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1.
Adv Sci (Weinh) ; : e2405741, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39248778

RESUMEN

Sonopiezocatalytic therapy is an emerging therapeutic strategy that utilizes ultrasound irradiation to activate piezoelectric materials, inducing polarization and energy band bending to facilitate the generation of reactive oxygen species (ROS). However, the efficient generation of ROS is hindered by the long distance of charge migration from the bulk to the material surface. Herein, atomically thin Bi2O2(OH)(NO3) (AT-BON) nanosheets are rationally engineered through disrupting the weaker hydrogen bonds within the [OH] and [NO3] layer in the bulk material. The ultrathin structure of AT-BON piezocatalytic nanosheets shortens the migration distance of carriers, expands the specific surface area, and accelerates the charge transfer efficiency, showcasing a natural advantage in ROS generation. Importantly, the non-centrosymmetric polar crystal structure grants the nanosheets the ability to separate electron-hole pairs. Under ultrasonic mechanical stress, Bi2O2(OH)(NO3) nanosheets with the remarkable piezoelectric feature exhibit the desirable in vivo antineoplastic outcomes in both breast cancer model and liver cancer model. Especially, the AT-BON-induced ROS bursts lead to the activation of the Caspase-1-driven pyroptosis pathway. This study highlights the beneficial impact of bulk material thinning on enhancing ROS generation efficiency and anti-cancer effects.

2.
Water Res ; 266: 122317, 2024 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-39260192

RESUMEN

The advanced oxidation process is an efficient technology for the degradation and detoxification of refractory organics to ensure water safety. However, most researches focus on improving pollutant degradation but overlook carbon emission and resource utilization. In this study, a flow-through electrochemical integrated system was constructed to simultaneously realize bisphenol A (BPA) oxidation into small non-toxic organics and CO2, and generated CO2 coupled with nitrate-containing wastewater conversion to urea and ammonia on a porous cathode (Zr-Fe/CN). The synergistic effect between anodic BPA oxidation with cathodic CO2 and NO3-reduction improves the electron utilization efficiency and thus increasing the BPA degradation, urea yield rate (UYR) and NH3 yield rate (NYR) by 13.4 % 18.4 % and 8.3 %, respectively. Furthermore, the flow-through operation mode significantly increased the mass transfer efficiency and quickly carried generated CO2 from the anode into the cathode to improve CO2 utilization efficiency. Compared to the parallel plate electrode reactor, the BPA degradation efficiency, UYR and NYR in the flow-through reactor increased from 59.46 % to 84.49 % (the initial concentration of BPA was 40 mg/L), 9.94 mmol h-1g-1 to 19.55 mmol h-1g-1, and 80.31 mmol h-1g-1 to 106.06 mmol h-1g-1 within 60 min, respectively. Moreover, the total carbon conversion efficiency (from BPA to urea) increased from 20.2 % to 42.4 % and the total Faraday efficiency (FE) increased from 78.6 % to 96.3 %. This work provides a multi-win strategy of harmless, resource-based and carbon emission reduction for wastewater treatment.

3.
Adv Mater ; : e2408680, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39258370

RESUMEN

Electrochemical nitrate reduction reaction (NO3RR) is a promising approach to realize ammonia generation and wastewater treatment. However, the transformation from NO3 - to NH3 involves multiple proton-coupled electron transfer processes and by-products (NO2 -, H2, etc.), making high ammonia selectivity a challenge. Herein, a two-phase nanoflower P-Cu/Co(OH)2 electrocatalyst consisting of P-Cu clusters and P-Co(OH)2 nanosheets is designed to match the two-step tandem process (NO3 - to NO2 - and NO2 - to NH3) more compatible, avoiding excessive NO2 - accumulation and optimizing the whole tandem reaction. Focusing on the initial 2e- process, the inhibited *NO2 desorption on Cu sites in P-Cu gives rise to the more appropriate NO2 - released in electrolyte. Subsequently, P-Co(OH)2 exhibits a superior capacity for trapping and transforming the desorbed NO2 - during the latter 6e- process due to the thermodynamic advantage and contributions of active hydrogen. In 1 m KOH + 0.1 m NO3 -, P-Cu/Co(OH)2 leads to superior NH3 yield rate of 42.63 mg h- 1 cm- 2 and NH3 Faradaic efficiency of 97.04% at -0.4 V versus the reversible hydrogen electrode. Such a well-matched two-step process achieves remarkable NH3 synthesis performance from the perspective of optimizing the tandem catalytic reaction, offering a novel guideline for the design of NO3RR electrocatalysts.

4.
J Environ Manage ; 370: 122456, 2024 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-39265493

RESUMEN

Traditional nitrogen fertilizers (TNF), such as urea, percolate easily in arid fields, posing low nitrogen use efficiency (NUE) and a high non-point pollution risk. Controlled-release fertilizers (CRF) exhibit significantly lower deep seepage, rendering it a favorable choice in arid fields due to its ability to enhance NUE through slow-release mechanisms. However, current models do not fully account for the soil nitrogen dynamics and crop interactions under controlled-release conditions, and lack quantification. This study improved the APSIM model by adjustment the urea hydrolysis rate to assess the impact of CRF and TNF applications on soil health, crop growth, and water quality. Calibration and validation were conducted through experiments in the Hetao Irrigation District of China from 2019 to 2020, with different nitrogen application rates (135, 225, and 315 kg/ha). The model accurately simulated soil NO3-N concentration (SNC), cumulative NO3-N leaching (CNL), nitrogen uptake (NU), and sunflower yield. During the validation process, R2 and Nash-Sutcliffe efficiency (NSE) values were both above 0.75. Results indicated that the average SNC, NU, and yield under CRF application were significantly higher than those under TNF application, with increases of 38.62%, 44.92%, and 18.38%, respectively. Notably, the proportion of soil nitrogen available (PSNA), a novel metric proposed in this study, was 159.50% higher in the 0-40 cm soil layer with CRF compared to TNF. Additionally, CNL and NO3-N leaching loss rate (NLLR) decreased by 25.76% and 25.77%, respectively. Scenario simulations indicated that the optimal fertilization strategy for this region is to use 180-193.5 kg/ha of CRF with a release period of 80-85.5 d to balance agricultural productivity and ecological protection. This study confirms the significant advantages of CRF in enhancing yield, improving nitrogen management, and promoting environmental sustainability, providing a scientific basis for CRF management strategies and supporting the shift towards more efficient and environmentally friendly agricultural practices.

5.
Sci Rep ; 14(1): 21286, 2024 09 12.
Artículo en Inglés | MEDLINE | ID: mdl-39266741

RESUMEN

In sweet potato, rational nitrogen (N) assimilation and distribution are conducive to inhibiting vine overgrowth. Nitrate (NO3-) is the main N form absorbed by roots, and cultivar is an important factor affecting N utilization. Herein, a hydroponic experiment was conducted that included four NO3- concentrations of 0 (N0), 4 (N1), 8 (N2) and 16 (N3) mmol L-1 with two cultivars of Jishu26 (J26, N-sensitive) and Xushu32 (X32, N-tolerant). For J26, with increasing NO3- concentrations, the root length and root surface area significantly decreased. However, no significant differences were observed in these parameters for X32. Higher NO3- concentrations upregulated the expression levels of the genes that encode nitrate reductase (NR2), nitrite reductase (NiR2) and nitrate transporter (NRT1.1) in roots for both cultivars. The trends in the activities of NR and NiR were subject to regulation of NR2 and NiR2 transcription, respectively. For both cultivars, N2 increased the N accumulated in leaves, growth points and roots. For J26, N3 further increased the N accumulation in these organs. Under higher NO3- nutrition, compared with X32, J26 exhibited higher expression levels of the NiR2, NR2 and NRT1.1 genes, a higher influx NO3- rate in roots, and higher activities of NR and NiR in leaves and roots. Conclusively, the regulated effects of NO3- supplies on root growth and NO3- utilization were more significant for J26. Under high NO3- conditions, J26 exhibited higher capacities of NO3- absorption and distributed more N in leaves and in growth points, which may contribute to higher growth potential in shoots and more easily cause vine overgrowth.


Asunto(s)
Regulación de la Expresión Génica de las Plantas , Ipomoea batatas , Nitratos , Nitrógeno , Raíces de Plantas , Nitratos/metabolismo , Ipomoea batatas/metabolismo , Ipomoea batatas/genética , Ipomoea batatas/crecimiento & desarrollo , Raíces de Plantas/metabolismo , Raíces de Plantas/crecimiento & desarrollo , Raíces de Plantas/genética , Nitrógeno/metabolismo , Nitrato-Reductasa/metabolismo , Nitrato-Reductasa/genética , Hojas de la Planta/metabolismo , Hojas de la Planta/crecimiento & desarrollo , Hojas de la Planta/genética , Transportadores de Nitrato , Hidroponía , Proteínas de Plantas/metabolismo , Proteínas de Plantas/genética , Nitrito Reductasas/metabolismo , Nitrito Reductasas/genética , Proteínas de Transporte de Anión/metabolismo , Proteínas de Transporte de Anión/genética
6.
Artículo en Inglés | MEDLINE | ID: mdl-39301617

RESUMEN

The deactivation of ozone decomposition catalysts has been a bottleneck in their industrial application. As an efficient catalyst regeneration method, the liquid-phase method has attracted wide attention due to its operability and universality. However, the amount of waste liquid generated by the used regeneration liquid is a major drawback of its application. Therefore, we propose an electrolytic regeneration method for cyclic regeneration of MnOx ozone decomposition catalysts by combining the advantages of the electrolytic process. In this method, NaNO2 solution is used to react with O22- to efficiently regenerate the inactivated MnOx catalysts, while NO2- is oxidized to NO3-, and then the oxidized NO3- can be efficiently reduced to NO2- through the electrolysis process at the cathode with an 88% Faraday efficiency, ultimately realizing the recycling of the NO2-/NO3- regeneration solution. By this method, the regeneration of inactivated MnOx ozone catalysts can be realized only using electricity.

7.
Adv Sci (Weinh) ; : e2404194, 2024 Aug 09.
Artículo en Inglés | MEDLINE | ID: mdl-39119933

RESUMEN

Electrochemical conversion of nitrate (NO3 -) to ammonia (NH3) is a potential way to produce green NH3 and remediate the nitrogen cycle. In this paper, an efficient catalyst of spherical CuO made by stacking small particles with oxygen-rich vacancies is reported. The NH3 yield and Faraday efficiency are 15.53 mg h-1 mgcat -1 and 90.69%, respectively, in a neutral electrolyte at a voltage of -0.80 V (vs. reversible hydrogen electrode). The high activity of the electrodes results from changes in the phase and structure during electrochemical reduction. Structurally, there is a shift from a spherical structure with dense accumulation of small particles to a layered network structure with uniform distribution of small particles stacked on top of each other, thus exposing more active sites. Furthermore, in terms of phase, the electrode transitions from CuO to Cu/Cu(OH)2. Density functional theory calculations showed that Cu(OH)2 formation enhances NO3- adsorption. Meanwhile, the Cu(OH)2 can inhibit the competing hydrogen evolution reaction, while the formation of Cu (111) crystal surfaces facilitates the hydrogenation reaction. The synergistic effect between the two promotes the NO3- to NH3. Therefore, this study provides a new idea and direction for Cu-based oxides in electrocatalytic NH3 production.

8.
Anal Sci ; 2024 Aug 14.
Artículo en Inglés | MEDLINE | ID: mdl-39143455

RESUMEN

The separation and detection of six common inorganic anions (iodate (IO3-), bromate (BrO3-), bromide (Br-), nitrite (NO2-), nitrate (NO3-), and iodide (I-)) in pure water and 35 ‰ artificial seawater were examined by ion chromatography (IC). As packing materials of separation columns, 1-aminoundecyl group chemically bonded silica (AUS) gels were prepared. Separation of the anions in pure water was achieved using separation columns (150 mm × 4.6 mm i.d.) packed with the AUS gels, 0.1 M NaCl + 5 mM phosphate buffer (pH 4.5) as eluent, and a UV detector (wavelength 225 nm). The anions in artificial seawater were separated and detected with a 300 mm-long column without interferences by matrix anions such as chloride (Cl-) and sulfate (SO42-). The stationary phases have high-capacity anion-exchange/hydrophilic/hydrophobic interaction mixed-modes. The IC system was applied to five inorganic anions, IO3-, Br-, NO2-, NO3-, and I- in seawater of the Seto-Inland Sea, Japan. The detection limits (DLs, S/N = 3) were 11 µg L-1 (IO3-), 93 (Br-), 1.3 (NO2-), 1.4 (NO3-), and 1.1 (I-) for a 100-µL sample injection.

9.
Angew Chem Int Ed Engl ; : e202413774, 2024 Aug 13.
Artículo en Inglés | MEDLINE | ID: mdl-39136239

RESUMEN

Developing sustainable energy solutions is critical for addressing the dual challenges of energy demand and environmental impact. In this study, a zinc-nitrate (Zn-NO3-) battery system was designed for the simultaneous production of ammonia (NH3) via the electrocatalytic NO3- reduction reaction (NO3RR) and electricity generation. Continuous wave CO2 laser irradiation yielded precisely controlled CoFe2O4@nitrogen-doped carbon (CoFe2O4@NC) hollow nanocubes from CoFe Prussian blue analogs (CoFe-PBA) as the integral electrocatalyst for NO3RR in 1.0-M KOH, achieving a remarkable NH3 production rate of 10.9 mgh-1cm-2 at -0.47 V versus RHE with exceptional stability. In-situ and ex-situ methods revealed that the CoFe2O4@NC surface transformed into high-valent Fe/CoOOH active-species, optimizing the adsorption energy of NO3RR (*NO2 and *NO species) intermediates. Furthermore, DFT calculations validated the possible NO3RR pathway on CoFe2O4@NC starting with NO3- conversion to *NO2 intermediates, followed by reduction to *NO. Subsequent protonation forms the *NH and *NH2 species, leading to NH3 formation via final protonation. The Zn-NO3- battery utilizing the CoFe2O4@NC cathode exhibits dual functionality by generating electricity with a stable open-circuit voltage of 1.38-V versus Zn/Zn2+ and producing NH3. This study inspires the simple design of low-cost catalysts for NO3RR-to-NH3 conversion and positions the Zn-NO3- battery as a promising technology for industrial applications.

10.
ACS Nano ; 2024 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-39023225

RESUMEN

Engineering fast-moving microrobot swarms that can physically disassemble bacterial biofilms and kill the bacteria released from the biofilms is a promising way to combat bacterial biofilm infections. Here, we report electrochemical design of Ag7O8NO3 microtorpedoes with outstanding antibacterial performance and meanwhile capable of moving at speeds of hundreds of body lengths per second in clinically used H2O2 aqueous solutions. These fast-moving antibacterial Ag7O8NO3 microtorpedoes could penetrate into and disintegrate the bacterial biofilms and, in turn, kill the bacteria released from the biofilms. Based on the understanding of the growth behavior of the microtorpedoes, we could fine-tune the morphology of the microtorpedoes to accelerate the moving speed and increase their penetration depth into the biofilms simply via controlling the potential waveforms. We further developed an automatic shaking method to selectively peel off the uniformly structured microtorpedoes from the electrode surface, realizing continuous electrochemical production of the microtorpedoes. Animal experiments proved that the microtorpedo swarms greatly increased the survival rate of the mice infected by lethal biofilms to >90%. We used the electrochemical method to design and massively produce uniformly structured fast-moving antibacterial microtorpedo swarms with application potentials in treatment of lethal bacterial biofilm infections.

11.
Sci Total Environ ; 948: 174956, 2024 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-39053523

RESUMEN

Biochar exhibits numerous advantages in enhancing the soil environment despite a few limitations due to its lower surface energy. Nanomodified biochar combines the advantages of biochar and nanoscale materials. However, its effects on water infiltration and N leaching in a clayey soil remain unclear. Therefore, this study prepared rice straw nano-biochar by a ball milling method, and investigated its physicochemical properties and effects of bulk biochar and nano-biochar at various addition rates (0 %, 0.5 %, 1 %, 2 %, 3 %, and 5 %) on wetting peak migration, cumulative infiltration, water absorption and retention, and N leaching. The results showed that, compared with bulk biochar, nano-biochar presented a more abundant pore structure with an increase in specific surface area of approximately 1.5 times, accompanied by a 20 % increase in acid functional groups. Compared with those for clayey soil without biochar addition, the wetting front migration time was increased by 10.2 %-123.9 % and 17.0 %-257.9 %, and the cumulative infiltration volume at 60 min was decreased by 26.0 %-48.4 % and 14.1 %-62.4 % for bulk biochar and nano-biochar, respectively. The parameter S of Philip model and the parameter a of Kostiakov model for nano-biochar were lower than those for bulk biochar, whereas the parameter b of Kostiakov model was greater, indicating that nano-biochar decreased initial soil infiltration rate and increased attenuation degree of the infiltration rate. Nano-biochar increased water absorption by 8.03 % and subsequently enhanced water retention capacity relative to bulk biochar. In addition, bulk biochar and nano-biochar reduced NH4+-N leaching by 3.0 %-13.1 % and 5.7 %-39.2 %, respectively, and NO3--N leaching by 2.7 %-3.6 % and 9.0 %-43.3 %, respectively, by decreasing N concentration and leachate volume relative to those with no biochar addition. This study provides new knowledge for nano-biochar application in a clayey soil.


Asunto(s)
Carbón Orgánico , Arcilla , Nitrógeno , Oryza , Suelo , Carbón Orgánico/química , Suelo/química , Nitrógeno/análisis , Arcilla/química , Contaminantes del Suelo/análisis , Agua/química
12.
ACS Nano ; 18(29): 19220-19231, 2024 Jul 23.
Artículo en Inglés | MEDLINE | ID: mdl-38976597

RESUMEN

Supported nonprecious metal catalysts such as copper (Cu) are promising replacements for Pt-based catalysts for a wide range of energy-related electrochemical reactions. Direct electrochemical deposition is one of the most straightforward and versatile methods to synthesize supported nonprecious metal catalysts. However, further advancement in the design of supported nonprecious metal catalysts requires a detailed mechanistic understanding of the interplay between kinetics and thermodynamics of the deposition phenomena under realistic reaction conditions. Here, we study the electrodeposition of Cu on carbon nanotubes and graphene derivatives under electrochemical conditions using in situ liquid cell transmission electron microscopy (TEM). By combining real-time imaging, electrochemical measurements, X-ray photoelectron spectroscopy (XPS), and finite-element analysis (FEA), we show that low-dimensional support materials, especially carbon nanotubes, are excellent for generating uniform and finely dispersed platinum group metal-(PGM)-free catalysts under mild electrochemical conditions. The electrodeposited Cu on graphene and carbon nanotubes is also observed to show good electrochemical activity toward nitrate reduction reactions (NO3RRs), further supported by density functional theory (DFT) calculations. Nitrogen doping plays an important role in guiding nonprecious metal deposition, but its low electrical conductivity may give rise to lower NO3RR activity compared to its nondoped analogue. The development of supported nonprecious metals through interfacial and surface engineering for the design of supported catalysts will substantially reduce the demand for precious metals and generate robust catalysts with better durability, thereby presenting opportunities for solving the critical problems in energy storage and electrocatalysis.

13.
Int J Mol Sci ; 25(14)2024 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-39063209

RESUMEN

'Duli' (Pyrus betulifolia Bunge) is one of the main rootstocks of pear trees in China. Gibberellin (GA) is a key plant hormone and the roles of GA in nitrate (NO3-) uptake and metabolism in plants remain unclear. In this study, we investigated the effects of exogenous GA3 on the N metabolism of 'Duli' seedlings under NO3- deficiency. The results showed that exogenous GA3 significantly improves 'Duli' growth under NO3- deficiency. On the one hand, GA3 altered the root architecture, increased the content of endogenous hormones (GA3, IAA, and ZR), and enhanced photosynthesis; on the other hand, it enhanced the activities of N-metabolizing enzymes and the accumulation of N, and increased the expression levels of N absorption (PbNRT2) and the metabolism genes (PbNR, PbGILE, PbGS, and PbGOGAT). However, GA3 did not delay the degradation of chlorophyll. Paclobutrazol had the opposite effect on growth. Overall, GA3 can increase NO3- uptake and metabolism and relieve the growth inhibition of 'Duli' seedlings under NO3- deficiency.


Asunto(s)
Giberelinas , Nitratos , Nitrógeno , Pyrus , Plantones , Plantones/metabolismo , Plantones/crecimiento & desarrollo , Plantones/efectos de los fármacos , Nitratos/metabolismo , Giberelinas/metabolismo , Nitrógeno/metabolismo , Pyrus/metabolismo , Pyrus/genética , Pyrus/crecimiento & desarrollo , Pyrus/efectos de los fármacos , Regulación de la Expresión Génica de las Plantas/efectos de los fármacos , Fotosíntesis/efectos de los fármacos , Raíces de Plantas/metabolismo , Raíces de Plantas/crecimiento & desarrollo , Raíces de Plantas/efectos de los fármacos , Reguladores del Crecimiento de las Plantas/metabolismo , Clorofila/metabolismo
14.
Sci Total Environ ; 945: 174145, 2024 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-38909795

RESUMEN

The coexistence of hexavalent chromium (Cr(VI)) and nitrate (NO3-) in groundwater and surface water presents a considerable challenge for the natural attenuation of these two contaminants because their interactions in nature remain contentious. This study investigated the interplay between Cr(VI) and NO3- in hyporheic zone (HZ) sediments by integrating Cr(VI) reduction kinetics, NO3- transformation, microbial community structure, and a three-rate model. The concurrent natural attenuation of Cr(VI) and NO3- in the sediments was significantly influenced by their initial concentrations and redox conditions. The reduction of low concentrations of Cr(VI) (37.1 and 96.2 µM) was slightly enhanced by NO3-, while inhibitory effects were observed at high concentrations of Cr(VI) (200.0 µM). However, except for an initial low concentration of Cr(VI) (37.1 µM) and NO3- (450 µM), the reduction of NO3- was adversely affected by Cr(VI). The reduction rates and efficiencies of Cr(VI) and NO3- were noticeably lower under aerobic conditions than under anaerobic conditions. This phenomenon can be attributed to the presence of O2, which decreased the selectivity of sediments-associated Fe(II) towards Cr(VI) and NO3- and induced alterations in the microbial community structure, leading to subsequent changes in NO3- transformation. Furthermore, the three-rate model represents a robust approach for elucidating the reduction of Cr(VI) in the presence of co-contaminants, such as NO3- contamination under diverse redox conditions. This study provides further insights into the interaction mechanism between Cr(VI) and NO3- within the HZ, necessitating the consideration of the microbial toxicity of Cr(VI) and electron competition among Cr(VI), NO3-, and O2.

15.
Bioresour Technol ; 403: 130882, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38788805

RESUMEN

This study successfully established Iron Sulfide-Mediated mixotrophic Partial Denitrification/Anammox system, achieving nitrogen and phosphorus removal efficiency of 97.26% and 78.12%, respectively, with COD/NO3--N of 1.00. Isotopic experiments and X-ray Photoelectron Spectroscopy analysis confirmed that iron sulfide enhanced autotrophic Partial Denitrification performance. Meanwhile, various sulfur valence states functioned as electron buffers, reinforcing nitrogen and sulfur cycles. Microbial community analysis indicated reduced heterotrophic denitrifiers (OLB8, OLB13) under lower COD/NO3--N, creating more niche space for autotrophic bacteria and other heterotrophic denitrifiers. The prediction of functional genes illustrated that iron Sulfide upregulated genes related to carbon metabolism, denitrification, anammox and sulfur oxidation-reduction, facilitating the establishment of carbon-nitrogen-sulfur cycle. Furthermore, this cycle primarily produced electrons via nicotinamide adenine dinucleotide and sulfur oxidation-reduction processes, subsequently utilized within the electron transfer chain. In summary, the Partial Denitrification/Anammox system under the influence of iron sulfide achieved effient nitrogen removal by expediting electron transfer through the carbon-nitrogen-sulfur cycle.


Asunto(s)
Carbono , Desnitrificación , Nitrógeno , Oxidación-Reducción , Azufre , Azufre/metabolismo , Nitrógeno/metabolismo , Carbono/metabolismo , Reactores Biológicos , Bacterias/metabolismo , Compuestos Ferrosos/metabolismo , Compuestos Ferrosos/química , Anaerobiosis
16.
Environ Pollut ; 352: 124141, 2024 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-38740243

RESUMEN

During the cold season in South Korea, NO3- concentrations are known to significantly increase, often causing PM2.5 to exceed air quality standards. This study investigated the formation mechanisms of NO3- in a suburban area with low anthropogenic emissions. The average PM2.5 was 25.3 µg m-3, with NO3- identified as the largest contributor. Ammonium-rich conditions prevailed throughout the study period, coupled with low atmospheric temperature facilitating the transfer of gaseous HNO3 into the particulate phase. This result indicates that the formation of HNO3 played a crucial role in determining particulate NO3- concentration. Nocturnal increases in NO3- were observed alongside increasing ozone (O3) and relative humidity (RH), emphasizing the significance of heterogeneous reactions involving N2O5. NO3- concentrations at the study site were notably higher than in Seoul, the upwind metropolitan area, during a high concentration episode. This difference could potentially attributed to lower local NO concentrations, which enhanced the reaction between O3 and NO2, to produce NO3 radicals. High concentrations of Cl- and dust were also identified as contributors to the elevated NO3- concentrations.


Asunto(s)
Contaminantes Atmosféricos , Ciudades , Monitoreo del Ambiente , Nitratos , Ozono , Material Particulado , Estaciones del Año , Material Particulado/análisis , Contaminantes Atmosféricos/análisis , República de Corea , Nitratos/análisis , Ozono/análisis , Contaminación del Aire/estadística & datos numéricos , Frío
17.
Angew Chem Int Ed Engl ; 63(35): e202407589, 2024 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-38703065

RESUMEN

Directly electrochemical conversion of nitrate (NO3 -) is an efficient and environmentally friendly technology for ammonia (NH3) production but is challenged by highly selective electrocatalysts. High-entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly for multi-step reactions. Herein, we first reported the application of HEA (FeCoNiAlTi) for electrocatalytic NO3 - reduction to NH3 (NRA). The bulk HEA is active for NRA but limited by the unsatisfied NH3 yield of 0.36 mg h-1 cm-2 and Faradaic efficiency (FE) of 82.66 %. Through an effective phase engineering strategy, uniform intermetallic nanoparticles are introduced on the bulk HEA to increase electrochemical active surface area and charge transfer efficiency. The resulting nanostructured HEA (n-HEA) delivers enhanced electrochemical NRA performance in terms of NH3 yield (0.52 mg h-1 cm-2) and FE (95.23 %). Further experimental and theoretical investigations reveal that the multi-active sites (Fe, Co, and Ni) dominated electrocatalysis for NRA over the n-HEA. Notably, the typical Co sites exhibit the lowest energy barrier for NRA with *NH2 to *NH3as the rate-determining step.

18.
Molecules ; 29(10)2024 May 11.
Artículo en Inglés | MEDLINE | ID: mdl-38792124

RESUMEN

The insight of the activity phase and reaction mechanism is vital for developing high-performance ammonia synthesis electrocatalysts. In this study, the origin of the electronic-dependent activity for the model Cu2O catalyst toward ammonia electrosynthesis with nitrate was probed. The modulation of the electronic state and oxygen vacancy content of Cu2O was realized by doping with halogen elements (Cl, Br, I). The electrocatalytic experiments showed that the activity of the ammonia production depends strongly on the electronic states in Cu2O. With increased electronic state defects in Cu2O, the ammonia synthesis performance increased first and then decreased. The Cu2O/Br with electronic defects in the middle showed the highest ammonia yield of 11.4 g h-1 g-1 at -1.0 V (vs. RHE), indicating that the pattern of change in optimal ammonia activity is consistent with the phenomenon of volcano curves in reaction chemistry. This work highlights a promising route for designing NO3-RR to NH3 catalysts.

19.
Plants (Basel) ; 13(10)2024 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-38794457

RESUMEN

Nitrogen (N) is the most important nutrient in coffee, with a direct impact on productivity, quality, and sustainability. N uptake by the roots is dominated by ammonium (NH4+) and nitrates (NO3-), along with some organic forms at a lower proportion. From the perspective of mineral fertilizer, the most common N sources are urea, ammonium (AM), ammonium nitrates (AN), and nitrates; an appropriate understanding of the right balance between N forms in coffee nutrition would contribute to more sustainable coffee production through the better N management of this important crop. The aim of this research was to evaluate the influences of different NH4-N/NO3-N ratios in coffee from a physiological and agronomical perspective, and their interaction with soil water levels. Over a period of 5 years, three trials were conducted under controlled conditions in a greenhouse with different growing media (quartz sand) and organic soil, with and without water stress, while one trial was conducted under field conditions. N forms and water levels directly influence physiological responses in coffee, including photosynthesis (Ps), chlorophyll content, dry biomass accumulation (DW), nutrient uptake, and productivity. In all of the trials, the plants group in soils with N ratios of 50% NH4-N/50% NO3-N, and 25% NH4-N/75% NO3-N showed better responses to water stress, as well as a higher Ps, a higher chlorophyll content, a higher N and cation uptake, higher DW accumulation, and higher productivity. The soil pH was significantly influenced by the N forms: the higher the NO3--N share, the lower the acidification level. The results allow us to conclude that the combination of 50% NH4-N/50% NO3-N and 25% NH4-N/75% NO3-N N forms in coffee improves the resistance capacity of the coffee to water stress, improves productivity, reduces the soil acidification level, and improves ion balance and nutrient uptake.

20.
Front Plant Sci ; 15: 1385980, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38693926

RESUMEN

Resource-based water shortages, uncoordinated irrigation, and fertilization are prevalent challenges in agricultural production. The scientific selection of appropriate water and fertilizer management methods is important for improving the utilization efficiency of agricultural resources and alleviating agricultural non-point source pollution. This study focused on wolfberry and compared the effects of four irrigation levels [full irrigation (W0, 75%-85% θf), slight water deficit (W1, 65%-75% θf), moderate water deficit (W2, 55%-65% θf), and severe water deficit (W3, 45%-55% θf)] and four nitrogen application levels [no nitrogen application (N0, 0 kg·ha-1), low nitrogen application (N1, 150 kg·ha-1), medium nitrogen application (N2, 300 kg·ha-1), and high nitrogen application (N3, 450 kg·ha-1)] on soil nitrate nitrogen (NO3 --N) transport, plant nitrogen allocation, and soil nitrous oxide (N2O) emissions during the harvest period of wolfberry. And this study used CRITIC-entropy weights-TOPSIS model to evaluate 16 water and nitrogen regulation models comprehensively. The results revealed the following: (1) The NO3 --N content of the soil decreased with increasing horizontal distance from the wolfberry. It initially decreased, then increased, and finally decreased with an increase in soil depth. The average NO3 --N content in the 0-100 cm soil layer ranged from 3.95-13.29 mg·kg-1, indicating that W0 > W1, W2, W3, and N3 > N2 > N1 > N0. (2) The soil NO3 --N accumulation ranged from 64.45-215.27 kg·ha-1 under varying water and nitrogen levels, demonstrating a decreasing trend with increasing horizontal distance. The NO3 --N accumulation at each horizontal distance increased with increasing irrigation and nitrogen application. The NO3 --N accumulation of W0N3 treatment increased by 5.55%-57.60% compared with the other treatments. (3) The total nitrogen content and nitrogen uptake in all wolfberry organs were W1 > W0 > W2 > W3, and N2 > N3 > N1 > N0. The maximum total nitrogen content and nitrogen uptake in W1N2 treatment were 3.25% and 27.82 kg·ha-1 in the roots, 3.30% and 57.19 kg·ha-1 in the stems, 3.91% and 11.88 kg·ha-1 in the leaves, and 2.42% and 63.56 kg·ha-1 in the fruits, respectively. (4) The emission flux and total emission of N2O increased with increasing irrigation and nitrogen application. The emission flux exhibited a transient peak (116.39-177.91 ug·m-2·h-1) after irrigation. The intensity of N2O emissions initially decreased and then increased with an increase in the irrigation amount. It also initially increased with increasing nitrogen application amount, then decreased, and finally increased again. The maximum emission intensity was observed under the W3N3 treatment (0.23 kg·kg-1). The N2O emission coefficients ranged from 0.17%-0.39%, in the order of W0 > W1 > W2 > W3 (except for N1) and N1 > N2 > N3. (5) Under varying water and nitrogen concentrations, N2O emission flux showed a positive linear correlation with soil pore water content and NO3 --N content and a negative linear correlation with soil temperature. The comprehensive evaluation revealed that a slight water deficit (65%-75% θf) combined with medium nitrogen application (300 kg·ha-1) decreased soil NO3 --N leaching, increased nitrogen uptake, and reduced N2O emission. These findings can serve as a reference for improving the efficiency and reducing emissions of wolfberry in the Yellow River irrigation region of Gansu Province and in similar climate zones.

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