rg/Ra = 60.3) to 50 ppb of NO2 at a low operating temperature of 80 °C. Notably, this sensor reached an outstanding low detection limit of 300 ppt. The enhancement in gas sensing capabilities can be attributed to the sensitization and synergistic effects imparted by the exceptional catalytic activity of Pd@Pt NCs, which significantly promoted the reaction. This research introduces a novel approach for the utilization of core-shell structured bimetallic nanocrystals as modifiers in metal-oxide-semiconductor (MOS) materials for NO2 detection.


Asunto(s)
Dióxido de Nitrógeno , Paladio , Platino (Metal) , Óxido de Zinc , Óxido de Zinc/química , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Paladio/química , Platino (Metal)/química , Nanopartículas del Metal/química , Límite de Detección
16.
ACS Sens ; 9(5): 2372-2382, 2024 05 24.
Artículo en Inglés | MEDLINE | ID: mdl-38401047

RESUMEN

Rapid and ultrasensitive detection of toxic gases at room temperature is highly desired in health protection but presents grand challenges in the sensing materials reported so far. Here, we present a gas sensor based on novel zero dimensional (0D)/two dimensional (2D) indium oxide (In2O3)/titanium carbide (Ti3C2Tx) Schottky heterostructures with a high surface area and rich oxygen vacancies for parts per billion (ppb) level nitrogen dioxide (NO2) detection at room temperature. The In2O3/Ti3C2Tx gas sensor exhibits a fast response time (4 s), good response (193.45% to 250 ppb NO2), high selectivity, and excellent cycling stability. The rich surface oxygen vacancies play the role of active sites for the adsorption of NO2 molecules, and the Schottky junctions effectively adjust the charge-transfer behavior through the conduction tunnel in the sensing material. Furthermore, In2O3 nanoparticles almost fully cover the Ti3C2Tx nanosheets which can avoid the oxidation of Ti3C2Tx, thus contributing to the good cycling stability of the sensing materials. This work sheds light on the sensing mechanism of heterojunction nanostructures and provides an efficient pathway to construct high-performance gas sensors through the rational design of active sites.


Asunto(s)
Indio , Dióxido de Nitrógeno , Temperatura , Titanio , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Titanio/química , Indio/química , Porosidad
17.
Environ Pollut ; 334: 122134, 2023 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-37414123

RESUMEN

Mineral particles in air could provide atmospheric chemical reaction interface for gaseous substances and participate in atmospheric chemical reaction process, and affecting the status and levels of gaseous pollutants in air. However, differences of the heterogenous reaction on the surface minerals particles are not very clear. Considering main mineral composition of ambient particles was from dust emission, therefore, typical clay minerals (chlorite, illite) and desert particles (Taklimakan Desert) were selected to analysize chemical reaction of NO2, one of major gaseous pollutants, on mineral particles by using of In-situ DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) under different condition. And In situ near-ambient pressure X-ray photoelectron spectroscopy (In situ NAP-XPS) was employed to investigate iron (one of the major metals) species variation on the surface of mineral dust particles during the heterogeneous reactions. Our data show that humidity controlled by deuterium oxide (D2O) has a greater effect on chemical reactions compared to light and temperature. Under dry conditions, the amount of heterogeneous reaction products of NO2 on the particles shows Xiaotang dust > chlorite > illite > Tazhong dust regardless of dark or light conditions. In contrast, under humidity conditions, the order of nitrate product quantity under moderate conditions was chlorite > illite > Xiaotang dust > Tazhong dust. In situ NAP-XPS results demonstrate that specie variation of the Fe could promote the heterogenous reactions. These data could provide useful information for understanding the formation mechanism of nitrate aerosols and removal of nitrogen oxides in the atmosphere.


Asunto(s)
Polvo , Contaminantes Ambientales , Polvo/análisis , Arcilla , Dióxido de Nitrógeno/química , Nitratos , Minerales/química , Gases , Aerosoles/química
18.
Chembiochem ; 24(12): e202200731, 2023 06 15.
Artículo en Inglés | MEDLINE | ID: mdl-36944581

RESUMEN

Kinetic studies revealed that nitrate radicals (NO3 ⋅), which are formed through reaction of the noxious air pollutants nitrogen dioxide (NO2 ⋅) and ozone (O3 ), very rapidly oxidize phenylalanine residues in an aqueous environment, with overall rate coefficients in the 108 -109  M-1 s-1 range. With amino acids and dipeptides as model systems, the data suggest that the reaction proceeds via a π-complex between NO3 ⋅ and the aromatic ring in Phe, which subsequently decays into a charge transfer (CT) complex. The stability of the π-complex is sequence-dependent and is increased when Phe is at the N terminus of the dipeptide. Computations revealed that the considerably more rapid radical-induced oxidation of Phe residues in both neutral and acidic aqueous environments, compared to acetonitrile, can be attributed to stabilization of the CT complex by the protic solvent; this clearly highlights the health-damaging potential of exposure to combined NO2 ⋅ and O3 .


Asunto(s)
Nitratos , Dióxido de Nitrógeno , Nitratos/química , Dióxido de Nitrógeno/química , Fenilalanina/química , Cinética , Oxidación-Reducción , Dipéptidos/química
19.
Sci Total Environ ; 838(Pt 1): 155973, 2022 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-35588848

RESUMEN

Urban grime represents an important environmental surface for heterogeneous reactions in urban environment. Here, we assess the physical and chemical properties of urban grime collected during six consecutive months in downtown of Guangzhou, China. There is a significant variation of the uptake coefficients of NO2 on the urban grime as a function of the relative humidity (RH). In absence of water molecules (0% RH), the light-induced uptake coefficients of NO2 on urban grime samples collected during six months are very similar in order of ≈10-6. At 80% RH, depending on the sampling month the light-induced uptake coefficient of NO2 can reach one order of magnitude higher values (1.5 × 10-5, at 80% RH) compared to those uptakes at 0% RH. In presence of 80% RH, there are strong correlations between the measured NO2 uptakes and the concentrations of the water soluble carbon, soluble anions, polycyclic aromatic hydrocarbons and n-alkanes depicted in the urban grime. These correlations, demonstrate that surface adsorbed water on urban grime play an important role for the uptakes of NO2. The heterogeneous conversion of NO2 on two-month old urban grime under sunlight irradiation (68 W m-2, 300 nm < λ < 400 nm) at 60% RH leads to the formation of unprecedented HONO surface flux of 4.7 × 1010 molecules cm-2 s-1 which is higher than all previously observed HONO fluxes, thereby affecting the oxidation capacity of the urban atmosphere. During the heterogeneous chemistry of NO2 with urban grime, the unsaturated and N-containing organic compounds are released in the gas phase which can affect the air quality in the urban environment.


Asunto(s)
Atmósfera , Dióxido de Nitrógeno , Atmósfera/química , China , Dióxido de Nitrógeno/química , Luz Solar , Agua/química
20.
Environ Pollut ; 304: 119124, 2022 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-35367103

RESUMEN

Responses to COVID-19 altered environmental exposures and health behaviours associated with non-communicable diseases. We aimed to (1) quantify changes in nitrogen dioxide (NO2), noise, physical activity, and greenspace visits associated with COVID-19 policies in the spring of 2020 in Barcelona (Spain), Vienna (Austria), and Stockholm (Sweden), and (2) estimated the number of additional and prevented diagnoses of myocardial infarction (MI), stroke, depression, and anxiety based on these changes. We calculated differences in NO2, noise, physical activity, and greenspace visits between pre-pandemic (baseline) and pandemic (counterfactual) levels. With two counterfactual scenarios, we distinguished between Acute Period (March 15th - April 26th, 2020) and Deconfinement Period (May 2nd - June 30th, 2020) assuming counterfactual scenarios were extended for 12 months. Relative risks for each exposure difference were estimated with exposure-risk functions. In the Acute Period, reductions in NO2 (range of change from -16.9 µg/m3 to -1.1 µg/m3), noise (from -5 dB(A) to -2 dB(A)), physical activity (from -659 MET*min/wk to -183 MET*min/wk) and greenspace visits (from -20.2 h/m to 1.1 h/m) were largest in Barcelona and smallest in Stockholm. In the Deconfinement Period, NO2 (from -13.9 µg/m3 to -3.1 µg/m3), noise (from -3 dB(A) to -1 dB(A)), and physical activity levels (from -524 MET*min/wk to -83 MET*min/wk) remained below pre-pandemic levels in all cities. Greatest impacts were caused by physical activity reductions. If physical activity levels in Barcelona remained at Acute Period levels, increases in annual diagnoses for MI (mean: 572 (95% CI: 224, 943)), stroke (585 (6, 1156)), depression (7903 (5202, 10,936)), and anxiety (16,677 (926, 27,002)) would be anticipated. To decrease cardiovascular and mental health impacts, reductions in NO2 and noise from the first COVID-19 surge should be sustained, but without reducing physical activity. Focusing on cities' connectivity that promotes active transportation and reduces motor vehicle use assists in achieving this goal.


Asunto(s)
Contaminantes Atmosféricos , Contaminación del Aire , COVID-19 , Accidente Cerebrovascular , Contaminantes Atmosféricos/análisis , Contaminación del Aire/análisis , COVID-19/epidemiología , Ciudades/epidemiología , Exposición a Riesgos Ambientales/análisis , Conductas Relacionadas con la Salud , Humanos , Salud Mental , Dióxido de Nitrógeno/análisis , Dióxido de Nitrógeno/química , Pandemias , Material Particulado/análisis
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