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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 324: 124962, 2025 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-39146628

RESUMO

Two isostructural, three-dimensional, interpenetrated amino-functionalized Metal-Organic Frameworks (Co-2AIN-MOF and Cd-2AIN-MOF) based on 2-aminoisonicotinic acid (2AIN) were synthesized, structurally characterized and determined. Based on the PXRD analysis, the solvent exchange hardly changed their framework structure, and the samples fully activated by methanol can be achieved and examined by infrared spectroscopy. Due to the presence of the carbonyl group and free amino groups in the pore of the framework, the NH3 uptakes of Co-2AIN-MOF and Cd-2AIN-MOF are 11.70 and 13.81 mmol/g and at 1 bar, respectively. In-situ Infrared spectroscopy and DFT calculations revealed the different adsorption sites and processes between Co-2AIN-MOF and Cd-2AIN-MOF.

2.
J Environ Sci (China) ; 150: 202-217, 2025 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-39306396

RESUMO

This study focuses on the spatiotemporal distribution, urban-rural variations, and driving factors of ammonia Vertical Column Densities (VCDs) in China's Yangtze River Delta region (YRD) from 2008 to 2020. Utilizing data from the Infrared Atmospheric Sounding Interferometer (IASI), Generalized Additive Models (GAM), and the GEOS-Chem chemical transport model, we observed a significant increase of NH3 VCDs in the YRD between 2014 and 2020. The spatial distribution analysis revealed higher NH3 concentrations in the northern part of the YRD region, primarily due to lower precipitation, alkaline soil, and intensive agricultural activities. NH3 VCDs in the YRD region increased significantly (65.18%) from 2008 to 2020. The highest growth rate occurs in the summer, with an annual average growth rate of 7.2% during the period from 2014 to 2020. Agricultural emissions dominated NH3 VCDs during spring and summer, with high concentrations primarily located in the agricultural areas adjacent to densely populated urban zones. Regions within several large urban areas have been discovered to exhibit relatively stable variations in NH3 VCDs. The rise in NH3 VCDs within the YRD region was primarily driven by the reduction of acidic gases like SO2, as emphasized by GAM modeling and sensitivity tests using the GEOS-Chem model. The concentration changes of acidic gases contribute to over 80% of the interannual variations in NH3 VCDs. This emphasizes the crucial role of environmental policies targeting the reduction of these acidic gases. Effective emission control is urgent to mitigate environmental hazards and secondary particulate matter, especially in the northern YRD.


Assuntos
Poluentes Atmosféricos , Amônia , Monitoramento Ambiental , Rios , China , Amônia/análise , Poluentes Atmosféricos/análise , Rios/química , Agricultura , Análise Espaço-Temporal , Estações do Ano
3.
J Environ Sci (China) ; 150: 490-502, 2025 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-39306423

RESUMO

The removal of ammonia nitrogen (NH4+-N) and bacteria from aquaculture wastewater holds paramount ecological and production significance. In this study, Pt/RuO2/g-C3N4 photocatalysts were prepared by depositing Pt and RuO2 particles onto g-C3N4. The physicochemical properties of photocatalysts were explored by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and UV-vis diffuse reflectance spectrometer (UV-vis DRS). The photocatalysts were then applied to the removal of both NH4+-N and bacteria from simulated mariculture wastewater. The results clarified that the removals of both NH4+-N and bacteria were in the sequence of g-C3N4 < RuO2/g-C3N4 < Pt/g-C3N4 < Pt/RuO2/g-C3N4. This magnificent photocatalytic ability of Pt/RuO2/g-C3N4 can be interpreted by the transfer of holes from g-C3N4 to RuO2 to facilitate the in situ generation of HClO from Cl- in wastewater, while Pt extracts photogenerated electrons for H2 formation to enhance the reaction. The removal of NH4+-N and disinfection effect were more pronounced in simulated seawater than in pure water. The removal efficiency of NH4+-N increases with an increase in pH of wastewater, while the bactericidal effect was more significant under a lower pH in a pH range of 6-9. In actual seawater aquaculture wastewater, Pt/RuO2/g-C3N4 still exhibits effective removal efficiency of NH4+-N and bactericidal performance under sunlight. This study provides an alternative avenue for removement of NH4+-N and bacteria from saline waters under sunlight.


Assuntos
Amônia , Bactérias , Eliminação de Resíduos Líquidos , Águas Residuárias , Poluentes Químicos da Água , Águas Residuárias/química , Amônia/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Rutênio/química , Luz , Aquicultura/métodos , Platina/química , Catálise , Grafite , Compostos de Nitrogênio
4.
J Colloid Interface Sci ; 677(Pt A): 369-377, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39096705

RESUMO

In the domain of electrocatalytic NO3- reduction (NO3-RR) for the treatment of low-concentration nitrate-containing domestic or industrial wastewater, the conversion of NO3- into NH4+ holds significant promise for resource recovery. Nevertheless, the central challenge in this field revolves around the development of catalysts exhibiting both high catalytic activity and selectivity. To tackle this challenge, we design a two-step hydrothermal combine with carbonization process to fabricate a cobalt-doped Fe-based MOF (MIL-101) catalyst at 800 °C temperatures. The aim was to fully leverage cobalt's demonstrated high selectivity in NO3- electroreduction and enhance activity by promoting electron transfer through the d-band of Fe. The results indicate that the synthesized catalyst inherits multiple active sites from its precursor, with the co-doping process optimized through the topological properties of the MOF. Elemental analysis and oxidation state testing were employed to scrutinize the fundamental characteristics of this catalyst type and comprehend how these features may influence its efficiency. Electrochemical analysis revealed that, even under conditions of low NO3- concentration, the Cox@MIL-Fe catalyst achieved an impressive nitrate conversion rate of 98 % at -0.9 V vs. RHE. NH4+ selectivity was notably high at 87 %, and the by-product NO2- levels remained at a minimal threshold. The Faradaic efficiency for NH4+ reached 74 %, with ammonia yield approaching 0.08 mmol h-1 cm-2. This study furnishes indispensable research data for the design of Fe-based electrocatalysts for nitrate reduction, offering profound insights into the modulation of catalysts to play a pivotal role in the electroreduction of nitrate ions.

5.
Talanta ; 281: 126916, 2025 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-39305764

RESUMO

In this work, three different dyes have been tested for the determination of gaseous ammonia. This gas is one of the products of microbial degradation and therefore its presence is an indicator of deterioration and could be used as a food freshness indicator. Three different sensors have been prepared and tested, two of them using the natural pigments curcumin and anthocyanin and the other one using bromothymol blue. All of them are biocompatible and therefore allowed to use in contact with food. Different compositions, materials for deposition, stability and reversibility for ammonia gas detection have been studied under high humidity conditions simulating real packaged food conditions. Colorimetry is the technique used to obtain the analytical parameter, the H coordinate of the HSV colour space, simply using a camera, avoiding the use of complex instrumentation. Sensibility, toxicity grade and stability found show that the sensor could be implemented in packaged food and form the basis of a freshness indicator for the food industry.


Assuntos
Amônia , Gases , Amônia/análise , Gases/análise , Gases/química , Materiais Biocompatíveis/química , Colorimetria/métodos , Curcumina/química , Curcumina/análise , Antocianinas/análise , Antocianinas/química , Embalagem de Alimentos , Corantes/química
6.
J Colloid Interface Sci ; 677(Pt B): 853-861, 2025 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-39173517

RESUMO

Electrocatalytic nitrate reduction reaction presents a promising avenue for environmentally friendly ammonia (NH3) synthesis and wastewater treatment. An essential aspect to consider is the meticulous design of electrocatalysts. This study explores the utilization of a Ni-Co alloy nanosheet-decorated three-dimensional titanium dioxide (3D-TiO2) nanobelts electrodeposited on titanium meshes (NixCoy@TiO2/TM) for efficient electrocatalytic NH3 production. The optimized Ni1Co3@TiO2/TM electrode achieves a significant NH3 yield of 676.3 ± 27.1 umol h-1 cm-2 with an impressive Faradaic efficiency (FE) of 95.1 % ± 2.1 % in a 0.1 M KOH solution containing 0.1 M NO3- at -0.4 V versus the reversible hydrogen electrode. Additionally, the electrode demonstrates exceptional electrochemical activity for NH3 synthesis in simulated wastewater, delivering an outstanding NH3 yield of 751.6 ± 44.3 umol h-1 cm-2 with a FE of 96.8 % ± 0.4 % at the same potential of -0.4 V. Moreover, the electrode exhibits minimal variation in current density, NH3 yields and FEs throughout the 24-h stability test and the 20-cycle test, demonstrating its excellent stability and durability. This study offers a straightforward electrodeposited approach for the development of 3D-nanostructured alloys as catalysts for NH3 electrosynthesis from nitrates at room temperature.

7.
J Environ Sci (China) ; 149: 638-650, 2025 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-39181674

RESUMO

High ammonia-nitrogen digestate has become a key bottleneck limiting the anaerobic digestion of organic solid waste. Vacuum ammonia stripping can simultaneously remove and recover ammonia nitrogen, which has attracted a lot of attention in recent years. To investigate the parameter effects on the efficiency and mass transfer, five combination conditions (53 °C 15 kPa, 60 °C 20 kPa, 65 °C 25 kPa, 72 °C 35 kPa, and 81 °C 50 kPa) were conducted for ammonia stripping of sludge digestate. The results showed that 80% of ammonia nitrogen was stripped in 45 min for all experimental groups, but the ammonia transfer coefficient varied under different conditions, which increased with the rising of boiling point temperature, and reached the maximum value (39.0 mm/hr) at 81 °C 50 kPa. The ammonia nitrogen removal efficiency was more than 80% for 30 min vacuum stripping after adjusting the initial pH to above 9.5, and adjustment of the initial alkalinity also affects the pH value of liquid digestate. It was found that pH and alkalinity are the key factors influencing the ammonia nitrogen dissociation and removal efficiency, while temperature and vacuum mainly affect the ammonia nitrogen mass transfer and removal velocity. In terms of the mechanism of vacuum ammonia stripping, it underwent alkalinity destruction, pH enhancement, ammonia nitrogen dissociation, and free ammonia removal. In this study, two-stage experiments of alkalinity destruction and ammonia removal were also carried out, which showed that the two-stage configuration was beneficial for ammonia removal. It provides a theoretical basis and practical technology for the vacuum ammonia stripping from liquid digestate of organic solid waste.


Assuntos
Amônia , Temperatura , Eliminação de Resíduos Líquidos , Amônia/química , Concentração de Íons de Hidrogênio , Vácuo , Eliminação de Resíduos Líquidos/métodos , Nitrogênio , Esgotos/química , Pressão
8.
J Environ Sci (China) ; 150: 385-394, 2025 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-39306414

RESUMO

The inhibitory effects of zinc oxide nanoparticles (ZnO NPs) and impacts of N-acyl-homoserine lactone (AHL)-based quorum sensing (QS) on biological nitrogen removal (BNR) performance have been well-investigated. However, the effects of ammonia nitrogen (NH4+-N) concentrations on NP toxicity and AHL regulation have seldom been addressed yet. This study consulted on the impacts of ZnO NPs on BNR systems when high NH4+-N concentration was available. The synergistic toxic effects of high-strength NH4+-N (200 mg/L) and ZnO NPs resulted in decreased ammonia oxidation rates and dropped the nitrogen removal efficiencies by 17.5% ± 0.2%. The increased extracellular polymeric substances (EPS) production was observed in response to the high NH4+-N and ZnO NP stress, which indicated the defense mechanism against the toxic effects in the BNR systems was stimulated. Furthermore, the regulatory effects of exogenous N-decanoyl-homoserine lactone (C10-HSL)-mediated QS system on NP-stressed BNR systems were revealed to improve the BNR performance under different NH4+-N concentrations. The C10-HSL regulated the intracellular reactive oxygen species levels, denitrification functional enzyme activities, and antioxidant enzyme activities, respectively. This probably synergistically enhanced the defense mechanism against NP toxicity. However, compared to the low NH4+-N concentration of 60 mg/L, the efficacy of C10-HSL was inhibited at high NH4+-N levels of 200 mg/L. The findings provided the significant application potential of QS system for BNR when facing toxic compound shock threats.


Assuntos
Amônia , Nitrogênio , Percepção de Quorum , Óxido de Zinco , Óxido de Zinco/toxicidade , Amônia/toxicidade , Percepção de Quorum/efeitos dos fármacos , Nanopartículas/toxicidade , 4-Butirolactona/análogos & derivados , 4-Butirolactona/toxicidade , Nanopartículas Metálicas/toxicidade
9.
Small ; : e2408566, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-39498700

RESUMO

Electrocatalytic nitrate (NO3 -) reduction to ammonia (NH3) is a green and efficient NH3 synthesis technology. Metallic silver (Ag) is one of the well-known electrocatalysts for NO3 - reduction. However, under alkaline conditions, its poor water-splitting ability fails to provide sufficient protonic hydrogen required for NH3 synthesis, resulting in low NH3 selectivity. Additionally, metal catalysts are prone to leaching and oxidation during electrocatalysis, resulting in poor stability. Herein, cobalt (Co) into Ag (CoAg) catalyst is doped, which not only increases the NH3 selectivity by 34.4%, but also reduces the reduction potential by 0.1 V. Meanwhile, reduced graphene oxide (rGO) as a protective "armor" is used to encapsulate the CoAg catalyst (rGO2.92@CoAg). The rGO2.92@CoAg catalyst shows excellent stability for over 300 hours (h) of continuous reaction. The Co and Ag contents in the rGO2.92@CoAg catalyst after continuous tests decreases by only 4.3% and 3.1%, respectively, which are much lower than those of the CoAg catalyst without the rGO (90.8%, 52.6%). Moreover, the rGO2.92@CoAg catalyst shows high Faradaic efficiency (99.3%) and NH3 yield rate (1.47 mmol h-1 cm-2). Therefore, a high performance and strong stability rGO2.92@CoAg catalyst is obtained by Co doping and rGO coating, which provides theoretical basis for practical industrial application.

10.
Angew Chem Int Ed Engl ; : e202416195, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-39498760

RESUMO

As a well-established topic, single-atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single-atom form, the intrinsic roles of single-atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co-Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co-Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat-1·min-1 at very low temperature (500 °C, GHSV = 840,000 mL·g-1·h-1) and Co-Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non-noble catalysts, and reaches or even exceeds numerous reported Ru-based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co-O-Ba-Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N-H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

11.
Aquat Toxicol ; 277: 107133, 2024 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-39500068

RESUMO

The toxic effects of ammonia exposure on Litopenaeus vannamei have been widely reported, including tissue damage, oxidative stress, and metabolic disorders, but the ability of L. vannamei to recover from ammonia damage is still unclear. To further understand the adaptation mechanism of L. vannamei to ammonia, this study explored the effects of ammonia exposure and recovery on histopathology, physiological indicators, and transcriptomic responses. In the ammonia exposure (NH4+-N 25 mg/L) and recovery experiment, shrimp were sampled at 0 h, 24 h, 48 h of exposure, and 24 h, 48 h of recovery. The results showed that histopathological damage to the hepatopancreas and gills caused by short-term ammonia exposure could be alleviated after recovery. Ammonia exposure inhibited superoxide dismutase (SOD) and catalase (CAT) activities, decreased total antioxidant capacity (T-AOC), and increased malondialdehyde (MDA) in shrimp. Restoration of the antioxidant system after exposure mitigated oxidative damage and reduced MDA levels. The inhibition of acid phosphatase (ACP) and alkaline phosphatase (AKP) activities in shrimp caused by ammonia exposure was reversible. Ammonia excretion and metabolism attenuate ammonia toxicity and promote recovery in L. vannamei. Transcriptome analysis identified 1690, 1568, and 1463 differentially expressed genes (DEGs) in the hepatopancreas at 48 h of stress, 24 h, and 48 h of recovery, respectively. KEGG enrichment analysis revealed that ammonia exposure induced oxidative damage, resulting in apoptosis. Furthermore, activation of antioxidant-related pathways, such as glutathione metabolism and peroxisomes, helped reduce oxidative damage during the post-exposure recovery period. The addition of exogenous spermine and spermidine may contribute to post-exposure recovery and enhance ammonia acclimation in L. vannamei. Differential expression of the inflammatory gene STEAP4 in the ammonia stress and recovery phases, as screened by transcriptome analysis, may play a positive role in post-stress recovery. This study demonstrated the reversibility of the toxic effects of ammonia exposure on L. vannamei, complemented the knowledge of the mechanisms of adaptation of shrimp under ammonia exposure, and provided a basis for subsequent ammonia tolerance studies in crustaceans.

12.
J Colloid Interface Sci ; 680(Pt A): 78-87, 2024 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-39500092

RESUMO

Catalytic methanolysis of ammonia borane is an integrated hydrogen production/storage technology with bright prospects, while its wide application is impeded by the high-cost of catalysts. In this work, hollow core@shell structured (HCSS) Co3O4@CuO-NiO with a size of 300-500 nm and a shell thickness of ca. 100 nm has been designed for ammonia borane (NH3BH3) methanolysis for rapid hydrogen release. The possible formation mechanism of HCSS-Co3O4@CuO-NiO is proposed based on a series of characterization results, which is crucial for the design and preparation of nanocatalysts with similar architectures. Benefiting from the optimized compositions and electronic structures, the best HCSS-Co3O4@CuO-NiO sample exhibits high catalytic activity in NH3BH3 methanolysis with a turnover frequency of 67.1 min-1, surpassing that of all the noble-metal-free catalysts in previous reports. A possible reaction mechanism of NH3BH3 methanolysis is put forward based on the in-situ Fourier transform infrared spectrometer (FTIR) characterization and kinetic isotope effect (KIE) experimental results. This work supplies a novel avenue for developing cheap and robust catalysts towards NH3BH3 methanolysis by tailoring the catalysts' morphology to hollow core@shell structures.

13.
J Environ Manage ; 371: 123173, 2024 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-39500158

RESUMO

As wastewater treatment aeration systems are embracing innovative solutions to data management for operational sustainability, deep learning approaches like long short-term memory (LSTM) networks become imperative. However, how to enhance LSTMs to forecast aeration status through ensemble learning is still in its infancy. This study tackles this challenge by comprehensively comparing two ensemble learning algorithms, AdaBoost and Bagging. Both one-step and multi-step predictions were compared using performance metrics like Z-score derived from aeration set-points. The robustness of models was evaluated under quantified extreme events, such as sudden spikes in ammonia concentration. The results indicate that while AdaBoost-LSTM models slightly outperformed Bagging-LSTM models in one-step-ahead predictions, their true advantage lies in enabling precise decisions for switching aeration blowers on or off, which could avoid excess energy usage of aeration systems. This advantage was even more pronounced in multi-step forecasting. In 4-step-ahead prediction, the AdaBoost-LSTM model attained an optimal precision of 92.77%, marking an 8.88% improvement over the Bagging-LSTM model. Furthermore, AdaBoost-LSTM models showed greater resilience to fluctuations in ammonia levels, ensuring continued stable aeration. Therefore, AdaBoost-LSTM ensembles demonstrate greater suitability for accurate and robust ammonia forecasting of aeration tanks, leading to sustainable operation and target costs/energy savings.

14.
Chembiochem ; : e202400585, 2024 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-39500732

RESUMO

Nitrogenases catalyze dinitrogen (N2) fixation to ammonia (NH3). While these enzymes are highly sensitive to deactivation by molecular oxygen (O2) they can be produced by obligate aerobes for diazotrophy, necessitating a mechanism by which nitrogenase can be protected from deactivation. In the bacterium Azotobacter vinelandii, one mode of such protection involves an O2-responsive ferredoxin-type protein ("Shethna protein II", or "FeSII") which is thought to bind with Mo-dependent nitrogenase's two component proteins (NifH and NifDK) to form a catalytically stalled yet O2-tolerant tripartite protein complex. This protection mechanism has been reported for Mo-nitrogenase, however, in vitro assays with V-nitrogenase suggest that this mechanism is not universal to the three known nitrogenase isoforms. Here we report that the reductase of the V-nitrogenase (VnfH) can engage in this FeSII-mediated protection mechanism when cross-coupled with Mo-nitrogenase NifDK. Interestingly, the cross-coupling of the Mo-nitrogenase reductase NifH with the V-nitrogenase VnfDGK protein does not yield such protection.

15.
Mar Pollut Bull ; 209(Pt B): 117215, 2024 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-39486197

RESUMO

Aquaculture intensification system is challenged by high ammonia concentrations, which can affect fish physiology. In the present study, we assessed the effects of ammonia on ussuri cisco based on histopathology, antioxidant enzyme activity, immune response, and integrated biomarker responses. After exposure to 60.0 mg/L ammonia, liver vacuolization, bruising, nucleolysis, cell swelling, cell rupture, and structural irregularities were observed. It was found that the degree of liver damage increased with the duration of stress and was most severe at 72 h. During ammonia stress, the serum levels of SOD, CAT, MDA and T-AOC in the treatment groups showed a tendency to increase and then decrease. In addition, the serum activities of GOT, GPT and AKP were significantly higher in the treatment group than in the control group after ammonia exposure. We also evaluated the immune regulatory mechanisms of the NF-κB pathway and showed that immune-related genes (TNF-α, TAK1, NFKBIA, IKBKB, P50, P65, IL-8, IL-1ß and A20) were differentially elevated during the exposure period, especially TNF-α, IL-8, IL-1ß and A20 which were all highly expressed. CAT, GPT, AKP and SOD were identified as representative markers of biotoxic effects. This will help to more accurately estimate the ecological risk of environmental ammonia to fish populations.

16.
Artigo em Inglês | MEDLINE | ID: mdl-39486896

RESUMO

The electrochemical reduction reaction of nitrate (NO3RR) is an attractive route to produce ammonia at ambient conditions, but the conversion from nitrate to ammonia, which requires nine protons, has to compete with both the two-proton process of nitrite formation and the hydrogen evolution reaction. Extensive research efforts have thus been made in recent studies to develop electrocatalysts for the NO3RR facilitating the production of ammonia. Rather than designing another better electrocatalyst, herein, we synthesize an electrochemically inactive, porous, and chemically robust zirconium-based metal-organic framework (MOF) with enriched intraframework sulfonate groups, SO3-MOF-808, as a coating deposited on top of the catalytically active copper-based electrode. Although both the overall reaction rate and electrochemically active surface area of the electrode are barely affected by the MOF coating, with negatively charged sulfonate groups capable of enriching more protons near the electrode surface, the MOF coating significantly promotes the selectivity of the NO3RR toward the production of ammonia. In contrast, the use of MOF coating with positively charged trimethylammonium groups to repulse protons strongly facilitates the conversion of nitrate to nitrite, with selectivity of more than 90% at all potentials. Under the optimal operating conditions, the copper electrocatalyst with SO3-MOF-808 coating can achieve a Faradaic efficiency of 87.5% for ammonia production, a nitrate-to-ammonia selectivity of 95.6%, and an ammonia production rate of 97 µmol/cm2 h, outperforming all of those achieved by both the pristine copper (75.0%; 93.9%; 87 µmol/cm2 h) and copper with optimized Nafion coating (83.3%; 86.9%; 64 µmol/cm2 h). Findings here suggest the function of MOF as an advanced alternative to the commercially available Nafion to enrich protons near the surface of electrocatalyst for NO3RR, and shed light on the potential of utilizing such electrochemically inactive MOF coatings in a range of proton-coupled electrocatalytic reactions.

17.
J Breath Res ; 2024 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-39496198

RESUMO

The measurement of trace breath gases is of growing interest for its potential to provide non-invasive physiological information in health and disease. While instrumental techniques such as selected-ion flow-tube mass spectrometry (SIFT-MS) can achieve this, these are less suitable for clinical application. Sensitive sensor-based systems for breath ammonia could be more widely deployed, but have proven challenging to develop. This work demonstrates the sequential analytical validation of an electrochemical impedance-based sensor system for the measurement of ammonia in breath using SIFT-MS. Qualitative and relative responses between the two methods were comparable, although there were consistent differences in absolute concentration. When tested in artificial breath ammonia, sensors had a relative impedance sensitivity of 3.43x10-5ppbv-1for each breath in the range of 249 to 1,653 ppbv (r2=0.87,p<0.05). When correlated with SIFT-MS using human breath (n=14), ammonia was detected in the range of 100 to 700 ppbv (r=0.78,p<0.001), demonstrating acceptable sensitivity, reproducibility and dynamic range for clinical application.

18.
Adv Mater ; : e2405578, 2024 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-39494957

RESUMO

The electrocatalytic synthesis of ammonia (NH3) through the nitrogen reduction reaction (NRR) under ambient temperature and pressure is emerging as an alternative approach to the conventional Haber-Bosch process. However, it remains a significant challenge due to poor kinetics, low nitrogen (N2) solubility in aqueous electrolytes, and the competing hydrogen evolution reaction (HER), which can significantly impact NH3 production rates and Faradaic efficiency (FE). Herein, a rationally designed boron-doped molybdenum sulfide (B-Mo-MoxSy) electrocatalyst is reported that effectively enhances N2 reduction to  NH3 with an onset potential of -0.15 V versus RHE, achieving a FE of 78% and an NH3 yield of 5.83 µg h⁻¹ cm⁻2 in a 0.05 m H2SO4(aq). Theoretical studies suggest that the effectiveness of NRR originates from electron density redistribution due to boron (B) doping, which provides an ideal pathway for nitrogenous species to bind with electron-deficient B sites. This work demonstrates a significant exploration, showing that Mo-based electrocatalysts are capable of facilitating artificial N2 fixation.

19.
J Hazard Mater ; 480: 136275, 2024 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-39490168

RESUMO

Postcatalyst ammonia emissions from gasoline vehicles recently received attentions because of their contribution to the formation of urban secondary aerosols. To better understand whether fuel formulation would curb ammonia, the influence of methyl tertiary-butyl ether (MTBE) additive in gasoline on the tailpipe ammonia emissions from six China-6 compliant vehicles was investigated over the World Harmonized Light-duty Test Cycle (WLTC) at -7 °C and 23 °C. Ammonia emissions were measured with MTBE-free and 10 % MTBE-containing China-6 compliant gasoline fuels on the test vehicles. At - 7 °C, the ammonia emissions with and without MTBE addition ranged from 0.15 - 17.07 mg/km and 0.81 - 25.13 mg/km, respectively. At 23 °C, ammonia emissions were 0 - 7.4 mg/km for MTBE-containing fuel and 0 - 8.76 mg/km for MTBE-free fuel. More ammonia emissions were often observed as a result of maneuvering of enriched air-fuel mixtures to improve the combustion stability after cold-start and for de-NOx purpose. Due to the oxygen-containing nature of MTBE, its addition favors ammonia reduction in cold-start tests at - 7 and 23 °C. It is noted that "λ sweep", an engine control strategy injecting extra fuel to deplete stored oxygen in the catalyst and suppress transient NOx formation during reacceleration after prolonged deceleration, may contribute to ammonia emissions due to the use of enriched air-fuel mixtures.

20.
J Food Prot ; : 100391, 2024 Oct 26.
Artigo em Inglês | MEDLINE | ID: mdl-39490688

RESUMO

Robust environmental monitoring for Listeria monocytogenes often may not be feasible for small and very small meat processors in the United States due to limitations in finances, staffing, or expertise. Three small/very small processors in Nebraska were sampled using sponge applicators in non-food contact surface areas to determine if biofilm and sanitizer resistance behaviors of Pseudomonas could relate to the prevalence of L. monocytogenes and Listeria spp. in ready-to-eat meat processing environments. Samples were 3.3% (3/90) positive for L. monocytogenes, and 12.2% (11/90) of samples were positive for Listeria spp. Pseudomonas spp. were also isolated. When Listeria spp. and Pseudomonas spp. were assayed for biofilm production and resistance to a quaternary ammonia sanitizer, multiple isolates belonging to both genera capable of forming biofilms were identified. Four Pseudomonas spp. isolates resisted the 200 ppm manufacturer recommended sanitizer concentration for food contact surface sanitation, and one Pseudomonas spp. isolated from a drain sample that was also positive for L. monocytogenes demonstrated a sanitizer minimum bactericidal concentration of 1000 ppm. These findings further support the need for monitoring of small and very small meat processors for L. monocytogenes as well as highlight the need to identify other bacteria in these processing environments, like Pseudomonas, that are resistant to environmental stressors.

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